CN107748156A - A kind of detection method of glyphosate - Google Patents
A kind of detection method of glyphosate Download PDFInfo
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- CN107748156A CN107748156A CN201711340438.4A CN201711340438A CN107748156A CN 107748156 A CN107748156 A CN 107748156A CN 201711340438 A CN201711340438 A CN 201711340438A CN 107748156 A CN107748156 A CN 107748156A
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- 238000001514 detection method Methods 0.000 title claims abstract description 77
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 75
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 75
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000012360 testing method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 77
- 239000002243 precursor Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003556 assay Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 244000046101 Sophora japonica Species 0.000 claims description 6
- 235000010586 Sophora japonica Nutrition 0.000 claims description 6
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003306 harvesting Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 abstract description 11
- 230000000171 quenching effect Effects 0.000 abstract description 11
- 239000003905 agrochemical Substances 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 3
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 2
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 abstract description 2
- 102000004190 Enzymes Human genes 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000000523 sample Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- -1 phosphonomethyl Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
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- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 231100000703 Maximum Residue Limit Toxicity 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006013 carbendazim Substances 0.000 description 2
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 239000013256 coordination polymer Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
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- WZSDWSACAGBYQU-UHFFFAOYSA-N 2-(dimethylamino)-3-phenylprop-2-enal Chemical compound CN(C)C(C=O)=CC1=CC=CC=C1 WZSDWSACAGBYQU-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005780 Fluazinam Substances 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
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- 239000005949 Malathion Substances 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- UZCGKGPEKUCDTF-UHFFFAOYSA-N fluazinam Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=C(Cl)C([N+]([O-])=O)=C1NC1=NC=C(C(F)(F)F)C=C1Cl UZCGKGPEKUCDTF-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229960000453 malathion Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010369 molecular cloning Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical group COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of detection method of glyphosate, the present invention utilizes Fe3+It can bring it about and assemble and fluorescent quenching with carboxyl and hydroxyl the generation coordination on carbon point surface.And the phosphono in glyphosate is for Fe3+There is stronger coordination, so can be by Fe3+Compete and come out from carbon point so that carbon point is disperseed and recovered fluorescence, therefore the concentration of solution glyphosate to be measured can be detected by fluorescence intensity.Inventive samples do not need pre-treatment, it is not necessary to large-scale instrument, it is simple to operate, it is not necessary to add enzyme, cost greatly reduces, detection selectivity is good, avoids other common agricultural chemicals interference, detection sensitivity is high, and test limit is low, and stability is good.It is widely used, it can be used for the detection of the sample glyphosate such as water fruits and vegetables, river.The present invention has a good application prospect and potential application value in detection and analysis field.
Description
Technical field
The present invention relates to technical field of food safety detection, and in particular to a kind of detection method of glyphosate.
Background technology
Glyphosate, chemical name N- ((phosphonomethyl)) amion acetic acid, it is that most widely used, output is maximum in the world at present
Wide spectrum nonselective herbicide, the effect toxicity of glyphosate mainly causes nervous system by suppressing the activity of CHE
The case such as dysfunction, the water pollution caused by glyphosate, vegetation deterioration, livestock poisoning increases year by year.Therefore, the world is each
State all strengthens the detection to food glyphosate residual, China's national standard " Pesticide MRL "
（GM2763-2005）And standards for drinking water quality（GB5749-2006）All to glyphosate in paddy, wheat, corn, water
Maximum residue limit (MRL) in the crops such as fruit, sugarcane and cottonseed oil and drinking water has strict limitation regulation.
At present the detection method of glyphosate mainly have high performance liquid chromatography, chromatography of ions, mass spectral analysis, chemical analysis and
Immunodetection.Although chromatography detection glyphosate residual generally has, accuracy is high, separating effect, result stability and operation
The advantages of reproducible.But because glyphosate lacks necessary functional group, thus sample detection need pre-treatment and post before, post
After derive, sample treatment operation is relatively complicated, and the professional requirement to experimental facilities and experiment operator is also higher, no
It is adapted to the detection of extensive sample, and needs the equipment of large and expensive, testing cost is high.Although the analysis of immunoassay
Capacity is big, and the advantages that suitable for on-site measurement, but the requirement to antibody mass and activity is high, and the quality of antibody directly affects detection
Sensitivity and specificity.Conventional chemical analysis mainly has：Silva etc. is by glyphosate and to dimethylaminocinnamaldehyde in acid
Property medium in diffusing reflection spectrum change, determine the glyphosate concentration in article of commerce and water sample, detection range reaches 50-500 μ g/
ml；Jan etc. reacts to form compound using glyphosate and carbon disulfide, and then is reacted under the conditions of containing ammonia with copper, then uses
AAS indirect determination glyphosate content, lowest detection are limited to 3.7 μ g/ml.It can be seen that existing chemical analysis is simply easy
OK, the problem of sensitivity is low, and detection range is small but be present.Therefore, these traditional methods are difficult to the fast of real-time online
Speed, selectivity detection.It is therefore necessary to find a kind of new detection method to solve these problems.
Carbon point refers to that size is less than 10nm carbon containing spherical nano-particle, and it has the fluorescence excitation dependence of characteristic.
The surface of carbon point has good water solubility often with groups such as carboxyls.Carbon point also has good photoluminescent property, and it
Itself do not contain that heavy metal element, bio-toxicity be small, good biocompatibility, thus it has in the field such as detection, sensing, photoelectricity
Wide application prospect.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of detection method of glyphosate,
Solve existing detection method time for sample pretreatment length, complex operation, sensitivity is low, detection range is small and testing cost is high asks
Topic.
To achieve the above object, the present invention adopts the following technical scheme that：A kind of detection method of glyphosate, including following step
Suddenly：
1）The foundation of standard curve：
Take carbon dots solution to be divided into several pieces, the PBS of same volume, mixing is added dropwise into every part of carbon dots solution respectively
Uniformly, make mixed solution in acidity, then Fe is separately added into above-mentioned mixed solution3+Solution, before obtaining detection after well mixed
Body, with fluorescence intensity of the above-mentioned detection precursor solution of fluorescent spectrophotometer assay at 412nm；Then respectively to detection precursor
Same volume but the different glyphosate standard liquid of concentration are added in solution, is incubated at room temperature, after the completion of reaction, then uses fluorescence
Spectrophotometer determines fluorescence intensity of the mixed solution for the glyphosate titer for adding various concentrations at 412nm respectively, obtains
To fluorescence intensity and do not add glyphosate detection precursor solution fluorescence intensity difference, as fluorescence recovery strength, with
Fluorescence recovery strength is ordinate, and the concentration of glyphosate is abscissa, draws standard curve, the recurrence of standard curve is calculated
Equation, the addition of the carbon point is relative to Fe3+Amount be excessive；
2）The measure of determinand glyphosate concentration：
Take step 1）The detection precursor being prepared, with the above-mentioned detection precursor solution of fluorescent spectrophotometer assay at 412nm
Fluorescence intensity；State then up and add solution to be measured in detection precursor solution and obtain reaction system, and be incubated at room temperature, instead
Should after the completion of, then add with fluorescent spectrophotometer assay fluorescence intensity of the mixed solution at 412nm of determinand, obtain
The difference of fluorescence intensity of the fluorescence intensity with not adding determinand, as fluorescence recovery strength, then obtained fluorescence is recovered strong
Degree substitutes into step 1）In obtained regression equation, that is, the concentration of determinand solution glyphosate is obtained, it is described to detect carbon in precursor
The addition of point is relative to Fe3+Amount be excessive；The addition volume of the testing sample solution and step 1）Glyphosate
The addition volume of titer is identical.
Further, the Fe3+Final concentration of 50 ~ 200 μM in reaction system.
Further, the brooding time is 14 ~ 18min.
Further, the pH value of the PBS is 3 ~ 6.
Further, the carbon dots solution is prepared using following methods：The fresh foreign leaves of Sophora japonica of harvesting is cleaned, drying,
The leaf liquid nitrogen grinding of drying is put into deionized water into powder, then by leaf powder, by leaf after abundant ultrasonic disperse
Powder solution is transferred in teflon lined stainless steel autoclave, is then placed in autoclave in freeze-day with constant temperature bellows instead
Should, reaction temperature is 200 ~ 300 DEG C, and the reaction time is 24 ~ 48h, naturally cools to room temperature, and centrifugation obtains supernatant, supernatant
Filtered with 0.22um miillpore filter, and solution after filtering is dialysed, that is, obtained carbon dots solution, be kept in dark place.
Further, the solid-to-liquid ratio of the leaf powder and deionized water is 3 ~ 5g：100ml.
Further, drying temperature is 60 ~ 70 DEG C in the leaf drying, and drying time is 24 ~ 36h.
Further, the molecular cut off of bag filter is 500Da in the dialysis procedure, and dialysis time is 24 ~ 48h.
The present invention proposes fluorescence turn-off-on principles to detect the concentration of determinand solution glyphosate.Present invention synthesis
Carbon point（CDs）Excitation wavelength be 325nm, launch wavelength 412nm, can be at 412nm so CDs is under excited state
Send fluorescence.In addition, there are substantial amounts of hydroxyl and carboxyl in CDs surfaces（Fig. 1）, Fe3+It can be sent out with the carboxyl and hydroxyl on carbon point surface
Raw coordination, which is brought it about, to be assembled and fluorescent quenching.And glyphosate（Glp）In contain substantial amounts of functionalization group-phosphono,
Because phosphono is for Fe3+There is stronger coordination, so can be by Fe3+Compete and come out from carbon point so that carbon point minute
Dissipate and recovered fluorescence（Fig. 2 and Fig. 3）.Therefore, the concentration of testing sample glyphosate is different, and CDs fluorescence can also be sent out
Raw different degrees of recovery, show fluorescence intensity difference.I.e. the concentration of glyphosate is linearly closed with carbon point fluorescence recovery strength
System.
Compared with prior art, the present invention has the advantages that：
1st, the present invention is linear by CDs fluorescence recovery strength and the concentration of glyphosate, realizes in solution to be measured
The quick detection of the concentration of glyphosate.During glyphosate is detected, sample does not need pre-treatment, it is not necessary to large-scale instrument,
Cost greatly reduces, simple to operate, detection selectivity is good, avoids other common agricultural chemicals interference, detection sensitivity is high, detection
Limit low, lower limit 5.99ppb, detection speed is fast, greatly improves detection efficiency, and stability is good, can realize real-time online
The detection of quick, selectivity.It is widely used, it can be used for the detection of the sample glyphosate such as water fruits and vegetables, river.The present invention
Had a good application prospect in detection and analysis field and potential using value.
2nd, carbon point, synthetic method is prepared using the polysaccharide in acacia leaf as carbon source, then by hydro-thermal method in the present invention
Simply, raw material is cheap and easy to get, and synthesis condition is gently controllable, and its building-up process need not add organic or inorganic chemical reagent,
Pollutant will not be produced, it is green.
Brief description of the drawings
Fig. 1 is CDs infrared spectrogram；
Fig. 2 is the detection principle diagram of glyphosate；
Fig. 3 is the design sketch for detecting glyphosate；
Fig. 4 is Fe3+Influence of the concentration of solution to CDs fluorescent quenchings；
Fig. 5 is the PBS cushioning liquid of different pH value to Fe3+With the influence of CDs complexings；
Fig. 6 is influence of the brooding time to glyphosate Detection results；
Fig. 7 is the CDs of synthesis optical characterisation figure；
Fig. 8 is the canonical plotting for detecting glyphosate；
Fig. 9 is influence of the different agricultural chemicals to detection glyphosate method.
Embodiment
The present invention is described in further detail with reference to specific embodiments and the drawings.
The PBS cushioning liquid used in embodiment（0.01M）Prepared according to molecular cloning texts guide.Main component is
NaCl、Na2HPO4•12H2O and NaH2PO4•2H2O。
First, a kind of detection method of glyphosate
Embodiment 1
1）The fresh foreign leaves of Sophora japonica of harvesting is washed with deionized water only, be put in after 60 DEG C of baking oven 24h taking-up liquid nitrogen grinding into
Powder, 1g leaves powder is weighed in 25mL deionized waters, ultrasonic disperse 5min, it is stainless to be transferred to 50mL teflon lineds
In steel autoclave, then it is placed in 200 DEG C of freeze-day with constant temperature bellows, reaction is taken out after 36 hours, naturally cools to room
Temperature.Reaction solution centrifuges 15 min to remove big particle on 10000rpm centrifuge, and supernatant is filtered with 0.22um micropore
Film is filtered, and is dialysed in deionized water 24h with 500D bag filter.The CDs solution storages finally obtained are in 4 DEG C of refrigerators
It is stand-by.
2）Take step 1）The CDs solution of preparation, 9 parts, every part of 30uL are divided into, are added into every part of CDs solution
2.91mLPBS buffer solution（0.01M, pH=4）, to be consistent reaction system, then 30uL deionized waters are added, are well mixed,
Make mixed solution in acidity, then be separately added into above-mentioned mixed solution the Fe of 30 μ L various concentrations3+Solution, it is well mixed,
So that Fe in solution3+Final concentration in reaction system is respectively 0 μM, 10 μM, 20 μM, 40 μM, 60 μM, 80 μM, 100 μM, 250
μM and 500 μM, obtain detecting precursor solution, it is strong to detect fluorescence of the precursor solution at 412nm with fluorescent spectrophotometer assay
Degree, obtained fluorescence intensity is not with adding Fe3+The difference of the fluorescence intensity of the detection precursor solution of solution, as fluorescent quenching are strong
Degree.Using fluorescent quenching intensity as ordinate, Fe3+Final concentration of abscissa, draw curve map.As a result it is as shown in Figure 4.
Ferric ion solutions concentration is to influence the principal element of this method Detection results, because under same volume, Fe3+Final concentration
Bigger, the iron ion being free in mixed solution is more（CDs and Fe3+Complexing reaches saturation）, therefore recover needed for CDs fluorescence
Glyphosate（Glp）More, now Detection results are poorer.From fig. 4, it can be seen that with Fe3+The rise of concentration, mixing are molten
CDs fluorescent quenching intensity constantly strengthens in liquid, works as Fe3+At final concentration of 250 μM, fluorescent quenching intensity tends towards stability；When
Fe3+At final concentration of 500 μM, fluorescent quenching intensity is not further added by, and the iron ion of the glyphosate complexing in mixed solution has reached
Saturation.It is preferred that final concentration of 100 μM of iron ion, because CDs fluorescent quenching intensity reaches three points in mixed solution under this concentration
Two or so, iron ion is all complexed by CDs, without free iron ion in mixed solution, it is ensured that detect the accuracy of data, and
And the iron concentration can detect glyphosate concentration range it is larger.
Embodiment 2
Test method wherein adds the Fe that 30 μ L concentration are 10mM with embodiment 1 in reaction system3+Solution, PBS
PH value is variable, respectively 3,3.5,4,4.5,5,5.5,6,6.5 and 7.Using fluorescent quenching intensity as ordinate, different pH value are
Abscissa, curve map is drawn, as a result as shown in Figure 5.
Main influence Fe of the pH value of solution on detection method3+With in CDs interaction.From fig. 5, it can be seen that with
PH value of buffer solution constantly increases, and is adding the Fe of same concentrations and same volume3+In the case of solution, CDs fluorescence is quenched
Intensity of going out also constantly is strengthening, and when pH value of buffer solution is more than 4, fluorescent quenching intensity is constantly weakening on the contrary, i.e., slow
Rush solution ph for 4 when, the Fe in mixed solution3+With CDs complexing best results.
Embodiment 3
1）The fresh foreign leaves of Sophora japonica of harvesting is washed with deionized water only, be put in after 70 DEG C of baking oven 12h taking-up liquid nitrogen grinding into
Powder, 1g leaves powder is weighed in 25mL deionized waters, ultrasonic disperse 5min, it is stainless to be transferred to 50mL teflon lineds
In steel autoclave, then it is placed in 200 DEG C of freeze-day with constant temperature bellows, reaction is taken out after 36 hours, naturally cools to room
Temperature.Reaction solution centrifuges 15 min to remove big particle on 10000rpm centrifuge, and supernatant is filtered with 0.22um micropore
Film is filtered, and is dialysed in deionized water 24h with 500D bag filter.The CDs solution storages finally obtained are in 4 DEG C of refrigerators
It is stand-by.
2）Take step 1）The CDs solution of preparation, 9 parts, every part of 30uL are divided into, are added into every part of CDs solution
2.91mLPBS buffer solution（0.01M, pH=4）It is well mixed, mixed solution is added respectively in acidity, then into above-mentioned mixed solution
Enter the Fe that 30 μ L concentration are 10mM3+Solution, it is well mixed to obtain detecting precursor solution, before being detected with fluorescent spectrophotometer assay
Fluorescence intensity of the liquid solution at 412nm, 30 μ l concentration then are separately added into as 1600ppm grass into detection precursor solution respectively
Sweet phosphine standard liquid, at room temperature respectively be incubated 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min and
18min, then determined respectively with sepectrophotofluorometer add glyphosate titer fluorescence of the mixed solution at 412nm it is strong
Degree, the difference of the fluorescence intensity of detection precursor solution of the obtained fluorescence intensity with not adding glyphosate, as fluorescence recover strong
Degree.Using fluorescence recovery strength as ordinate, different incubation times are abscissa, draw curve map, as shown in Figure 6.
From fig. 6, it can be seen that with the growth of brooding time, the glyphosate solution of same concentrations and same volume is being added
Under, CDs fluorescence recovery strength is also constantly strengthening, and when brooding time is more than 14min, the change of fluorescence recovery strength is little
Tend towards stability, i.e., when brooding time is 14min, the iron ion of the glyphosate complexing in mixed solution has reached saturation, is further added by
Brooding time will not also increase fluorescence recovery strength, i.e., glyphosate is complexed Fe when brooding time is 14min3+Time be sufficient
's.
Embodiment 4
1）CDs synthesis：
The fresh foreign leaves of Sophora japonica of harvesting is washed with deionized water only, is put in after 60 DEG C of baking oven 24h taking-up liquid nitrogen grinding into powder
End, 1g leaves powder is weighed in 25mL deionized waters, ultrasonic disperse 10min, it is stainless to be transferred to 50mL teflon lineds
In steel autoclave, then it is placed in 250 DEG C of freeze-day with constant temperature bellows, reaction is taken out after 24 hours, naturally cools to room
Temperature.Reaction solution centrifuges 15min to remove big particle, supernatant 0.22um miillpore filter on 10000rpm centrifuge
Filtered, dialysed in deionized water 24h with 500D bag filter.The CDs solution storages finally obtained are treated in 4 DEG C of refrigerators
With.The CDs of synthesis is subjected to optical characterisation, as shown in Figure 7.
From figure 7 it can be seen that the CDs of synthesis excitation wavelength is 325nm, launch wavelength 412nm.
2）The foundation of standard curve
Take step 1）The CDs solution of preparation, 13 parts, every part of 30uL are divided into, 2.91mLPBS is added into every part of CDs solution
Buffer solution（0.01M, pH=4）It is well mixed, make mixed solution in acidity, then to add into every part of mixed solution 30 μ L respectively dense
Spend the Fe for 10mM3+Solution, it is well mixed to obtain detecting precursor solution, existed with fluorescent spectrophotometer assay detection precursor solution
Fluorescence intensity at 412nm, the glyphosate standard that 30 μ l concentration are various concentrations is then added into detection precursor solution respectively
Solution, the final concentration for making solution glyphosate be respectively 0ppm, 0.1ppm, 0.4ppm, 0.8ppm, 1ppm, 2ppm, 4ppm,
6ppm, 8ppm, 10ppm, 12ppm, 14ppm and 16ppm, then it is incubated 14min at room temperature respectively and ensures that it fully reacts；Again
Determine fluorescence intensity of the mixed solution for adding glyphosate titer at 412nm, specific number respectively with sepectrophotofluorometer
According to as shown in table 1.
Table 1
| Experiment | Glp final concentrations（ppm） | Fluorescence intensity（a.u.） | Experiment | Glp final concentrations（ppm） | Fluorescence intensity（a.u.） |
| 1 | 0 | 290.19 | 8 | 6 | 406.33 |
| 2 | 0.1 | 298.63 | 9 | 8 | 451.54 |
| 3 | 0.4 | 307.95 | 10 | 10 | 489.10 |
| 4 | 0.8 | 316.78 | 11 | 12 | 520.02 |
| 5 | 1 | 320.45 | 12 | 14 | 572.66 |
| 6 | 2 | 335.21 | 13 | 16 | 617.73 |
| 7 | 4 | 370.81 |
The difference of the fluorescence intensity of detection precursor solution of the obtained fluorescence intensity with not adding glyphosate, as fluorescence recover strong
Degree.Using fluorescence recovery strength as ordinate, glyphosate concentration is abscissa, draws standard curve.As shown in Figure 8.
It can be drawn by Fig. 8, the range of linearity of standard curve is 0.1-16ppm, and linear equation is：Y=19.0306X+
9.4162 R2=0.9973, detection line 5.99ppb, less than international standard.It can be seen that the range of linearity of the present invention is wide, detection is sensitive
Degree is high, can realize the detection to low concentration glyphosate.
2nd, the selectivity of the detection method of glyphosate
1）The fresh foreign leaves of Sophora japonica of harvesting is washed with deionized water only, be put in after 70 DEG C of baking oven 24h taking-up liquid nitrogen grinding into
Powder, 1g leaves powder is weighed in 25mL deionized waters, ultrasonic disperse 5min, it is stainless to be transferred to 50mL teflon lineds
In steel autoclave, then it is placed in 300 DEG C of freeze-day with constant temperature bellows, reaction is taken out after 24 hours, naturally cools to room
Temperature.Reaction solution centrifuges 15 min to remove big particle on 10000rpm centrifuge, and supernatant is filtered with 0.22um micropore
Film is filtered, and is dialysed in deionized water 48h with 500D bag filter.The CDs solution storages finally obtained are in 4 DEG C of refrigerators
It is stand-by.
2）Take step 1）The CDs solution of preparation, 12 parts, every part of 30uL are divided into, are added into every part of CDs solution
2.91mLPBS buffer solution（0.01M, pH=4）Well mixed, making mixed solution, it is 10mM then to add 30uL concentration in acidity
Fe3+Solution, it is well mixed to obtain detecting precursor solution, precursor solution is detected at 412nm with fluorescent spectrophotometer assay
Fluorescence intensity, then to detection precursor solution in be separately added into 30 μ L concentration be 16000ppm other common agricultural chemicals：Omethoate
（OM）, sevin (CP), fluazinam（FA）, parathion-methyl（MP）, Mobucin（IP）, malathion（MT）, triazolone（TA）,
Carbendazim (CB), Bravo（CR）, chlopyrifos（CP）, cartap（CT）With the glyphosate that concentration is 1600ppm（Glp）, then
Above-mentioned mixed liquor is put in incubation 14min at room temperature and ensures that it fully reacts.Determined respectively with sepectrophotofluorometer added with
Fluorescence intensity of the mixed liquor of different common agricultural chemicals 412nm at, obtained fluorescence intensity with do not add the detection of glyphosate before
The difference of the fluorescence intensity of liquid solution, as fluorescence recovery strength.Then the fluorescence recovery strength of different common agricultural chemicals is calculated,
Draw influence of the different common agricultural chemicals to CDs fluorescence recovery strength in mixed solution.As shown in Figure 9.
From fig. 9, it can be seen that other common agricultural chemicals are little to change in fluorescence in mixed solution after adding, its influence can neglect
Slightly, it is seen then that this method has specificity well to detection glyphosate, has good anti-interference energy to other common agricultural chemicals
Power.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (8)
1. a kind of detection method of glyphosate, it is characterised in that comprise the following steps：
1）The foundation of standard curve：
Take carbon dots solution to be divided into several pieces, the PBS of same volume, mixing is added dropwise into every part of carbon dots solution respectively
Uniformly, make mixed solution in acidity, then Fe is separately added into above-mentioned mixed solution3+Solution, before obtaining detection after well mixed
Body, with fluorescence intensity of the above-mentioned detection precursor solution of fluorescent spectrophotometer assay at 412nm；Then respectively to detection precursor
Same volume but the different glyphosate standard liquid of concentration are added in solution, and is incubated at room temperature, after the completion of reaction, then with glimmering
Light spectrophotometer determines fluorescence intensity of the mixed solution for the glyphosate titer for adding various concentrations at 412nm respectively,
The difference of the fluorescence intensity of detection precursor solution of the obtained fluorescence intensity with not adding glyphosate, as fluorescence recovery strength,
Using fluorescence recovery strength as ordinate, the concentration of glyphosate is abscissa, draws standard curve, and returning for standard curve is calculated
Return equation, the addition of the carbon point is relative to Fe3+Amount be excessive；
2）The measure of determinand glyphosate concentration：
Take step 1）The detection precursor being prepared, with the above-mentioned detection precursor solution of fluorescent spectrophotometer assay at 412nm
Fluorescence intensity；State then up and add solution to be measured in detection precursor solution and obtain reaction system, be incubated at room temperature, react
After the completion of, then fluorescence intensity of the mixed solution at 412nm of determinand is added with fluorescent spectrophotometer assay, what is obtained is glimmering
The difference of the fluorescence intensity of detection precursor solution of the luminous intensity with not adding determinand, as fluorescence recovery strength, then will obtain
Fluorescence recovery strength substitute into step 1）In obtained regression equation, that is, the concentration of determinand solution glyphosate is obtained, it is described
The addition of carbon point in precursor is detected relative to Fe3+Amount be excessive；The addition volume of the testing sample solution and step
Rapid 1）The addition volume of glyphosate titer is identical.
2. the detection method of glyphosate according to claim 1, it is characterised in that the Fe3+End in reaction system is dense
Spend for 50 ~ 200 μM.
3. the detection method of glyphosate according to claim 1, it is characterised in that the brooding time is 14 ~ 18min.
4. the detection method of glyphosate according to claim 1, it is characterised in that the pH value of the PBS is 3 ~ 6.
5. the detection method of glyphosate according to claim 1, it is characterised in that the carbon dots solution uses following methods system
It is standby：The fresh foreign leaves of Sophora japonica of harvesting is cleaned, drying, by the leaf liquid nitrogen grinding of drying into powder, then by leaf powder
It is put into deionized water, leaf powder solution is transferred to teflon lined stainless steel autoclave after abundant ultrasonic disperse
In, then autoclave is placed in freeze-day with constant temperature bellows and reacted, reaction temperature is 200 ~ 300 DEG C, and the reaction time is 24 ~ 48h,
Naturally cool to room temperature, centrifugation obtains supernatant, and supernatant is filtered with 0.22um miillpore filter, and will solution after filtering
Dialysed, that is, obtain carbon dots solution, be kept in dark place.
6. the detection method of glyphosate according to claim 5, it is characterised in that the leaf powder and deionized water are consolidated
Liquor ratio is 3 ~ 5g：100ml.
7. the detection method of glyphosate according to claim 5, it is characterised in that temperature is 60 ~ 70 in the leaf drying
DEG C, the time is 24 ~ 36h.
8. the detection method of glyphosate according to claim 5, it is characterised in that the retention of bag filter in the dialysis procedure
Molecular weight is 500Da, and dialysis time is 24 ~ 48h.
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| CN108593613A (en) * | 2018-04-27 | 2018-09-28 | 重庆大学 | A kind of detection method of glyphosate |
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