CN103995045A - Application and method for detecting dimethoate and malathion residues by ionic migration spectrometer - Google Patents
Application and method for detecting dimethoate and malathion residues by ionic migration spectrometer Download PDFInfo
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- CN103995045A CN103995045A CN201410232482.3A CN201410232482A CN103995045A CN 103995045 A CN103995045 A CN 103995045A CN 201410232482 A CN201410232482 A CN 201410232482A CN 103995045 A CN103995045 A CN 103995045A
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- malathion
- rogor
- crops
- ionic migration
- ion mobility
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- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical group CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000009791 electrochemical migration reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000005947 Dimethoate Substances 0.000 title abstract 6
- 239000005949 Malathion Substances 0.000 claims abstract description 108
- 229960000453 malathion Drugs 0.000 claims abstract description 108
- 238000001514 detection method Methods 0.000 claims abstract description 23
- 239000012488 sample solution Substances 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000012086 standard solution Substances 0.000 claims description 25
- 238000001871 ion mobility spectroscopy Methods 0.000 claims description 22
- 239000000523 sample Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000013508 migration Methods 0.000 claims description 7
- 230000005012 migration Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000001186 cumulative effect Effects 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000703 Maximum Residue Limit Toxicity 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000003987 organophosphate pesticide Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100001228 moderately toxic Toxicity 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides application and a method for detecting dimethoate and malathion residues in crops by an ionic migration spectrometer and expands a usage range of the ionic migration spectrometer. According to the invention, the ionic migration spectrometer is used for detecting the dimethoate and malathion residues for the first time, the method for detecting dimethoate and malathion by the ionic migration spectrometer is also provided, the rapid and convenient detection on dimethoate and malathion is realized, the operation method is simple, the detection sensitivity is high and the accuracy of a detection result is great. The detection on dimethoate and malathion can be realized in a laboratory or in supermarkets and farmer markets, and law enforcement officers can conveniently screen and detect crops in the field.
Description
Technical field
The present invention relates to ionic migration spectrometer and agriculture residue detection technical field, relate in particular to a kind of ionic migration spectrometer for detection of residual purposes and the method for Rogor in crops and malathion.
Background technology
Rogor is a kind of efficient moderately toxic organophosphorus pesticide, chemistry O by name, O-dimethyl-S-(N-methylamino formyl methyl) phosphorodithioate (C6H12NO3PS2), because of its instant effect, the advantage such as cheap, be widely used in desinsection, the sterilization of the crops such as vegetable and fruit in China and kill mite.
Malathion is that upper widely used efficient, the low toxicity of a kind of agricultural, contact organophosphorus insecticides can be used as protective agent, also can be used for the sterilization of hole capital after selling all securities, equipment and processing factory etc.Chemistry O by name, O-dimethyl-S-[1,2-bis-(ethoxy carbonyl) ethyl] phosphorodithioate (C10H19O6PS2), this agricultural chemicals is lower to person poultry toxicity.Fast in higher mammal internal metabolism speed, metabolism toxicity is little, the longevity of residure is short and have the effect such as tag, stomach toxicity is stifling.
But the excessive use of Rogor and malathion, makes its high residue in vegetable and fruit, bring huge threat to people's health, therefore China's use of having limited the quantity.In November, 2012, Ministry of Health of the People's Republic of China and the issue GB2763-2012 of The Ministry of Agriculture of the People's Republic of China, MOA were defined in maximum residue limit (the maximum residue limits of Rogor in fruits jujube, MRL) be 2mg/kg, malathion MRL is 6mg/kg.
At present, to the detection of organophosphorus pesticide residual quantity in fruit, what mostly adopt is standard GB/T/T 20769-2008 method (the mensuration Liquid Chromatography-Tandem Mass Spectrometry of 450 kinds of agricultural chemicals and related chemicals residual quantity in fruits and vegetables), the method extraction and cleaning process more complicated, consuming time longer, efficiency is lower.
The method of measuring Rogor and malathion mainly contains the methods such as gas chromatography, liquid chromatography, immunoassay, gas chromatography-mass spectrum (GC-MS) and liquid chromatography-mass spectrum (LC-MS).Detect and have the loaded down with trivial details defect of instrument and equipment complexity, Sample pretreatment and measurement operation with said method, be not suitable for great amount of samples screening, and costly, it is promoted the use of and be restricted.
Summary of the invention
For this reason, technical matters to be solved by this invention is: a kind of residual method of Rogor and malathion in fast detecting crops is provided, detects with the rapid and convenient that realizes Rogor and malathion, method of operating is simple, detection sensitivity is high, and testing result accuracy rate is large.
The invention provides a kind of residual method of Rogor and malathion in fast detecting crops, the method comprises:
Prepare Rogor and the malathion standard solution of preset concentration gradient, and put it in ionic migration spectrometer, obtain ion mobility spectrometry spectrogram and Rogor and the malathion typical curve of this standard solution;
Prepare crops sample solution to be measured, and put it in ionic migration spectrometer, obtain the ion mobility spectrometry spectrogram of this sample solution;
By the ion mobility spectrometry spectrogram comparison of the ion mobility spectrometry spectrogram of sample solution and standard solution, calculate Rogor and the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor and malathion.
Wherein, described Rogor and the malathion standard solution prepared, comprising:
The Rogor and the malathion standard articles for use that take preset value, be diluted with an organic solvent to preset concentration, and lucifuge stores;
When use, the mixed mark of the Rogor of described storage and malathion dilution is diluted to again to Rogor and the malathion standard solution of preset concentration gradient.
Described ionic migration spectrometer is on-radiation ion gun, operating voltage is 220V/50HZ, source of the gas is independent source of the gas, for dry air, migration electric field intensity is 200 V/cm to 500V/cm, migration tube temperature is 40 DEG C to 200 DEG C, and sample introduction temperature is 170 DEG C to 250 DEG C, and sample size is 1 uL to 10uL.
Described acquisition Rogor and malathion typical curve, comprising:
Qualitative with Rogor, the relative ion mobility in malathion, with characteristic peak intensity or the area quantitative of Rogor, malathion standard solution, draw the typical curve of Rogor, malathion standard solution concentration gradient and Rogor, malathion characteristic peak intensity or area.
Wherein, by the ion mobility spectrometry spectrogram comparison of the ion mobility spectrometry spectrogram of sample solution and standard solution, calculate Rogor, the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor, malathion, comprising:
Qualitative with Rogor, the relative ion mobility in malathion, with crops sample solution characteristic peak intensity to be measured or area quantitative, calculate Rogor, the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor, malathion.
The linear equation of described typical curve is: Y=2580.4X+71.885, and R2=0.9912, wherein, and the degree of fitting of the curve that R2 represents, Y is Rogor characteristic peak intensity, X is Rogor concentration.
Y=2841.8X+93.782, R2=0.9924, wherein, and the degree of fitting of the curve that R2 represents, Y is malathion characteristic peak intensity, X is malathion concentration.
Described preparation crops sample solution to be measured, comprising:
Take crops sample to be measured, and put into centrifuge tube mesoscale eddies after adding organic solvent, put into again afterwards oscillator and vibrate;
Solution after vibration is crossed to 0.45 μ m miillpore filter, obtain described crops sample solution to be measured.
Described organic solvent is acetonitrile.
Described crops are date.
The present invention also provides a kind of ionic migration spectrometer for detection of the residual purposes of Rogor in crops and malathion, and this purposes is: use ionic migration spectrometer and right to use to require method described in 1 to 9 any one to detect the residual of Rogor and malathion in crops.
Ionic migration spectrometer of the present invention is for detection of residual purposes and the method for Rogor in crops and malathion, expand the use of ionic migration spectrometer, propose for the first time to use ionic migration spectrometer to detect the idea of Rogor and malathion, and provide the implementation method that uses ionic migration spectrometer to detect Rogor and malathion, the rapid and convenient that has realized Rogor and malathion detects, method of operating is simple, and detection sensitivity is high, and testing result accuracy rate is large.The detection of Rogor and malathion both can be carried out in laboratory, also can in supermarket, the market of farm produce, carry out, be convenient to law enfrocement official's field screening and detect.
Brief description of the drawings
Fig. 1 is the residual method flow schematic diagram of Rogor and malathion in fast detecting crops described in the embodiment of the present invention;
Fig. 2 is the typical curve of the cumulative peak intensity of Rogor characteristic peak and concentration;
Fig. 3 is the typical curve of the cumulative peak intensity of malathion characteristic peak and concentration;
Fig. 4 is the standard feature peak of Rogor and the mixed mark of malathion acetonitrile solution described in the embodiment of the present invention, 0.20ug/ml Rogor-malathion.
Embodiment
Below, describe the present invention by reference to the accompanying drawings.
As shown in Figure 1, the present embodiment provides a kind of residual method of Rogor and malathion in fast detecting crops, and the method comprises:
Prepare Rogor and the malathion standard solution of finite concentration gradient, and put it in ionic migration spectrometer, obtain ion mobility spectrometry spectrogram and Rogor and the malathion typical curve of this standard solution;
Prepare crops sample solution to be measured, and put it in ionic migration spectrometer, obtain the ion mobility spectrometry spectrogram of this sample solution;
The ion mobility spectrometry standard spectrogram of the ion mobility spectrometry spectrogram of sample solution and standard solution is compared, calculate Rogor and the malathion actual content in sample solution according to the ion mobility spectrometry typical curve of standard solution.
The present embodiment is illustrated as an example of the detection method of Rogor in date and malathion example.
First step, need to prepare Rogor and malathion hybrid standard and use liquid, and this preparation method comprises:
Accurately take Rogor and the malathion standard articles for use of preset value, with organic solvent, in the present embodiment, use dilution in acetonitrile to arrive preset concentration, be stored in the vial of airtight brown lucifuge.In use, can be according to actual concentrations needs, then be diluted to Rogor and the malathion acetonitrile standard solution of finite concentration gradient.For ensureing the precision of ion mobility spectrometry typical curve of standard solution, describedly accurately take the Rogor of preset value and the precision that takes of malathion standard articles for use is generally 0.01mg.
Second step, obtains Rogor and malathion typical curve.This preparation method comprises: draw above-mentioned Rogor and malathion acetonitrile standard solution 4 μ L with 10 μ L micropipettors, inject or put into ionic migration spectrometer, qualitative with Rogor, malathion relative ion mobility (K0), with characteristic peak intensity or the area quantitative of standard solution, the typical curve of drawing concentration gradient and Rogor, the cumulative peak intensity of malathion characteristic peak or area, obtains Rogor typical curve as shown in Figure 2.The linear equation of described typical curve is: Y=2580.4X+71.885, and R2=0.9912, wherein, and the degree of fitting of the curve that R2 represents, Y is Rogor characteristic peak intensity, and the unit of characteristic peak intensity is volt, and X is Rogor concentration.Cumulative peak is the summation of characteristic peak intensity or area.
Malathion typical curve as shown in Figure 3.The linear equation of described typical curve is: Y=2841.8X+93.782, and R2=0.9924, wherein, and the degree of fitting of the curve that R2 represents, Y is malathion characteristic peak intensity, X is malathion concentration.
Here, describedly qualitatively just refer to whether tested thing has Rogor and malathion, quantitatively just refer to tested species Rogor and malathion content number.
Wherein, draw Rogor and malathion acetonitrile hybrid standard and use the dosage of liquid to determine according to the sample introduction range of capacity of ionic migration spectrometer, generally at 1-10uL.
The ionic migration spectrometer of above-mentioned use is on-radiation ion gun, operating voltage is 220V/50HZ, source of the gas is independent source of the gas, for dry air, migration electric field intensity is 200 V/cm to 500V/cm, migration tube temperature is 40 DEG C to 200 DEG C, and sample introduction temperature is 170 DEG C to 250 DEG C, and sample size is 1 uL to 10uL.
Described ionic migration spectrometer can use the ionic migration spectrometer of realizing by common ion mobility, also can use the ionic migration spectrometer of realizing by relative ion mobility.
Wherein, the ionic migration spectrometer that uses relative ion mobility to realize, by the applicant's patent No. ZL201110175660.X, denomination of invention is to utilize the method for relative ion mobility spectrometry recognition material open.And, be ZL201110212235.3 by the applicant's the patent No., denomination of invention is that ion migration ratio spectrometer is open.
Third step, prepares crops sample solution to be measured, and puts it in ionic migration spectrometer, obtains the ion mobility spectrometry spectrogram of this sample solution;
The present embodiment is taking crops date as example, weigh date 5.0g, add organic solvent, for example HPLC level acetonitrile 10mL, and the potpourri of date and acetonitrile is put into and in centrifuge tube, carried out vortex, general vortex is after 5 minutes, more described potpourri is put into oscillator vibrates, generally vibrate again 5 minutes, obtain date extract.The present embodiment centrifuge tube used is 50mL teflon centrifuge tube.
Date extract is crossed to 0.45 μ m miillpore filter, collect filtrate, as the sample solution of crops date to be measured.
Get the sample solution of 4uL crops date to be measured, put in described ionic migration spectrometer and test, the general test time is 2 minutes, ionic migration spectrometer is qualitative with the relative ion mobility (K0) of Rogor, malathion in the sample solution of crops date to be measured, with characteristic peak intensity or area quantitative.
The 4th step, by the sample solution Rogor obtaining in third step, malathion characteristic peak superposed strength or area, in substitution Rogor, malathion typical curve, calculates Rogor, malathion actual content in sample solution.Transverse axis in Fig. 4 is 1/K0, and K0 is relative ion mobility, and the longitudinal axis is Rogor and malathion intensity.
Be specially: the ion mobility spectrometry spectrogram of the ion mobility spectrometry spectrogram of date sample solution and Rogor, malathion standard solution is compared, qualitative with Rogor, malathion relative ion mobility (K0), with actual measurement solution Rogor, malathion characteristic peak intensity or area quantitative, calculate the actual content of Rogor, malathion in date sample solution according to Rogor, malathion typical curve.
By foregoing description, can see, use the residual method of Rogor and malathion in ionic migration spectrometer test crops, can realize the fast detecting of Rogor and malathion, method of operating is simple, and detection sensitivity is high, and testing result accuracy rate is large.Overcome the pretreatment process described in background technology, with an organic solvent, for example acetonitrile, can directly carry out the extraction of test fluid to crops, and whole testing process is consuming time is less than 10 minutes.And ionic migration spectrometer instrument performance is stable, automaticity is high.Tester can detection on duty through simple training, both can carry out in laboratory, also can be in supermarket, the market of farm produce and law enforcement related personnel carry out examination test.
The embodiment of the present invention also provides a kind of ionic migration spectrometer for detection of the residual purposes of Rogor in crops and malathion, this purposes is: use ionic migration spectrometer and use the residual method of Rogor and malathion in the use ionic migration spectrometer test crops described in above-described embodiment, detect the residual of Rogor and malathion in crops.
The purposes that the present embodiment provides, open up a new use of ionic migration spectrometer, in the detection of Rogor and malathion, propose for the first time to use ionic migration spectrometer to detect the idea of Rogor and malathion, and provided the concrete methods of realizing that uses ionic migration spectrometer detection Rogor and malathion.
In sum, described in the present embodiment, ionic migration spectrometer is for detection of residual purposes and the method for Rogor in crops and malathion, expand the use of ionic migration spectrometer, propose for the first time to use ionic migration spectrometer to detect the idea of Rogor and malathion, and provided the implementation method that uses ionic migration spectrometer to detect Rogor and malathion, and the rapid and convenient that has realized Rogor and malathion detects, and method of operating is simple, detection sensitivity is high, and testing result accuracy rate is large.The detection of Rogor and malathion both can be carried out in laboratory, also can in supermarket, the market of farm produce, carry out, be convenient to law enfrocement official's field screening and detect.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the residual method of Rogor and malathion in fast detecting crops, is characterized in that, comprising:
Prepare Rogor and the malathion standard solution of preset concentration gradient, and put it in ionic migration spectrometer, obtain ion mobility spectrometry spectrogram and Rogor and the malathion typical curve of this standard solution;
Prepare crops sample solution to be measured, and put it in ionic migration spectrometer, obtain the ion mobility spectrometry spectrogram of this sample solution;
By the ion mobility spectrometry spectrogram comparison of the ion mobility spectrometry spectrogram of sample solution and standard solution, calculate Rogor and the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor and malathion.
2. method according to claim 1, is characterized in that, described Rogor and the malathion standard solution prepared, comprising:
The Rogor and the malathion standard articles for use that take preset value, be diluted with an organic solvent to preset concentration, and lucifuge stores;
When use, the mixed mark of the Rogor of described storage and malathion dilution is diluted to again to Rogor and the malathion standard solution of preset concentration gradient.
3. method according to claim 1, it is characterized in that, described ionic migration spectrometer is on-radiation ion gun, operating voltage is 220V/50HZ, and source of the gas is independent source of the gas, is dry air, migration electric field intensity is 200 V/cm to 500V/cm, migration tube temperature is 40 DEG C to 200 DEG C, and sample introduction temperature is 170 DEG C to 250 DEG C, and sample size is 1 uL to 10uL.
4. method according to claim 1, is characterized in that, described acquisition Rogor and malathion typical curve, comprising:
Qualitative with Rogor, the relative ion mobility in malathion, with characteristic peak intensity or the area quantitative of Rogor, malathion standard solution, draw the typical curve of Rogor, malathion standard solution concentration gradient and Rogor, malathion characteristic peak intensity or area.
5. method according to claim 1, it is characterized in that, by the ion mobility spectrometry spectrogram comparison of the ion mobility spectrometry spectrogram of sample solution and standard solution, calculate Rogor, the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor, malathion, comprising:
Qualitative with Rogor, the relative ion mobility in malathion, with crops sample solution characteristic peak intensity to be measured or area quantitative, calculate Rogor, the malathion actual content in crops sample solution to be measured according to the typical curve of Rogor, malathion.
6. method according to claim 5, is characterized in that, the linear equation of described typical curve is: Y=2580.4X+71.885, and R2=0.9912, wherein, and the degree of fitting of the curve that R2 represents, Y is Rogor characteristic peak intensity, X is Rogor concentration;
Y=2841.8X+93.782, R2=0.9924, wherein, and the degree of fitting of the curve that R2 represents, Y is malathion characteristic peak intensity, X is malathion concentration.
7. method according to claim 1, is characterized in that, described preparation crops sample solution to be measured, comprising:
Take crops sample to be measured, and put into centrifuge tube mesoscale eddies after adding organic solvent, put into again afterwards oscillator and vibrate;
Solution after vibration is crossed to 0.45 μ m miillpore filter, obtain described crops sample solution to be measured.
8. according to the method described in claim 1 to 7 any one, it is characterized in that, described organic solvent is acetonitrile.
9. according to the method described in claim 1 to 8 any one, it is characterized in that, described crops are date.
10. an ionic migration spectrometer is for detection of the residual purposes of Rogor in crops and malathion, it is characterized in that, use ionic migration spectrometer and use method described in the claims 1 to 9 any one to detect the residual of Rogor and malathion in crops.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101852766A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for detecting phthalate ester plasticizer in plastic |
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| CN103675081A (en) * | 2012-09-13 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for quickly and sensitively detecting pesticide residues on surfaces of fruits and vegetables |
| CN103808792A (en) * | 2014-02-19 | 2014-05-21 | 中国农业科学院农业质量标准与检测技术研究所 | Ionic migration spectrum-based method for performing aided inspection on isocarbophos, moncrotophos and/or phosphamidon in cowpea |
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- 2014-05-29 CN CN201410232482.3A patent/CN103995045A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852766A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for detecting phthalate ester plasticizer in plastic |
| CN103097390A (en) * | 2010-07-22 | 2013-05-08 | 塞拉莫普泰克公司 | Application of beta-functionalized dihydroxy-chlorins for PDT |
| CN103675081A (en) * | 2012-09-13 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for quickly and sensitively detecting pesticide residues on surfaces of fruits and vegetables |
| CN103808792A (en) * | 2014-02-19 | 2014-05-21 | 中国农业科学院农业质量标准与检测技术研究所 | Ionic migration spectrum-based method for performing aided inspection on isocarbophos, moncrotophos and/or phosphamidon in cowpea |
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