CN111111629B - Adsorbing material and method for detecting carbamate pesticide residue content in tobacco leaves - Google Patents

Adsorbing material and method for detecting carbamate pesticide residue content in tobacco leaves Download PDF

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CN111111629B
CN111111629B CN202010014635.2A CN202010014635A CN111111629B CN 111111629 B CN111111629 B CN 111111629B CN 202010014635 A CN202010014635 A CN 202010014635A CN 111111629 B CN111111629 B CN 111111629B
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carbamate
monomer
adsorbing material
pesticide residues
tobacco leaves
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李冉
宋旭艳
魏敏
董爱君
何昀潞
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China Tobacco Hubei Industrial LLC
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Abstract

The application discloses an adsorbing material and a method for detecting the content of carbamate pesticide residues in tobacco leaves. The absorbing material is an oxime polymer which is connected with an aromatic conjugated ring in a side mode, and the aromatic conjugated ring is capable of generating pi-p electron stacking effect with a carbamate group of carbamate substances, so that reliable absorbing force is formed. The adsorbing material firstly adsorbs carbamate pesticide residues contained in the tobacco sample liquid, and then performs chromatographic analysis after desorption, so that the problems that quantitative analysis cannot be performed and types cannot be qualitatively analyzed due to the fact that the content of the carbamate pesticide residues is trace are solved.

Description

Adsorbing material and method for detecting carbamate pesticide residue content in tobacco leaves
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 carbamate pesticide residue content in tobacco leaves.
Background
With 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, influence 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 for controlling the harm of pesticide residue to human body is characterized by that it can raise the detection capability and efficiency of pesticide residue in food. 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 detecting more than 100 pesticides is formulated successively for agricultural products such as fruits, vegetables, grains, tea leaves, 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 carbamate 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 the adsorbing material and the method for detecting the content of the carbamate pesticide residues in the tobacco leaves, so that quantitative detection and qualitative analysis of specific types of the carbamate pesticide residues are realized.
The inventor unexpectedly finds that an imine chain formed by a plurality of imine groups (-C = N-) through single bonds in an alternating manner has a larger conjugated system, and 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 group oxime polymer formed by the method has adsorbability on carbamate compounds. The structure determining the adsorption property is that the carbamate compound has aminocarbonyl-NH-C = O-, the group is a p-p conjugated system formed by the p orbital of carbonyl and the p orbital of lone pair electron of N atom of amino, and the electron delocalization of the p-p 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-p conjugated system of the aminocarbonyl group at such a long distance of action is called pi-p electron stacking, whereby stacking of molecules occurs, thereby forming a wider area of electron delocalization toward a more stable state. Based on this, the invention of the present application has been completed.
Carbamate compounds
Refers to compounds containing-NH-C = O-in their molecular structure and mixtures thereof. In order to improve the adsorption easiness, the carbamate compound of the present application preferably has a structure with aromatic conjugated ring side groups, because the aromatic conjugated ring side groups can form pi-pi electron accumulation with the aromatic conjugated rings of the adsorbing material, thereby improving the adsorption force. Some of the characteristics of the carbamate pesticides are shown in the table below.
Figure DEST_PATH_IMAGE001
According to a first embodiment of the present application, an adsorption material for adsorbing carbamates, which is an oxime polymer obtained by polycondensation of a monomer a having an amino group as a reactive group and a monomer B having an aldehyde group as a reactive group;
wherein monomer A has the structure shown in formula I:
Figure DEST_PATH_IMAGE003
；
monomer B has the structure shown in formula II:
Figure DEST_PATH_IMAGE005
；
in the formula I and the formula II,
Figure DEST_PATH_IMAGE007
represents an aromatic conjugated ring;
Figure DEST_PATH_IMAGE009
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
Figure DEST_PATH_IMAGE011
、
Figure DEST_PATH_IMAGE013
Preferred as the monocyclic ring of the aromatic ring are monocyclic rings, monocyclic rings of five-or six-membered carbon heterocycles and condensed rings thereof, and specific examples of the monocyclic rings of five-or six-membered carbon heterocycles include monocyclic rings such as pyridine ring, pyrimidine ring, pyrrole ring, furan ring, thiophene ring and imidazole, or monocyclic rings such as purine, quinoline, naphthalene, etc,Anthracene is a representative example of a condensed ring. It is understood that the aromatic conjugated ring of the present application may also be exemplified by a ring having negative or positive electricity, such as a dicyclopentadienyl ring, etc.
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 ratios 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 these groups can form intermolecular hydrogen bonds with the amino groups of the carbamate to improve the adsorption force to the carbamate.
One of the more readily available examples of monomer A, monomer B, being melamine, and 3, 5-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2-carboxybenzaldehyde or 3-carboxybenzaldehyde, may be cited.
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, a neon atmosphere or the like.
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 carbamate pesticide residues in tobacco leaves by using the adsorbing material, and the method comprises the following steps:
(1) putting the adsorbing material into the tobacco leaf sample liquid to obtain the adsorbing material adsorbing the carbamate pesticide residues;
(2) desorbing the adsorbed carbamate pesticide residues 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 solution may be a solvent for carbamate, such as acetonitrile. As for the amount of the stripping solution, it is conceivable that the concentration of the carbamate-based pesticide residue diluted is 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 it is preferable to dissolve the pesticide residues 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 absorbing material is an oxime polymer which is connected with an aromatic conjugated ring in a side mode, and the aromatic conjugated ring is capable of generating pi-p electron stacking effect with a carbamate group of carbamate substances, so that reliable absorbing force is formed. The adsorbing material firstly adsorbs carbamate pesticide residues contained in the tobacco sample liquid, and then performs chromatographic analysis after desorption, so that the problems that quantitative analysis cannot be performed and types cannot be qualitatively analyzed due to the fact that the content of the carbamate pesticide residues is trace are solved.
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 (5) detecting carbamate 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 (3) synthesizing the 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 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. The carbamate 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 carbamate 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 carbamate 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 carbamate 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 vibrations at 3419 cm-1Dynamic peak, 1654 cm -1 The bending vibration at (A) and the characteristic absorption band at-CHO at 2700-.
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 The methiocarb is prepared from isoprocarb, carbaryl, carbofuran, 3-hydroxy carbofuran, propoxur and methiocarb which are six carbamate pesticides, and the obtained mixture is placed in a 45vo% methanol-water solution at room temperature for 20min, and then a chromatograph is used for detecting the concentration C of the carbamate pesticide contained in the residual solution 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 rates
Figure DEST_PATH_IMAGE014
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 results of performance test of various carbamates pesticides
Figure DEST_PATH_IMAGE015
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 in detecting the content of carbamate pesticide residues in tobacco leaves is characterized in that the adsorption material is used for adsorbing carbamate substances in the tobacco leaves, and the adsorption material is an imino polymer obtained by condensation polymerization 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:
Figure DEST_PATH_IMAGE002
；
monomer B has the structure shown in formula II:
Figure DEST_PATH_IMAGE004
；
in the formula I and the formula II,
Figure DEST_PATH_IMAGE006
represents an aromatic conjugated ring;
Figure DEST_PATH_IMAGE008
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.
2. Use according to claim 1, characterized in that said monomer a is melamine and said 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 carbamate pesticide residues in tobacco leaves by adopting the adsorbing material used in any one of the applications of claim 1 to 6, which is characterized by comprising the following steps:
(1) putting the adsorbing material into the tobacco leaf sample liquid to obtain the adsorbing material adsorbing the carbamate pesticide residues;
(2) desorbing the adsorbed carbamate pesticide residues into desorption liquid by using the adsorbing material to obtain sample injection liquid to be injected;
(3) and (3) 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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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152632A (en) * 2019-05-27 2019-08-23 浙江省农业科学院 A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152632A (en) * 2019-05-27 2019-08-23 浙江省农业科学院 A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ismet Kaya等.Synthesis and characterization of graft copolymers of melamine: Thermal stability, electrical conductivity, and optical properties.《Synthetic Metals》.2009,第159卷第1572-1582页. *
Synthesis and characterization of graft copolymers of melamine: Thermal stability, electrical conductivity, and optical properties;Ismet Kaya等;《Synthetic Metals》;20090520;第159卷;参见第2. Experimental、Scheme 1 *

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