CN114486876A - Rapid detection method for amitraz residue in agricultural products - Google Patents
Rapid detection method for amitraz residue in agricultural products Download PDFInfo
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- CN114486876A CN114486876A CN202210390872.8A CN202210390872A CN114486876A CN 114486876 A CN114486876 A CN 114486876A CN 202210390872 A CN202210390872 A CN 202210390872A CN 114486876 A CN114486876 A CN 114486876A
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- amitraz
- chloroform
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- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical group C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 title claims abstract description 51
- 238000001514 detection method Methods 0.000 title abstract description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 107
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 41
- 229960002587 amitraz Drugs 0.000 claims abstract description 32
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 21
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 21
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 claims abstract description 13
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 93
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 58
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000001476 alcoholic effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 235000013311 vegetables Nutrition 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000013399 edible fruits Nutrition 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000008055 phosphate buffer solution Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000010511 deprotection reaction Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000000007 visual effect Effects 0.000 abstract description 2
- 229960001701 chloroform Drugs 0.000 description 44
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 239000003814 drug Substances 0.000 description 11
- 229940079593 drug Drugs 0.000 description 10
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 9
- 150000003141 primary amines Chemical class 0.000 description 9
- 238000007086 side reaction Methods 0.000 description 9
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- GWLFXUUYBRACSN-UHFFFAOYSA-N 2,4-dimethylbenzamide Chemical compound CC1=CC=C(C(N)=O)C(C)=C1 GWLFXUUYBRACSN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 125000006239 protecting group Chemical group 0.000 description 4
- -1 2, 4-dimethylphenyl Chemical group 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000642 acaricide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- UKTHBCMHYFIUQD-UHFFFAOYSA-N n,n-bis(2,4-dimethylphenyl)methanimidamide Chemical compound CC1=CC(C)=CC=C1N(C=N)C1=CC=C(C)C=C1C UKTHBCMHYFIUQD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Classifications
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for rapidly detecting amitraz residue in agricultural products, which comprises the following steps: step a, preparing a homogeneous sample to be detected; step b, extracting and concentrating; step c, re-dissolving; step d, adding a chloroform solution of phthalic anhydride for protection reaction; step e, performing deprotection reaction to generate xylidine; step f, color reaction; and g, judging the result. The method has the advantages of simple and understandable principle, strong specificity, high sensitivity, visual detection result, high accuracy of the detection result, no need of large-scale analytical instruments, relatively less time consumption, extremely low analysis cost, special suitability for on-site rapid detection of the residue of the amitraz in agricultural products and strong practicability.
Description
Technical Field
The invention relates to the field of agricultural product detection, in particular to a method for rapidly detecting amitraz residue in agricultural products.
Background
Amitraz is also called as mite, amitraz and fruit mite killer, is a broad-spectrum amitraz mite killing insecticide, and belongs to moderate toxicity acaricide. Chemical name: 1, 5-bis- (2, 4-dimethylphenyl) -3-methyl-1, 3, 5-triazapentadiene-1, 4, wherein the raw medicine is white or yellow needle crystal, is slightly soluble in water, and is soluble in various organic solvents such as dimethylbenzene, acetone, methanol and the like. Is stable to temperature and light under anhydrous conditions and is unstable under acidic conditions. The latest national standard GB/T2763-2021 maximum residual limit of pesticide in food requires that the limit value of amitraz in vegetables and fruits is 0.5 mg/kg.
At present, commercial methods for detecting amitraz mainly comprise the following methods, and firstly, a gas chromatography-mass spectrometry method for rapidly determining residual amounts of amitraz and metabolites in fruits and vegetables is established by optimizing a pretreatment process. Hydrolyzing amitraz in a sample in a microwave digestion tank by acid to obtain 2, 4-dimethylaniline, alkalinizing, extracting by using normal hexane, detecting by using a gas chromatography-mass spectrometer, and quantifying by using an external standard method (reference: Liang Xiao Hou, Dang Zheng Ya, Yang Yaya, Wang Dan. residual quantity of amitraz in fruits and vegetables is subjected to gas chromatography-mass spectrometry rapid determination method [ J ]. tropical agricultural science, 2019, 39(06):67-73 ]); secondly, establishing a gas chromatography for rapidly detecting amitraz in the milk. In the method, amitraz in a sample is hydrolyzed into 2, 4-dimethylaniline by acid, alkalized and extracted by normal hexane, derived by heptafluorobutyric anhydride, detected by a gas chromatography-electron capture detector and quantified by an external standard method. Results the method detects that the recovery rate of the amitraz is between 83.6% and 97.4%, the relative standard deviation is between 1.02% and 4.23%, and the lowest detection limit is 5 mug/kg (refer to Wuteng, Weiwenping, Zamu Keren, Jianjian, Song dao Dong, Gaoyangliang. research on the rapid detection method of the amitraz content in milk [ J ] the food safety quality detection statement, 2015, 6(10): 4225-; thirdly, the interaction between the removed tert-butyl calixarene and the amitraz is researched by a fluorescence spectrum titration method. Experiments show that after different amounts of amitraz is added, fluorescence of the removed tert-butyl aromatic hydrocarbon is quenched, so that a rapid and simple method for determining amitraz is established, the linear range of the method is 1.00-60.0 mu g/mL, and the addition and recovery experiments show that the method is feasible (refer to the method for determining trace amitraz [ J ]. Anhui agricultural bulletin (Shangyue), 2012, 18(15): 158-159.) by using a fluorescence spectrum titration method.
The three methods all belong to the existing effective methods for detecting, but the limitations are obvious. The method adopts chromatography, and has the advantages of high operation difficulty, complex processing steps, long time consumption, low fault tolerance rate and high requirement on operators. In the second method, although the operation is simpler than that in the first method, the amount of the dimethylaniline as the hydrolysis product is greatly different due to the influence of the hydrolysis conditions, and only the data described in the literature are studied. The third method, which is not a common laboratory detection method, has higher synthesis difficulty of calixarene, so that the cost of the method is increased, the practicability is greatly reduced, and the method is only suitable for research and is not applied to actual detection scenes. The methods are not suitable for field rapid analysis and detection, and cannot meet the increasing detection requirements.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting amitraz residue in agricultural products.
According to one aspect of the invention, a method for rapidly detecting amitraz residue in agricultural products is provided, which comprises the following steps:
step a, weighing a sample to be detected, from which sludge is removed, in a homogenizer, and homogenizing to obtain a homogeneous sample to be detected;
b, weighing a to-be-detected homogeneous sample in a first centrifuge tube, adding a phosphate buffer solution, uniformly mixing by shaking, adding a mixed solution of chloroform and m-xylene, extracting by shaking, centrifuging, taking a lower-layer solution out of a second centrifuge tube, and drying by blowing;
step c, adding ethanol into the dried second centrifugal tube, transferring the dried second centrifugal tube into a beaker after redissolution, stirring, adding deionized water, and adding a hydrochloric acid solution to adjust the pH value to 2 +/-0.1;
in the reaction system, the reaction temperature is increased to 60 ℃ and kept, and the following reactions (1) to (5) theoretically occur with continuous stirring:
in the reaction formula (1), amitraz (I) is hydrolyzed under an acidic condition to generate monoaminatraz (II) and 2, 4-dimethyl benzamide (III);
hydrolyzing the formamidine in the reaction formula (2) continuously under an acidic condition to generate 2, 4-dimethylaniline ((r)) and methyl formamide ((v));
when the reaction of the reaction formula (2) is carried out, the formamidine also has side reaction of the reaction formula (3) to generate 2, 4-dimethyl benzamide (③) and methylamine (sixth);
2, 4-dimethyl benzamide (c) is subjected to acid hydrolysis reaction in the reaction (4) to generate 2, 4-dimethyl aniline (c) and formic acid (c);
the acidic hydrolysis reaction of the reaction formula (5) is carried out on the methyl formamide (a fifth step) generated by hydrolyzing the formamidine in the reaction formula (2), and the products are methylamine and formic acid;
it can be concluded from the above reaction processes of equations (1) to (5) that the hydrolysis reaction is theoretically initiated with amitraz, and the final products produced should be xylidine, formic acid and methylamine. However, in the actual reaction process, due to different hydrolysis degrees of the reactions under the same condition, the products (i) to (c) are simultaneously present in the reaction system, which results in the occurrence of side reactions affecting the yield of the final product dimethylaniline, wherein the side reactions are shown in the reaction formula (6):
in the side reaction process of the reaction formula (6), mono-formamidine and xylidine are subjected to substitution reaction under the condition to generate N, N-bis (2, 4-dimethylphenyl) formamidine (viii) and methylamine. The reaction rate of the reaction is far higher than that of the hydrolysis reaction (reaction formulas (1) - (4)), the hydrolysis reaction of the reaction formula (1- (4) needs multiple steps to generate the xylidine, and the reaction rate is gradually reduced as the reaction proceeds, while the substitution reaction of the reaction formula (6) needs only one step, and the reaction of the formamidine and the xylidine consumes the formamidine and the xylidine in the system, and for other hydrolysis reactions, the content of the formamidine and the xylidine in the system is reduced, and the hydrolysis reactions are promoted to proceed.
Under the condition that hydrolysis reaction is not influenced, the side reaction shown in the reaction formula (6) of the monoamitraz and the dimethylaniline is avoided by controlling the reaction time and adding a protective agent to react with primary amine in the dimethylaniline, the dimethylaniline is reduced by extracting and removing a protective group after the hydrolysis of the diamitraz is finished, and the diaminadine is used as a substance to be detected and is identified by furfural, so that the identification of the diamitraz in a sample is realized;
step d, raising the reaction temperature to 60 ℃, adding chloroform, starting timing and stirring, stopping stirring every 5min, layering the solution, adding a chloroform solution of phthalic anhydride into the lower layer solution, then stirring again, repeating the operation after 5min, standing and layering until 25min later, taking the lower layer solution, placing the lower layer solution into a flask, and evaporating to dryness to obtain an intermediate product;
in the step d, carrying out acylation reaction of primary amine on dimethylaniline and phthalic anhydride under the condition of chloroform, carrying out acylation protection on the primary amine in the dimethylaniline to produce a protected product, avoiding side reaction between the dimethylaniline generated by hydrolysis reaction and the formamidine, and reducing the consumption of the dimethylaniline in a reaction system;
step e, adding an alcoholic solution of hydrazine hydrate into the intermediate product, keeping the temperature of 35-45 ℃, heating in a water bath for reaction to generate xylidine to obtain a mixed solution, adding a hydrochloric acid solution at room temperature, adjusting the pH value of the mixed solution to 2, filtering, treating the filtrate with solid sodium carbonate until the pH value of the filtrate reaches 9-10, adding chloroform for extraction, taking a chloroform layer, drying by using a drying agent, and performing air blowing concentration to obtain a product to be detected;
in the step e, adding an alcoholic solution of hydrazine hydrate as a deprotection agent, reacting the protected product generated in the reaction formula (7), removing a protective group of primary amine, reducing to generate dimethylaniline, avoiding the side reaction shown in the reaction formula (6) of the dimethylaniline generated in the hydrolysis reaction and the formamidine, reducing the consumption of the dimethylaniline, and identifying the dimethylaniline as a product to be detected;
step f, redissolving the product to be detected by using glacial acetic acid and transferring the product to a third centrifugal tube to obtain a liquid to be detected, dropwise adding a furfural aqueous solution into the liquid to be detected, and observing the phenomenon;
dimethylaniline and furfural undergo a color reaction under an acidic condition to generate a red compound, and the reaction is used for identifying whether the liquid to be detected contains the dimethylaniline.
Step g, result judgment:
after the furfural aqueous solution is dripped, the color of the solution is changed into bright red, which indicates that the solution to be detected contains higher-concentration dimethylaniline, and the solution to be detected is judged to be positive, namely the sample to be detected contains amitraz; and (3) after the furfural aqueous solution is dripped, the color of the solution is not changed, which indicates that the solution to be detected does not contain dimethylaniline or the concentration of the dimethylaniline is low, and the solution is judged to be negative, namely the sample to be detected does not contain amitraz. And (3) dropping a furfural aqueous solution into the solution to be detected, wherein the solution to be detected is bright red, which indicates that the solution to be detected contains dimethylaniline, the dimethylaniline reacts with the furfural, and the dimethylaniline in the solution to be detected is converted from the amitraz in the sample to be detected, so that the sample to be detected is judged to be positive, namely the sample to be detected contains the amitraz. And (3) after the furfural aqueous solution is dropwise added into the solution to be detected, the color is unchanged, which indicates that the solution to be detected does not contain dimethylaniline or the concentration of the dimethylaniline is low, and the solution to be detected cannot perform a color reaction with furfural, the dimethylaniline is converted from amitraz, and the solution to be detected does not contain the dimethylaniline or the concentration of the dimethylaniline is low, so that the color reaction is not enough to occur, and the solution to be detected is judged to be negative, namely the sample to be detected does not contain the amitraz or the content of the amitraz is lower than the detection limit.
The invention has the beneficial effects that: compared with a chromatography method and a conventional spectrophotometry method, the detection method provided by the invention has the advantages that a target substance of the diformamidine is extracted from agricultural products by means of chemical reaction, a series of hydrolysis reactions are carried out to generate the dimethylaniline, the primary amine group of the dimethylaniline is protected, side reactions consuming the dimethylaniline are reduced, the hydrolysis reactions are carried out in the direction of producing the dimethylaniline, the generation amount of the dimethylaniline in a reaction system is increased, then the deprotection reactions are carried out, the protecting group on the primary amine of the dimethylaniline is removed to obtain the dimethylaniline, the dimethylaniline in the liquid to be detected is identified by utilizing the color reaction of a furfural aqueous solution and the dimethylaniline, and further, the detection of the residual diformamidine in the sample to be detected is realized. The method has the advantages of simple and understandable principle, strong specificity, high sensitivity, visual detection result, high accuracy of the detection result, no need of large-scale analytical instruments, relatively less time consumption, extremely low analysis cost, special suitability for on-site rapid detection of the residue of the amitraz in agricultural products and strong practicability.
In some embodiments, the sample to be tested is one of a vegetable sample to be tested or a fruit sample to be tested.
In some embodiments, the phosphate buffer solution has a pH of 6.8 to 7.2.
In some embodiments, the volume ratio of chloroform to meta-xylene in the mixed solution of chloroform and meta-xylene is 9.5: 0.5.
In some embodiments, the centrifugation speed in step b is 4000 rpm/min.
In some embodiments, the concentration of the hydrochloric acid solution is 1 mol/L. The hydrochloric acid solution is used for providing an acidic environment, facilitating subsequent hydrolysis reaction and adjusting the pH value of the solution.
In some embodiments, the chloroform solution of phthalic anhydride is a 1.0g/L concentration of phthalic anhydride in chloroform. Phthalic anhydride is used as a protective agent of primary amine of dimethylaniline, and the phthalic anhydride and the dimethylaniline react in a reaction formula (7) under the condition of chloroform to protect the primary amine of the dimethylaniline, so that the side reaction shown in the reaction formula (6) of the dimethylaniline and the formamidine is avoided, and the consumption of the dimethylaniline is reduced.
In some embodiments, the volume ratio of hydrazine hydrate to ethanol in the alcoholic solution of hydrazine hydrate is 0.1: 6. And the alcoholic solution of hydrazine hydrate is used as a protective agent for removing the protective group of primary amine of dimethylaniline, and the dimethylaniline is obtained by reduction, so that the subsequent color reaction with the furfural aqueous solution is facilitated.
In some embodiments, the desiccant is anhydrous sodium sulfate. And e, using anhydrous sodium sulfate for drying the filtrate obtained in the step e, so as to be convenient for subsequent quick blow drying and concentration of dimethylaniline.
In some embodiments, the aqueous furfural solution is an aqueous furfural solution at a concentration of 10 g/L. The furfural aqueous solution and the solution to be detected are subjected to color development reaction, so that whether the solution to be detected contains the xylidine or not can be conveniently identified.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
In the embodiment, chloroform is analytically pure trichloromethane supplied by national drug group chemical reagent company Limited, anhydrous sodium sulfate is 99% anhydrous sodium sulfate supplied by national drug group chemical reagent company Limited, m-xylene is analytically pure m-xylene supplied by national drug group chemical reagent company Limited, ethanol is analytically pure ethanol supplied by national drug group chemical reagent company Limited, phthalic anhydride is analytically pure phthalic anhydride supplied by national drug group chemical reagent company Limited, hydrazine hydrate is 98% synthetic hydrazine hydrate supplied by national drug group chemical reagent company Limited, and hydrochloric acid is hydrochloric acid solution with mass fraction of 36% -38% supplied by national drug group chemical reagent company Limited; the anhydrous sodium sulfate is analytically pure anhydrous sodium sulfate supplied by national drug group chemical reagent company Limited, the glacial acetic acid is analytically pure glacial acetic acid supplied by national drug group chemical reagent company Limited, and the furfural is analytically pure furfural supplied by national drug group chemical reagent company Limited;
1mol/L hydrochloric acid solution: measuring 43ml of 36% hydrochloric acid by using a measuring cylinder, pouring the hydrochloric acid into a beaker, dissolving the hydrochloric acid by using deionized water, then injecting the hydrochloric acid into a 500ml volumetric flask by using a glass rod for drainage, and then fixing the volume to a scale mark;
10g/L furfural aqueous solution: weighing 10g of furfural, pouring into a beaker, diluting with deionized water, draining with a glass rod, injecting into a 1000ml volumetric flask, and then fixing the volume to a scale mark;
1.0g/L in chloroform of phthalic anhydride: weighing 1.0g of phthalic anhydride, pouring the phthalic anhydride into a beaker, diluting the phthalic anhydride with deionized water, draining the phthalic anhydride with a glass rod, injecting the phthalic anhydride into a 1000ml volumetric flask, and then fixing the volume to a scale mark;
alcoholic solution of hydrazine hydrate: respectively measuring 1ml of hydrazine hydrate and 60ml of ethanol, pouring into a beaker, and uniformly mixing;
the reagents of this example 1 were used in the following examples 2 to 4.
Example 2
The invention discloses a method for rapidly detecting amitraz residues in agricultural products, which comprises the following steps:
step a, weighing 100g of a vegetable sample to be tested without sludge in a homogenizer, and homogenizing to obtain a homogenized vegetable sample to be tested;
step b, weighing 5g of a to-be-detected homogeneous vegetable sample into a 50ml first centrifuge tube, adding 10ml of phosphate buffer solution with the pH value of 6.8, shaking and uniformly mixing for 1min, adding 5ml of mixed solution of chloroform and m-xylene, shaking and extracting for 3min, centrifuging for 1min at 4000prm/min, taking 2ml to 15ml of lower layer solution into a second centrifuge tube, drying by air blowing at 60 ℃ in a fume hood, wherein the volume ratio of chloroform to m-xylene in the mixed solution of chloroform and m-xylene is 9.5: 0.5;
step c, adding 2ml of ethanol into the dried second centrifugal tube, transferring the dried second centrifugal tube into a 500ml beaker after redissolution, placing the beaker on a constant-temperature magnetic stirrer for stirring, adding 150ml of deionized water, and adding 1mol/L hydrochloric acid solution to adjust the pH value to 2 +/-0.1;
step d, raising the reaction temperature to 60 ℃, adding 10ml of chloroform, timing and stirring, stopping stirring every 5min, layering the solution, adding 1ml of 1.0g/L chloroform solution of phthalic anhydride into the lower layer solution (namely chloroform phase), then continuing stirring, repeating the operation after 5min, standing and layering until 25min later, taking the lower layer solution (namely chloroform phase) out of the flask, and performing rotary evaporation and evaporation to obtain an intermediate product;
step e, adding 5ml of alcoholic solution of hydrazine hydrate into the intermediate product, keeping the temperature of 35 ℃, heating in a water bath for 1h to react to generate xylidine, obtaining mixed solution, returning to room temperature, adding 1mol/L hydrochloric acid solution at room temperature, adjusting the pH value of the mixed solution to 2, filtering, treating the filtrate with solid sodium carbonate until the pH value of the filtrate reaches 9, adding chloroform for extraction, taking a chloroform layer, drying the chloroform layer with anhydrous sodium sulfate, drying and concentrating under nitrogen to obtain a product to be detected, wherein the volume ratio of hydrazine hydrate to ethanol in the alcoholic solution of hydrazine hydrate is 0.1: 6;
step f, re-dissolving the product to be detected by using 1ml of glacial acetic acid, transferring the re-dissolved product to a 2ml third centrifuge tube to obtain a liquid to be detected, dropwise adding 10g/L furfural aqueous solution into the liquid to be detected, and observing the phenomenon;
step g, result judgment:
and (3) after the furfural aqueous solution is dripped, the color of the solution is changed into bright red, which indicates that the solution to be detected contains higher-concentration dimethylaniline, and the solution to be detected is judged to be positive, namely the vegetable sample to be detected contains amitraz.
Example 3
The invention discloses a method for rapidly detecting amitraz residues in agricultural products, which comprises the following steps:
step a, weighing 100g of a to-be-detected fruit sample without sludge in a homogenizer, and homogenizing to obtain a to-be-detected homogenized fruit sample;
b, weighing 10g of a to-be-detected homogeneous fruit sample into a 50ml first centrifuge tube, adding 10ml of phosphate buffer solution with the pH value of 7.2, shaking and uniformly mixing for 1min, adding 5ml of mixed solution of chloroform and m-xylene, shaking and extracting for 3min, centrifuging for 1min at 4000prm/min, taking 2.5ml to 15ml of lower-layer solution into a second centrifuge tube, drying by air blowing at 70 ℃ in a ventilation cabinet, wherein the volume ratio of chloroform to m-xylene in the mixed solution of chloroform and m-xylene is 9.5: 0.5;
step c, adding 2ml of ethanol into the dried second centrifugal tube, transferring the dried second centrifugal tube into a 500ml beaker after redissolution, placing the beaker on a constant-temperature magnetic stirrer for stirring, adding 150ml of deionized water, and adding 1mol/L hydrochloric acid solution to adjust the pH value to 2 +/-0.1;
step d, raising the reaction temperature to 60 ℃, adding 10ml of chloroform, timing and stirring, stopping stirring every 5min, layering the solution, adding 1ml of 1.0g/L chloroform solution of phthalic anhydride into the lower layer solution (namely chloroform phase), then continuing stirring, repeating the operation after 5min, standing and layering until 25min later, taking the lower layer solution (namely chloroform phase) out of the flask, and performing rotary evaporation and evaporation to obtain an intermediate product;
step e, adding 5ml of alcoholic solution of hydrazine hydrate into the intermediate product, keeping the temperature at 45 ℃, heating in a water bath for 1h to react to generate xylidine, obtaining mixed solution, returning to room temperature, adding 1mol/L hydrochloric acid solution at room temperature, adjusting the pH value of the mixed solution to 2, filtering, treating the filtrate with solid sodium carbonate until the pH value of the filtrate reaches 10, adding chloroform for extraction, taking a chloroform layer, drying the chloroform layer with anhydrous sodium sulfate, drying and concentrating under nitrogen to obtain a product to be detected, wherein the volume ratio of hydrazine hydrate to ethanol in the alcoholic solution of hydrazine hydrate is 0.1: 6;
step f, re-dissolving the product to be detected by using 1ml of glacial acetic acid, transferring the re-dissolved product to a 2ml third centrifuge tube to obtain a liquid to be detected, dropwise adding 10g/L furfural aqueous solution into the liquid to be detected, and observing the phenomenon;
step g, result judgment:
and (3) after the furfural aqueous solution is dripped, the color of the solution is not changed, which indicates that the solution to be detected does not contain dimethylaniline or the concentration of the dimethylaniline is low, and the solution is judged to be negative, namely the fruit sample to be detected does not contain amitraz.
Example 4
The invention discloses a method for rapidly detecting amitraz residues in agricultural products, which comprises the following steps:
step a, weighing 100g of a vegetable sample to be tested without sludge in a homogenizer, and homogenizing to obtain a homogenized vegetable sample to be tested;
b, weighing 10g of a to-be-detected homogeneous vegetable sample into a 50ml first centrifuge tube, adding 10ml of phosphate buffer solution with the pH value of 7.0, shaking and uniformly mixing for 1min, adding 5ml of mixed solution of chloroform and m-xylene, shaking and extracting for 3min, centrifuging for 1min at 4000prm/min, taking 2.25ml to 15ml of lower-layer solution into a second centrifuge tube, drying the lower-layer solution in a ventilation cabinet by air drying at 65 ℃, wherein the volume ratio of chloroform to m-xylene in the mixed solution of chloroform and m-xylene is 9.5: 0.5;
step c, adding 2ml of ethanol into the dried second centrifugal tube, transferring the dried second centrifugal tube into a 500ml beaker after redissolution, placing the beaker on a constant-temperature magnetic stirrer for stirring, adding 150ml of deionized water, and adding 1mol/L hydrochloric acid solution to adjust the pH value to 2 +/-0.1;
step d, raising the reaction temperature to 60 ℃, adding 10ml of chloroform, timing and stirring, stopping stirring every 5min, layering the solution, adding 1ml of 1.0g/L chloroform solution of phthalic anhydride into the lower layer solution (namely chloroform phase), then continuing stirring, repeating the operation after 5min, standing and layering until 25min later, taking the lower layer solution (namely chloroform phase) out of the flask, and performing rotary evaporation and evaporation to obtain an intermediate product;
step e, adding 5ml of alcoholic solution of hydrazine hydrate into the intermediate product, keeping the temperature of 40 ℃, heating in a water bath for 1h to react to generate xylidine, obtaining mixed solution, returning to room temperature, adding 1mol/L hydrochloric acid solution at room temperature, adjusting the pH value of the mixed solution to 2, filtering, treating the filtrate with solid sodium carbonate until the pH value of the filtrate reaches 9.5, adding chloroform for extraction, taking a chloroform layer, drying the chloroform layer with anhydrous sodium sulfate, drying and concentrating under nitrogen to obtain a product to be detected, wherein the volume ratio of hydrazine hydrate to ethanol in the alcoholic solution of hydrazine hydrate is 0.1: 6;
step f, re-dissolving the product to be detected by using 1ml of glacial acetic acid, transferring the re-dissolved product to a 2ml third centrifuge tube to obtain a liquid to be detected, dropwise adding 10g/L furfural aqueous solution into the liquid to be detected, and observing the phenomenon;
step g, result judgment:
and (3) after the furfural aqueous solution is dripped, the color of the solution is not changed, which indicates that the solution to be detected does not contain dimethylaniline or the concentration of the dimethylaniline is low, and the solution is judged to be negative, namely the vegetable sample to be detected does not contain amitraz.
The above description is only for the embodiments of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A method for rapidly detecting amitraz residue in agricultural products comprises the following steps:
step a, weighing a sample to be detected, from which sludge is removed, in a homogenizer, and homogenizing to obtain a homogeneous sample to be detected;
b, weighing the homogeneous sample to be detected in a first centrifuge tube, adding a phosphate buffer solution, shaking and uniformly mixing, adding a mixed solution of chloroform and m-xylene, shaking and extracting, centrifuging, taking a lower-layer solution into a second centrifuge tube, and drying by blowing;
step c, adding ethanol into the dried second centrifugal tube, transferring the dried second centrifugal tube into a beaker after redissolution, stirring, adding deionized water, and adding a hydrochloric acid solution to adjust the pH value to 2 +/-0.1;
step d, raising the reaction temperature to 60 ℃, adding chloroform, starting timing and stirring, stopping stirring every 5min, layering the solution, adding a chloroform solution of phthalic anhydride into the lower layer solution, then stirring again, repeating the operation after 5min, standing and layering until 25min later, taking the lower layer solution, placing the lower layer solution into a flask, and evaporating to dryness to obtain an intermediate product;
step e, adding an alcoholic solution of hydrazine hydrate into the intermediate product, keeping the temperature of 35-45 ℃, heating in a water bath for reaction to generate xylidine to obtain a mixed solution, adding a hydrochloric acid solution at room temperature, adjusting the pH value of the mixed solution to 2, filtering, treating the filtrate with solid sodium carbonate until the pH value of the filtrate reaches 9-10, adding chloroform for extraction, taking a chloroform layer, drying by using a drying agent, and performing air blowing concentration to obtain a product to be detected;
step f, re-dissolving the product to be detected by using glacial acetic acid, transferring the re-dissolved product to a third centrifugal tube to obtain a liquid to be detected, dropwise adding a furfural aqueous solution into the liquid to be detected, and observing the phenomenon;
step g, result judgment:
after the furfural aqueous solution is dripped, the color of the solution is changed into bright red, which indicates that the solution to be detected contains higher-concentration dimethylaniline and is judged to be positive, namely the sample to be detected contains amitraz; and (3) after the furfural aqueous solution is dripped, the color of the solution is not changed, which indicates that the solution to be detected does not contain dimethylaniline or the concentration of the dimethylaniline is low, and the solution to be detected is judged to be negative, namely the sample to be detected does not contain amitraz.
2. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the sample to be detected is one of a vegetable sample to be detected or a fruit sample to be detected.
3. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the pH value of the phosphate buffer solution is 6.8-7.2.
4. The method for rapidly detecting amitraz residues in agricultural products as claimed in claim 1, wherein the volume ratio of chloroform to m-xylene in the mixed solution of chloroform and m-xylene is 9.5: 0.5.
5. The method for rapidly detecting amitraz residues in agricultural products of claim 1, wherein the centrifugation speed in step b is 4000 rpm/min.
6. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the concentration of the hydrochloric acid solution is 1 mol/L.
7. The method for rapidly detecting amitraz residues in agricultural products as claimed in claim 1, wherein the chloroform solution of phthalic anhydride is a chloroform solution of phthalic anhydride with a concentration of 1.0 g/L.
8. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the volume ratio of hydrazine hydrate to ethanol in the alcoholic solution of hydrazine hydrate is 0.1: 6.
9. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the drying agent is anhydrous sodium sulfate.
10. The method for rapidly detecting amitraz residues in agricultural products according to claim 1, wherein the furfural aqueous solution is a 10g/L furfural aqueous solution.
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