CN111111624B - Adsorbing material and method for detecting content of pyrethroid pesticide residues in tobacco leaves - Google Patents
Adsorbing material and method for detecting content of pyrethroid pesticide residues in tobacco leaves Download PDFInfo
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- CN111111624B CN111111624B CN202010014174.9A CN202010014174A CN111111624B CN 111111624 B CN111111624 B CN 111111624B CN 202010014174 A CN202010014174 A CN 202010014174A CN 111111624 B CN111111624 B CN 111111624B
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- 239000002728 pyrethroid Substances 0.000 title claims abstract description 41
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 32
- 241000208125 Nicotiana Species 0.000 title claims abstract description 28
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 11
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical group OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012488 sample solution Substances 0.000 claims description 6
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Chemical group OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 5
- HAQLHRYUDBKTJG-UHFFFAOYSA-N 3,5-dihydroxybenzaldehyde Chemical group OC1=CC(O)=CC(C=O)=C1 HAQLHRYUDBKTJG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical group OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 2
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical group OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004587 chromatography analysis Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000575 pesticide Substances 0.000 description 16
- 238000001514 detection method Methods 0.000 description 14
- 239000003463 adsorbent Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 125000000879 imine group Chemical group 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- 239000005951 Methiocarb Substances 0.000 description 2
- CFZLNRGUBAVQNO-UHFFFAOYSA-N N-(3,5-Dichlorophenyl)succinimide Chemical compound ClC1=CC(Cl)=CC(N2C(CCC2=O)=O)=C1 CFZLNRGUBAVQNO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YFBPRJGDJKVWAH-UHFFFAOYSA-N methiocarb Chemical compound CNC(=O)OC1=CC(C)=C(SC)C(C)=C1 YFBPRJGDJKVWAH-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000004885 tandem mass spectrometry Methods 0.000 description 2
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 description 1
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical compound NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 description 1
- RHSUJRQZTQNSLL-UHFFFAOYSA-N 3-Hydroxy-carbofuran Chemical group CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2O RHSUJRQZTQNSLL-UHFFFAOYSA-N 0.000 description 1
- SPNQRCTZKIBOAX-UHFFFAOYSA-N Butralin Chemical compound CCC(C)NC1=C([N+]([O-])=O)C=C(C(C)(C)C)C=C1[N+]([O-])=O SPNQRCTZKIBOAX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005978 Flumetralin Substances 0.000 description 1
- PWNAWOCHVWERAR-UHFFFAOYSA-N Flumetralin Chemical compound [O-][N+](=O)C=1C=C(C(F)(F)F)C=C([N+]([O-])=O)C=1N(CC)CC1=C(F)C=CC=C1Cl PWNAWOCHVWERAR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005807 Metalaxyl Substances 0.000 description 1
- IQGAMYRKFBNTFD-UHFFFAOYSA-N NC1=C(C(=C(C(=C1C(=O)O)N)C(=O)O)N)C(=O)O Chemical compound NC1=C(C(=C(C(=C1C(=O)O)N)C(=O)O)N)C(=O)O IQGAMYRKFBNTFD-UHFFFAOYSA-N 0.000 description 1
- 239000005591 Pendimethalin Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000004303 annulenes Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 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
- 229960005286 carbaryl Drugs 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019990 fruit wine Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- QBSJMKIUCUGGNG-UHFFFAOYSA-N isoprocarb Chemical compound CNC(=O)OC1=CC=CC=C1C(C)C QBSJMKIUCUGGNG-UHFFFAOYSA-N 0.000 description 1
- 239000005910 lambda-Cyhalothrin Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZQEIXNIJLIKNTD-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alaninate Chemical compound COCC(=O)N(C(C)C(=O)OC)C1=C(C)C=CC=C1C ZQEIXNIJLIKNTD-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- CHIFOSRWCNZCFN-UHFFFAOYSA-N pendimethalin Chemical compound CCC(CC)NC1=C([N+]([O-])=O)C=C(C)C(C)=C1[N+]([O-])=O CHIFOSRWCNZCFN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- XELRMPRLCPFTBH-UHFFFAOYSA-N quinazoline-2,4-diamine Chemical compound C1=CC=CC2=NC(N)=NC(N)=C21 XELRMPRLCPFTBH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The application discloses an adsorption material and a method for detecting the content of pyrethroid pesticide residues in tobacco leaves. The adsorption material is an oxime polymer which is flanked by aromatic conjugated rings, and the aromatic conjugated rings have the capability of generating pi-pi electron stacking effect with pyrethroid ester groups of pyrethroid substances, so that reliable adsorption force is formed. The adsorption material firstly adsorbs pyrethroid pesticide residues contained in the tobacco sample liquid, then carries out chromatographic analysis after desorption, and avoids the problems that the content of the pyrethroid pesticide residues is trace, so that the quantitative analysis cannot be carried out and the species cannot be qualitatively analyzed.
Description
Technical Field
The invention relates to the technical field of tobacco leaf pesticide residue detection, in particular to an adsorbing material and a method for detecting the content of pyrethroid pesticide residue in tobacco leaves.
Background
The development of agricultural industrialization, the production of agricultural products increasingly depends on chemical and biological products such as pesticides, antibiotics and hormones. The unreasonable use of the substances can lead to the overproof residue in agricultural products, affect the edible safety of consumers, and cause the consumers to have diseases and abnormal development in serious cases, even directly cause poisoning and death. The method controls the harm of pesticide residue to human body, one of the most effective methods is to strengthen the supervision of chemical and biological product use, and the capability level and efficiency of pesticide residue detection in food must be improved for ensuring the supervision. The pesticide residue detection in the world is developed to multi-residue and rapid analysis at present, and the multi-residue detection is an important trend of pesticide residue analysis and has three advantages of multi-, quick-and quasi-advantages. From 2006 to 2008, the multi-residue detection standard for simultaneously determining more than 100 pesticides is formulated successively for agricultural products such as fruits, vegetables, grains, tea, fruit and vegetable juice, fruit wine, milk powder, edible fungi and the like.
Tobacco is used as a special economic crop, various types of pesticides are commonly used in order to effectively control plant diseases and insect pests in the production process, the phenomenon that pesticide residues exceed standards often occurs, the pesticide residues in tobacco leaves become an important factor influencing the safety of the tobacco leaves, 3 tobacco multiple pesticide residue detection industry standards are released in 2011 in the tobacco industry, and the series of standards can detect 146 pesticides by using 4 pretreatment methods and 3 analysis methods. The 73 pesticides with larger polarity are purified by QuEChERS and then analyzed by LC/MS/MS, the 38 pesticides with non-polarity or medium polarity are treated by the QuEChERS method and then purified by silica gel and Flori silica gel small columns, and analyzed by GC/MS and GC/ECD, and the 35 pesticides with organochlorine and pyrethroid are independently used as one class, and analyzed by GC/ECD after passing through a solid phase extraction small column. The industrial standards are used for analyzing a plurality of pesticides with wide application range in tobacco, such as 6 pesticides of metalaxyl, butralin, pendimethalin, flumetralin, lambda-cyhalothrin and dimethachlon (the above 3 standards do not contain dimethachlon), 4 pretreatment methods are also needed, the time and the labor are consumed, and the efficiency is low.
In order to shorten the analysis time and improve the detection efficiency, the Chinese tobacco general company releases an enterprise standard for detecting multiple pesticide residues in tobacco and tobacco products in 2014, and gas chromatography-tandem mass spectrometry and liquid chromatography-tandem mass spectrometry are used for detection, wherein 169 pesticides are detected by a gas-mass tandem method, and 141 pesticides are detected by a liquid-mass tandem method. In both methods, a QuEChERS method is adopted for sample pretreatment, and a tandem mass spectrometry method is adopted for analysis. Compared with the prior industry standard, the working efficiency can be greatly improved, and the labor burden is reduced.
However, the content of the pyrethroid pesticide residues in the tobacco leaves reaches a trace level basically. Chromatographic peaks are difficult to separate by adopting a chromatograph, the qualitative analysis effect is not ideal, and quantitative detection is more difficult.
Disclosure of Invention
In order to solve the problems, the application provides an adsorbing material and a method for detecting the content of the pyrethroid pesticide residues in the tobacco leaves, so that quantitative detection and qualitative analysis of specific types of the pyrethroid pesticide residues are realized.
The inventor unexpectedly finds that an imine chain formed by alternately forming a plurality of imine groups (-C = N-) through single bonds has a larger conjugated system, when an aromatic conjugated ring is connected to the imine chain, the aromatic conjugated ring can form pi-pi conjugation with the imine chain conjugated system, so that an electron delocalized orbit of the imine chain conjugated system is remarkably expanded, and the side-connected oxime polymer formed by the method has adsorbability on pyrethroid compounds. The structure determining the adsorbability is that the pyrethroid compound has a ph-O-ph group, the diphenyl ether group forms a p-pi conjugated system by a pi orbit of a benzene ring and a p orbit of lone pair electrons of an O atom, and the electron delocalization of the p-pi conjugated system is smaller than that of the pi-pi conjugated system. Whereas oxime polymers have large pi electrons capable of forming with the p electrons of the p-pi conjugated system at such longer distances, known as pi-p electron stacking, whereby molecular stacking occurs, resulting in a wider range of electron delocalization toward more stable states. Based on this, the invention of the present application has been completed.
Pyrethroid substance
Generally refers to compounds having the general structural formula,. Some of the properties of pyrethroid pesticides are shown in the table below.
According to a first embodiment of the application, the adsorption material is used for adsorbing pyrethroid substances, and is an oxime polymer obtained by condensation polymerization of a monomer A with an amino group as a reactive group and a monomer B with an aldehyde group as a reactive group;
wherein monomer A has the structure shown in formula I:
monomer B has the structure shown in formula II:
in the formula I and the formula II,represents an aromatic conjugated ring;represents an aromatic conjugated ring; y, X is unsubstituted or substituted carboxyl or hydroxyl at any position, a and b are positive integers and are not simultaneously 1, and c and d are both positive integers.
Aromatic conjugated ring
It means that it conforms to Huckel's rule (Huckel's rule), and it means that when the pi-electron number of the conjugated polyene (annulene) of the closed cyclic planar type is (4 n + 2), where n is 0 or a positive integer. This application、The monocyclic ring of the five-membered or six-membered carbon heterocycle is preferably a monocyclic ring of an aromatic ring, a monocyclic ring of a five-membered or six-membered carbon heterocycle, and a condensed ring thereof, and specific examples of the monocyclic ring of the five-membered or six-membered carbon heterocycle include monocyclic rings such as a pyridine ring, a pyrimidine ring, a pyrrole ring, a furan ring, a thiophene ring, and imidazole, or condensed ring examples represented by purine, quinoline, naphthalene, and anthracene. It is understood that the examples of aromatic conjugated rings of the present application are also illustrativeIt may be a ring having a negative or positive charge, such as a metallocene ring or the like.
Regarding the number of the reactive groups in the monomer A and the monomer B, namely the values of a and B, when one of the two is 1, the obtained oxime polymer is a branched polymer; when both values are not 1, the resulting oxime polymer is a linear polymer or a bulk polymer. Branched polymers are preferred in this application, which gives the advantage of better solvent in organic solvents and lower viscosity, which sacrifices the size of the conjugated system of the imine chain.
In order to avoid the formation of a branched polymer, the oxime polymer of the present invention preferably has an average functionality of 2.2 to 3, preferably 2.4 to 2.8. Here, the average functionality is obtained from the reactive groups contained in the molecular structures of the monomers A and B and the reaction ratio of the two. Specifically, for example, if the number of reactive groups per molecule of monomer a is 3, the number of reactive groups per molecule of monomer B is 1, and the molar ratio of the reaction of monomer a and monomer B is 1.5:1, the average functionality = (1.8 × 3 +1 × 1)/(1.8 + 1) = 2.28.
The pendant group of the non-reactive group on the aromatic conjugated ring in the above-mentioned monomer A or monomer B is preferably a group having an active hydrogen, such as a carboxyl group or a hydroxyl group. The monomers A and B with the groups can form intermolecular hydrogen bonds with amino groups of the pyrethroid so as to improve the adsorption force on the pyrethroid.
There may be mentioned a relatively easily available example of the monomer A, the monomer B being melamine and the monomer B being 3, 5-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2-carboxybenzaldehyde or 3-carboxybenzaldehyde.
For the polycondensation reaction, the temperature of the polycondensation reaction can be 160-200 ℃, preferably 170-190 ℃, and particularly preferably 180 ℃; on the basis of the above, the time of the polycondensation reaction is 48 to 96 hours, preferably 60 to 84 hours, and particularly preferably 72 hours.
The solvent for the polycondensation reaction is an inert solvent, preferably DMSO or carbon tetrachloride.
As for the atmosphere of the reaction, it may be carried out in an inert atmosphere, such as a nitrogen atmosphere, a helium atmosphere, or a neon atmosphere, etc.
As for the manner of separating the reaction product from the reaction system, it can be adjusted according to the product characteristics. For reference, after the reaction is completed, the reaction mixture is washed with a mixture of DMF, methanol and THF in equal volume, dried at 60 deg.C and ground.
According to a second embodiment of the application, the application provides a method for detecting the content of pyrethroid pesticide residues in tobacco leaves by using the adsorbing material, which comprises the following steps:
(1) putting the adsorbing material into a tobacco leaf sample solution to obtain the adsorbing material adsorbing pyrethroid pesticide residues;
(2) desorbing the adsorbed pyrethroid pesticide residue into desorption liquid by using the adsorbing material to obtain sample injection liquid to be injected;
(3) and (4) enabling the sample injection liquid to pass through a chromatograph to obtain the pesticide residue content.
The stripping solution may be a solvent for pyrethroids, such as acetonitrile. As for the amount of the stripping solution, it is conceivable that the concentration of the pyrethroid type pesticide residue diluted can be within the detection accuracy of a chromatograph.
The desorption time is 10-30 min, preferably 12-20 min. The temperature of desorption may be room temperature.
The solvent of the sample solution is preferably a methanol-water solution, as a solvent for preferably dissolving the pesticide residue contained in the tobacco leaves to the maximum extent.
As regards the type of chromatograph and the chromatographic operating conditions, which are not the object of the present application, any chromatograph known in the art can carry out the present solution, for example HPLC-UV.
The adsorption material is an oxime polymer which is flanked by aromatic conjugated rings, and the aromatic conjugated rings can generate pi-pi electron stacking effect with pyrethroid groups of pyrethroid substances, so that reliable adsorption force is formed. The adsorption material firstly adsorbs pyrethroid pesticide residues contained in the tobacco sample liquid, then carries out chromatographic analysis after desorption, and avoids the problems that the content of the pyrethroid pesticide residues is trace, so that the quantitative analysis cannot be carried out and the species cannot be qualitatively analyzed.
Drawings
FIG. 1 is an infrared spectrum of the adsorbent synthesized in example 1.
Detailed Description
The following are specific examples of the present application and further describe the technical solutions of the present application, but the present application is not limited to these examples.
Example 1
And (4) synthesizing an adsorbing material. 0.126 g of melamine (molar mass 126.12), 0.245 g of 3, 5-dihydroxybenzaldehyde (molar mass 138.12) and DMSO (25 ml) were placed in a flask under a nitrogen atmosphere, and the mixture was refluxed at 180 ℃ for 72 hours, cooled, washed with a mixture of DMF (40 ml), methanol (40 ml) and THF (40 ml), dried at 60 ℃ and ground to obtain an adsorbent.
And (4) detecting pyrethroid pesticide residues. Weighing 0.3 g of tobacco leaves into a 4mL EP tube, adding 2mL of 45 vol% methanol-water solution, carrying out ultrasonic extraction for 5 min, taking 1mL of supernate, and diluting to 30 mL with 45% methanol-water solution for later use. The method comprises the steps of putting 30 mg of SNW material into 30 mL of sample solution (without adjusting pH), extracting for 50 min at the rotating speed of 600 rpm, removing the sample solution through centrifugal separation, adding 0.5 mL of acetonitrile, performing ultrasonic desorption for 15 min, performing centrifugal separation, and sampling 30 muL of sample to HPLC-UV analysis.
Example 2
And (4) synthesizing an adsorbing material. 0.252g of melamine (molar mass 126.12), 0.138 g of 3, 5-dihydroxybenzaldehyde (molar mass 138.12) and DMSO (25 ml) were added to a flask under a nitrogen atmosphere, and the mixture was refluxed at 180 ℃ for 72 hours, cooled, washed with a mixture of DMF (40 ml), methanol (40 ml) and THF (40 ml), dried at 60 ℃ and ground to obtain an adsorbent. The pyrethroid pesticide residue was detected as in example 1.
Example 3
And (4) synthesizing an adsorbing material. 0.595g of 2,4, 6-triaminobenzene-1, 3, 5-tricarboxylic acid (molar mass 297.264), 0.138 g of 3, 4-dihydroxybenzaldehyde (molar mass 138.12) and carbon tetrachloride (25 ml) were added to a flask under a nitrogen atmosphere, and then the mixed solution was refluxed at 180 ℃ for 72 hours, cooled, washed with a mixed solution composed of DMF (40 ml), methanol (40 ml) and THF (40 ml), dried at 60 ℃ and ground to obtain an adsorbent. The pyrethroid pesticide residue was detected as in example 1.
Example 4
And (4) synthesizing an adsorbing material. 0.480g of 2, 4-diaminoquinazoline (molar mass 160.176), 0.138 g of 3, 4-dihydroxybenzaldehyde (molar mass 138.12) and carbon tetrachloride (25 ml) were added to a flask under a nitrogen atmosphere, and then the mixture was refluxed at 180 ℃ for 72 hours, cooled, washed with a mixture of DMF (40 ml), methanol (40 ml) and THF (40 ml), dried at 60 ℃ and ground to obtain an adsorbent. The pyrethroid pesticide residue was detected as in example 1.
Example 5
And (4) synthesizing an adsorbing material. 0.246g of 2-aminopyrrole (molar mass 82.12), 0.138 g of 3, 4-dihydroxybenzaldehyde (molar mass 138.12) and carbon tetrachloride (25 ml) were added to the flask under a nitrogen atmosphere, and then the mixture was refluxed at 180 ℃ for 72 hours, cooled, washed with a mixture of DMF (40 ml), methanol (40 ml) and THF (40 ml), dried at 60 ℃ and ground to obtain an adsorbent. The pyrethroid pesticide residue was detected as in example 1.
Evaluation of
1. Infrared characterization
The adsorbing material synthesized in example 1, monomeric melamine, and 3, 5-dihydroxybenzaldehyde were subjected to infrared measurement by a fourier infrared spectrometer, and the obtained IR spectrum is shown in fig. 1. As can be seen, the triazine ring is 1557 cm -1 、1456cm -1 The characteristic absorption peak proves that triazine environment is remained in the adsorbing material, and Ar-OH is 1200-1300 cm -1 The stretching vibration peak still exists in SNWs, and-NH 2 is 3469cm -1 And antisymmetric and symmetric telescopic vibration peak at 3419 cm-1, 1654 cm -1 Bending vibration of (A) and characteristic absorption at 2700-The absence of bands in the adsorbent material indicates that the synthesis of the adsorbent material was successful.
2. Adsorption Rate test
0.1g of the adsorbent synthesized in example was charged into 100ml of each adsorbent charged with C having a known concentration 0 Methiocarb
The concentration C of pyrethroid pesticide contained in the rest solution is detected by a chromatograph after the pyrethroid pesticide is placed in a 45vo% methanol-water solution prepared from six pyrethroid pesticides including isoprocarb, carbaryl, carbofuran, 3-hydroxy carbofuran, propoxur and methiocarb for 20min at room temperature 1 . Calculation of adsorption Rate = (C) 0 - C 1 )/ C 0 X 100%. The calculation results are shown in Table 2.
Table 2 test results of adsorption rate
3. Detection precision of residual agriculture detection in tobacco leaves
The performance of the adsorbing material synthesized in example 1 on the detection of the content of the residual agricultural crops in tobacco leaves is shown in table 3.
TABLE 3 test results for various pyrethroid pesticides
The specific embodiments described herein are merely illustrative of the spirit of the application. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the present application as defined by the appended claims.
Claims (9)
1. The application of the adsorption material for detecting the content of the pyrethroid pesticide residue in the tobacco leaves is characterized in that the adsorption material is used for adsorbing the pyrethroid pesticide residue in the tobacco leaves, and the adsorption material is an imino polymer obtained by polycondensation of a monomer A taking amino as a reactive group and a monomer B taking aldehyde as a reactive group;
wherein monomer A has the structure shown in formula I:
monomer B has the structure shown in formula II:
2. Use according to claim 1, characterized in that monomer a is melamine and monomer B is 3, 5-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2-carboxybenzaldehyde or 3-carboxybenzaldehyde.
3. The use according to claim 1 or 2, wherein the imino polymer has an average functionality of 2.2 to 3.
4. Use according to claim 1 or 2, characterized in that the imine-based polymer is a branched polymer.
5. Use according to claim 1 or 2, wherein the temperature of the polycondensation reaction is 160 to 200 ℃ and the time of the polycondensation reaction is 48 to 96 hours.
6. Use according to claim 1 or 2, characterized in that the solvent of the polycondensation reaction is an inert solvent.
7. A method for detecting the content of pyrethroid pesticide residues in tobacco leaves by adopting an adsorbing material used in any one of the applications of claim 1-6, which is characterized by comprising the following steps:
(1) putting the adsorbing material into a tobacco leaf sample solution to obtain the adsorbing material adsorbing pyrethroid pesticide residues;
(2) desorbing the adsorbed pyrethroid pesticide residue into desorption liquid by using the adsorbing material to obtain sample injection liquid to be injected;
(3) and (4) enabling the sample injection liquid to pass through a chromatograph to obtain the pesticide residue content.
8. The method of claim 7, wherein the stripping solution is acetonitrile.
9. The method according to claim 7, wherein the solvent of the tobacco sample solution is a methanol-water solution.
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