CN114324717B - High-throughput detection method for carbamates and thio-compounds thereof - Google Patents
High-throughput detection method for carbamates and thio-compounds thereof Download PDFInfo
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Abstract
The invention provides a high-throughput detection method for carbamates and thio-compounds thereof, and belongs to the technical field of detection methods. The invention applies the MWCNTs@SiO 2 @PANI novel solid phase extraction adsorbent to the purification of samples of Chinese medicinal materials, tea, mushrooms and the like, can effectively reduce the complex matrix interference in the Chinese medicinal materials, tea, mushrooms and the like, can be repeatedly utilized for a plurality of times after being repeatedly washed by alcohol and water, and adopts high performance liquid chromatography mass spectrometry (HPLC-MS/MS) to carry out measurement, thereby establishing a high-efficiency, accurate and simple rapid detection method for pesticide residues of various carbamates and thio-type pesticides in the Chinese medicinal materials, tea and mushrooms, and the detection limit, the recovery rate and the precision of the method are all satisfactory.
Description
Technical Field
The invention belongs to the technical field of detection methods, and particularly relates to a high-throughput detection method for carbamates and thio-compounds thereof.
Background
The carbamate pesticide is a novel pesticide, and has the characteristics of high degradation rate, short residual period, strong selectivity and the like, so that the carbamate pesticide has been widely applied to agricultural production processes such as crop protection and the like, and is a key detection variety of pesticide residues in plant-derived agricultural products. However, some highly toxic pesticides such as carbofuran and aldicarb have long half-lives and are abused for a long period of time, and are extremely harmful to the human body through food chain enrichment. The thiocarbamate pesticide is a thiocarbamate pesticide, has the advantages of strong water solubility, easy adhesion, good efficacy and the like, has moderate toxicity, is a plant growth inhibitor with multiple functions of contact killing, systemic, antagonism, hormone and the like, is mainly used as herbicide, and can damage the nervous system and the liver and kidney system through the food chain enrichment function.
The quality safety of Chinese medicine, tea and mushroom is relevant to the growth of trade and the health of people. In recent years, developed countries strictly prescribe carbamate and thio residue limit-rate standards for Chinese medicinal materials, tea and mushrooms. In many domestic and foreign researches, more reports are given to residual analysis of carbamate, but few reports are given to residual analysis of thiocarbamate, reported research objects mainly concentrate on compounds such as molinate, dichlorvos and dicamba, detected target compounds are single, and the research objects are water samples and soil with relatively simple matrixes, and a high-flux multi-component simultaneous online measurement method for multiple carbamates and thio compounds in complex matrixes such as traditional Chinese medicinal materials, tea leaves, mushrooms and the like is lacked.
In the current research on pesticide residue detection of traditional Chinese medicinal materials, tea, mushrooms and the like, on the sample pretreatment method, methods such as a direct extraction method, solid-phase extraction column purification, dispersion solid-phase extraction and the like are mainly adopted, but the original extract produced by the direct extraction method contains very complex components, and the obtained spectrograms of the detected object with serious interference and mutual overlapping of chromatographic peaks have poor identification degree, so that the method cannot be directly used for instrument chromatographic analysis. The commercialized solid-phase extraction column is expensive, the dosage of organic reagent is large, the treatment time is long, and the process of complex activation, leaching, elution, collection and concentration is time-consuming and labor-consuming, so that the method is not suitable for popularization in a basic layer. And the dispersion solid phase extraction relies on proper extraction materials, so that batch sample pretreatment can be completed through a rapid adsorption and desorption mechanism, and time and labor are saved. Solid phase extraction materials based on commercialized or prepared synthetic multi-walled carbon nanotubes and composite materials thereof are increasingly used for enrichment and purification of complex samples as a high-efficiency and low-cost solid phase extraction adsorbent by virtue of a strong surface adsorption effect. In the inspection and detection method, the test of carbamates and their thio compounds mainly includes gas chromatography, liquid chromatography mass spectrometry, and the like. However, the sensitivity of the gas chromatography technology is difficult to meet the analysis requirement due to the poor thermal stability and high detection limit requirement; when the liquid chromatography is adopted for detection, the post-derivatization treatment of the fluorescent column is needed, the steps are complicated, and the derivatization method sometimes causes the loss of target products due to operation errors and influences the test result; the liquid chromatography mass spectrometry is adopted for detection, and the multi-component high-flux simultaneous online measurement can be carried out in batches without derivatization, so that the method is convenient and quick, and has high sensitivity and strong selectivity. The liquid chromatography mass spectrometry analysis adopts a multi-reaction monitoring scanning mode to provide characteristic parent ion and child ion information and provide reliable basis for qualitative and quantitative analysis of target compounds. The carbamate and its thio standard solutions by autosampling were scanned in esi+ ionization mode to select the appropriate ionization mode and excimer ion peaks. After determining the parent ions of the target component, adjusting instrument parameters to maximize the abundance of the parent ions; continuing to perform secondary mass spectrometry, selecting two pairs of ions with stronger abundance and smaller interference as qualitative and quantitative ions, optimizing mass spectrometry parameters such as capillary voltage, collision energy, fragmentation voltage and the like, and ensuring that the molecular ions and characteristic fragment ions of different components reach the maximum intensity.
For three types of actual samples such as traditional Chinese medicine materials, tea and mushroom, the vast majority of sample matrixes are very complex, pretreatment is more complex, and trace measurement of toxic and harmful substances has a certain problem. How to effectively reduce or eliminate the matrix effect, realize high-flux multi-component rapid and accurate simultaneous online measurement of batch samples, and develop new pretreatment methods and instrument conditions to meet the multi-component analysis requirements of high sensitivity and small matrix interference of sample testing.
Disclosure of Invention
Based on the defects and shortcomings existing in the prior art, the method provided by the invention takes various carbamates and thio-compound pesticide residues as research objects, establishes a brand-new method for rapidly pre-treating and accurately and efficiently detecting multi-component carbamates and thio-compound pesticide residues in various foods, is simple, rapid, efficient, sensitive and good in selectivity, can realize the high-flux multi-component simultaneous on-line accurate quantitative determination of various target objects of different samples without sample derivatization treatment, is suitable for the rapid determination requirement of low-residual-level target objects in a large number of samples, has good practicability and basic popularization, can solve the problems of incomplete coverage of detection components or incomplete matrix effect removal of detection sample types of the existing method, provides new technical data for improvement of food risk monitoring methods and establishment of relevant standards, and has important significance for guaranteeing food safety and import and export trade.
Chemical name abbreviations interpretation:
PSA is ethylenediamine-N-propyl silanized silica gel: 40-60 μm.
C 18 is octadecylsilane chemically bonded silica: 40-60 μm.
MWCNTs are multiwall carbon nanotubes: 15-25nm
SiO 2 is silicon dioxide.
PANI is polyaniline.
At present, the research of the novel solid-phase extraction adsorbent of MWCNTs@SiO 2 @PANI for carbamate pesticides in traditional Chinese medicinal materials, tea and mushrooms has not been reported yet. The MWCNTs@SiO 2 @PANI novel solid phase extraction adsorbent is used for purifying samples such as traditional Chinese medicinal materials, tea, mushrooms and the like, complex matrix interference in the traditional Chinese medicinal materials, tea, mushrooms and the like can be effectively reduced, the material can be repeatedly utilized for a plurality of times after being repeatedly washed by alcohol-water, and high performance liquid chromatography mass spectrometry (HPLC-MS/MS) is adopted for measurement, so that a high-efficiency, accurate and simple rapid detection method for pesticide residues of various carbamates and thio-type pesticides in the traditional Chinese medicinal materials, tea and mushrooms is established, and the detection limit, the recovery rate and the precision of the method are all satisfactory.
In one aspect, the invention provides a preparation method of a novel solid-phase extraction adsorbent multiwall carbon nanotube @ silicon dioxide @ polyaniline, which comprises the following steps: and firstly wrapping a layer of SiO 2 on the surface of the MWCNTs to generate MWCNTs@SiO 2, and then continuously compositing the PANI particles to generate the MWCNTs@SiO 2 @PANI.
Further, the preparation method of the multi-wall carbon nano tube @ silicon dioxide @ polyaniline comprises the following steps:
(1) Preparation of MWCNTs@SiO 2
Adding a mixed solution of cyclohexane, n-hexanol and Triton X-100 into the multiwall carbon nanotube, stirring and dispersing, sequentially adding HPTS, TEOS and concentrated ammonia water, stirring uniformly to carry out hydrolysis polymerization reaction, demulsifying acetone after the reaction is finished, centrifuging, discarding supernatant, cleaning and removing surfactant until the mixture is neutral, and vacuum drying to obtain the multiwall carbon nanotube@silicon dioxide composite material;
(2) Preparation of MWCNTs@SiO 2 @PANI
Adding the multi-wall carbon nano tube @ silicon dioxide composite material prepared in the step (1) after introducing nitrogen into ethanol for deoxidization, adding ultrapure water of hydrochloric acid after uniform dispersion, adding dodecyl alcohol polyoxyethylene ether sulfuric acid, stirring at a high speed, adding aniline, dropwise adding ammonium persulfate aqueous solution dropwise, stirring at a high speed for reaction in an ice bath state, demulsifying the product after the reaction is finished, filtering the product by using acetone, centrifuging, repeatedly washing the emulsion by using ethanol-water until the emulsion is neutral, and freeze-drying by a freeze dryer to obtain the MWCNTs@SiO 2 @PANI polymer.
The volume ratio of HPTS, TEOS and concentrated ammonia water in the step (1) is 4.5-5:1-1.2:1-1.5.
The pipe diameter of the multi-wall carbon nano-pipe @ silicon dioxide composite material in the step (1) is 50nm.
The speed of dropwise adding the ammonium persulfate aqueous solution in the step (2) is 20-30 drops/min.
Specifically, the preparation method of the multi-wall carbon nano tube @ silicon dioxide @ polyaniline comprises the following steps:
(1) The preparation method of the MWCNTs@SiO 2 comprises the following steps:
Adding 2.0-3.0g of multi-wall carbon nano tube into a 250mL beaker, adding 70-100mL of mixed solution of cyclohexane, normal hexanol and Triton X-100, performing ultrasonic dispersion for 10-20min, sequentially adding 4.5-5.0mL of HPTS, 1.0-1.2mL of TEOS and 1.0-1.5mL of concentrated ammonia water under magnetic stirring, uniformly stirring, and performing hydrolysis polymerization at room temperature for 12-16h; after the reaction is finished, acetone demulsifies, centrifugal separation is carried out at the rotating speed of 5000-8000 r/min, supernatant is removed, ethanol and pure water are used for circulating and cleaning for 3-5 times to remove surfactant until the surfactant is neutral, and vacuum drying is carried out at the temperature of 40-60 ℃ to obtain the multi-wall carbon nano tube@silicon dioxide composite material;
(2) The preparation method of the MWCNTs@SiO 2 @PANI comprises the following steps:
Adding 5.0-15.0mL of ethanol into a round-bottom three-neck flask, introducing nitrogen to remove oxygen for 10-15min, adding 1.0-2.0g of the multi-wall carbon nano tube @ silicon dioxide composite material prepared in the step 1, performing short-term ultrasonic homogenization for 30 seconds, firstly adding 50-80mL of ultrapure water containing 0.05-0.15mol of hydrochloric acid, then adding 1.0-1.5g of dodecyl alcohol polyoxyethylene ether sulfuric acid, rapidly stirring at a constant temperature for 10-20min, then adding 2.2-8.8mL of aniline, dropwise adding 0.04-0.15mol of ammonium persulfate aqueous solution, controlling the reaction temperature in an ice bath state (0-4 ℃), and performing high-speed stirring reaction for 10-20h; and demulsifying the product by using acetone, filtering the emulsion by using a G3/G4 funnel, centrifuging, repeatedly washing the emulsion to be neutral by using ethanol-water, and freeze-drying the emulsion by using a freeze dryer to obtain the MWCNTs@SiO 2 @PANI polymer.
The volume ratio of the mixed solution of cyclohexane, n-hexanol and Triton X-100 in the step (1) is 2-5:1-1.5:1.
The volume ratio of HPTS, TEOS and concentrated ammonia water in the step (1) is 4.5-5:1-1.2:1-1.5.
The pipe diameter of the multi-wall carbon nano-pipe @ silicon dioxide composite material in the step (1) is 50nm.
The speed of dropwise adding the ammonium persulfate aqueous solution in the step (2) is 20-30 drops/min.
The process has the advantages of easily available raw materials, simple preparation process and suitability for popularization and application.
The high-throughput detection method of the carbamates and the thio-compounds thereof comprises the following steps:
S1, preparing carbamate and thio standard solution thereof
S2, preparation of sample solution to be tested
S2-1, sample preparation: weighing solid sample, slicing, grinding, pulverizing, sieving with 0.5mm sample sieve, mixing, homogenizing by four-way method, and sealing at-20deg.C to-18deg.C;
S2-2, extracting: weighing 2.0g of sample in a sample tube, adding 15-25mL of water-acetonitrile mixed solution, vibrating and extracting for 20-30min, then adding 1.0-2.0g of sodium chloride and 3.0-5.0g of anhydrous magnesium sulfate at a time, vibrating for 1-2min, centrifuging for 5-10min at 4000-6000r/min, and taking supernatant for later use.
S2-3, purifying: removing 1.0-2.0mL of supernatant, adding 0.20-0.40g of anhydrous magnesium sulfate water scavenger, and centrifuging to extract supernatant; then adding 0.04-0.08g MWCNTs@SiO 2 @PANI adsorbent, vigorously swirling for 1-2min, fully dispersing and purifying, centrifuging for 5-10min at 4000-6000r/min, and sucking the supernatant to pass through a 0.22 mu m microporous filter membrane to obtain a sample solution to be detected;
S3, drawing a standard curve
Injecting the standard solution series into a liquid chromatograph-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of carbamate and thio-compounds thereof as an ordinate and the concentration of the corresponding carbamate and thio-compounds thereof as an abscissa;
S4, analysis and detection
And (3) measuring the sample solution to be measured configured in the step (S2) and the standard solution configured in the step (S1) on a machine, and calculating the concentration of carbamate and thio-compounds in the sample solution to be measured according to a standard curve by an external standard method.
The preparation of the standard solution of carbamate and its thio compounds described in the above step S1 comprises the following steps:
S1-1, standard intermediate solution for preparing carbamate and thioxo thereof: respectively transferring 20 mu L of single standard solution of carbamate and thio-compound thereof, and using acetonitrile to fix the volume to 1mL to prepare 20 mu g/mL standard intermediate solution;
S1-2, preparing standard working solution of carbamate and thioxo thereof: and (3) gradually diluting the standard intermediate liquid of the carbamate and the thio-compound thereof obtained in the step S1-1 by a plurality of times to obtain standard working liquids with the serial concentrations of 0.1,0.5,1.0,5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively.
A single standard solution of the carbamate and its thio as described in step S1-1 above was purchased from Shanghai Annotation reagent Co., ltd (1000. Mu.g/mL).
The standard working solution needs to be prepared at present.
The volume ratio of water to acetonitrile in the water-acetonitrile mixed solution in the step S2-2 is 1-2:2-3; the acetonitrile contains 1% acetic acid.
The mass ratio of the anhydrous magnesium sulfate of sodium chloride in the step S2-2 is 1-2:3-5.
The mass ratio of the anhydrous magnesium sulfate water scavenger to the MWCNTs@SiO 2 @PANI adsorbent in the step S2-3 is 5-10:1-2.
The detection method of the invention also comprises the detection of a blank sample, i.e. a test sample is not added, and the rest steps are the same as the analysis steps when the test sample is contained.
Preferably, the chromatographic conditions in the step S3 are as follows:
Liquid chromatography conditions:
Instrument: agilent 1260 high performance liquid chromatograph tandem 6460 triple quadrupole mass spectrometer;
Chromatographic column: agilent ZORBAX SB-C 18 (2.1 x 100mm x 3.5 μm);
flow rate: 0.4mL/min;
column temperature: 40 ℃;
Sample injection amount: 5. Mu.L;
Mobile phase: a is 0.1% formic acid water solution, B is acetonitrile;
Gradient elution procedure: 0-1min,5% B;1-5min,5% -60% B;5-20min,60% -100% B;20-25min,100% B;25-26min,100% -5% B;26-35min,5% B;
Mass spectrometry conditions:
scanning mode: positive ion scan (esi+);
spray voltage: 4000V;
Atomization gas pressure GS1:45psi;
Ion source: ESI;
Mass spectrometry scanning mode: MRM;
heating air temperature: 350 ℃;
Ion source temperature: 100 ℃;
Desolventizing gas: 10L/min;
Residence time: 25ms.
The invention has the beneficial effects that:
(1) According to the method, a brand-new method for rapidly preprocessing samples and accurately and efficiently detecting multi-component carbamate and thio pesticide residues in various foods is established by taking various carbamate and thio pesticide residues as research objects, the established method is simple, rapid, efficient, sensitive and good in selectivity, high-flux multi-component simultaneous and online accurate quantitative determination of various targets of different samples can be realized without sample derivatization treatment, the method is suitable for rapid determination requirements of low-residual-level targets in a large number of samples, has good practicability and basic popularization, can solve the problems that the detection components of the existing method are not fully covered or the detection sample types are not completely short or matrix effects are not completely removed, provides new technical data for improvement of food risk monitoring methods and establishment of related standards, and has important significance for guaranteeing food safety and trade import and export;
(2) The MWCNTs@SiO 2 @PANI novel solid phase extraction adsorbent is used for purifying samples of Chinese medicinal materials, tea, mushrooms and the like, so that the interference of complex matrixes in the Chinese medicinal materials, the tea, the mushrooms and the like can be effectively reduced, the material can be reused, namely, after the material is used, the material is circularly washed for 3-5 times by ethanol and pure water, the material is washed to be neutral, the material can be reused for 3-5 times after being dried in vacuum at 40-60 ℃, and the adsorption efficiency of the adsorbent can be still maintained at 60-85%;
(3) The invention adopts high performance liquid chromatography mass spectrometry (HPLC-MS/MS) to carry out determination, establishes a high-efficiency, accurate and simple rapid detection method for various carbamate and thio-compound pesticide residues in traditional Chinese medicinal materials, tea and mushrooms, and can realize rapid separation and detection of 28 common carbamate and thio-compound in samples within 13 minutes, and the detection limit, recovery rate and precision of the method are all satisfactory.
Drawings
FIG. 1 is a high resolution scanning electron microscope image of a multiwall carbon nanotube prepared according to a basic embodiment of the present invention;
FIG. 2 is a high resolution scanning electron microscope image of a multiwall carbon nanotube @ silica prepared in accordance with a basic embodiment of the present invention;
FIG. 3 is a high resolution scanning electron microscope image of a multiwall carbon nanotube @ silica @ polyaniline prepared in accordance with a basic embodiment of the present invention;
FIG. 4 is an ion flow chromatogram of a 200 μg/L mixed standard solution of 28 carbamates and their thio-compounds;
FIG. 5 is a quantitative ion flow chromatogram of a 200 μg/L single component standard solution of 28 carbamates and their thio-groups;
Wherein,
FIG. 5-1 is a quantitative ion flow chromatogram of 200. Mu.g/L methomyl oxime standard solution;
FIG. 5-2 is a quantitative ion flow chromatogram of 200. Mu.g/L methomyl standard solution;
FIG. 5-3 is a quantitative ion flow chromatogram of a 200 μg/L standard solution of pirimicarb;
FIGS. 5-4 are quantitative ion flow chromatograms of 200 μg/L3-hydroxy carbofuran standard solution;
FIGS. 5-5 are quantitative ion flow chromatograms of 200 μg/L of a methomyl standard solution;
FIGS. 5-6 are quantitative ion flow chromatograms of 200 μg/L propoxur standard solution;
FIGS. 5-7 are quantitative ion flow chromatograms of 200 μg/L carbofuran standard solution;
FIGS. 5-8 are quantitative ion flow chromatograms of 200 μg/L oxacarb standard solution;
FIGS. 5-9 are quantitative ion flow chromatograms of 200 μg/L carbaryl standard solution;
FIGS. 5-10 are quantitative ion flow chromatograms of 200 μg/L isoprocarb standard solution;
FIGS. 5-11 are quantitative ion flow chromatograms of 200 μg/L2, 3, 5-mixed carbofuran standard solution;
FIGS. 5-12 are quantitative ion flow chromatograms of 200 μg/L of clomazone standard solution;
FIGS. 5-13 are quantitative ion flow chromatograms of 200 μg/L of a standard solution of fenobucarb;
FIGS. 5-14 are quantitative ion flow chromatograms of 200 μg/L of a warfare standard solution;
FIGS. 5-15 are quantitative ion flow chromatograms of 200 μg/L thiodicarb standard solution;
FIGS. 5-16 are quantitative ion flow chromatograms of 200 μg/L indoxacarb standard solution;
FIGS. 5-17 are quantitative ion flow chromatograms of 200 μg/L benfuracarb standard solution;
FIGS. 5-18 are quantitative ion flow chromatograms of 200 μg/L methiocarb standard solution;
FIGS. 5-19 are quantitative ion flow chromatograms of 200 μg/L of a phenyl ether power standard solution;
FIGS. 5-20 are quantitative ion flow chromatograms of 200 μg/L butachlor standard solution;
FIGS. 5-21 are quantitative ion flow chromatograms of 200 μg/L Avena sativa enemy standard solution;
FIGS. 5-22 are quantitative ion flow chromatograms of 200 μg/L prosulfocarb standard solution;
FIGS. 5-23 are quantitative ion flow chromatograms of 200 μg/L of a gram standard solution;
FIGS. 5-24 are quantitative ion flow chromatograms of 200 μg/L of a standard solution of wild wheat intolerance;
FIGS. 5-25 are quantitative ion flow chromatograms of 200 μg/L molinate standard solution;
FIGS. 5-26 are quantitative ion flow chromatograms of 200 μg/L of a benazelate standard solution;
FIGS. 5-27 are quantitative ion flow chromatograms of 200 μg/L standing solution of molinate;
FIGS. 5-28 are quantitative ion flow chromatograms of 200 μg/L of a standard solution of graminium;
FIG. 6 is a quantitative ion flow chromatogram of 200 μg/LD 7 carbaryl standard solution;
FIG. 7 is a total ion flow chart of carbofuran detected by a traditional Chinese medicine honeysuckle sample under different pretreatment conditions;
wherein FIG. 7a is comparative examples 1,7b is comparative examples 2,7c is comparative examples 3,7d is comparative examples 4,7e is example 1.
FIG. 8 is a total ion flow chart of 3-hydroxy carbofuran detected by a Chinese medicinal material honeysuckle sample under different pretreatment conditions;
Wherein FIG. 8a is comparative examples 1,8b is comparative example 2,8c is comparative example 3,8d is comparative example 4,8e is example 1.
FIG. 9 is a total ion flow diagram of traditional Chinese medicine honeysuckle samples under different pretreatment conditions;
Wherein FIG. 9a is comparative example 1,9b is comparative example 2,9c is comparative example 3,9d is comparative example 4,9e is example 1.
Figure 10 is a total ion flow diagram of a tea sample under different pretreatment conditions;
Wherein, fig. 10a is comparative example 1, 10b is comparative example 2, 10c is comparative example 3, 10d is comparative example 4, 10e is example 1.
FIG. 11 is a total ion flow diagram of a sample of mushrooms under different pretreatment conditions;
wherein, fig. 11a is comparative example 1, 11b is comparative example 2, 11c is comparative example 3, 11d is comparative example 4, 11e is example 1.
Detailed Description
The above-mentioned features of the invention, or of the embodiments, may be combined in any desired manner. All of the features explained in this specification can be used in combination with any form of method, and each feature disclosed in this specification can be replaced by any alternative feature serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the disclosed features are merely general examples of equivalent or similar features.
The invention will be further illustrated with reference to specific examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The following examples are presented to illustrate specific conditions, generally according to conventional conditions or according to manufacturer's recommended conditions. All percentages and fractions are by weight unless specifically indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are exemplary only.
Reagents and drugs used in the following examples:
the reagents and drug types and the manufacturer required for the synthetic materials are shown in Table 3 below:
TABLE 3 Table 3
| Reagent/drug | Manufacturer/model |
| Tetraethoxysilane (TEOS) | U.S., sigma |
| 8-Hydroxy-1, 3, 6-trisulfonic acid pyrene (HPTS) | Aldrich in the United states |
| Triton X-100 | Analytical grade |
| Ammonia water | Analytical grade |
| Cyclohexane | Analytical grade |
| N-hexanol | Analytical grade |
| Acetone (acetone) | Analytical grade |
| Ethanol | Analytical grade |
| MWCNTs | Commercially available, 10 to 20nm |
| Aniline | Analytical grade (distillation under reduced pressure before use) |
| Ammonium persulfate | Chemical purity |
| Ethoxylated alkyl sulfuric acid | Industrial grade |
| Dodecyl alcohol polyoxyethylene ether sulfuric acid | Industrial grade |
| Hydrochloric acid | Chemical purity |
| Ammonium persulfate | Chemical purity |
A single standard solution of the carbamates and their thio used in the examples below was purchased from Shanghai Annotation reagent Co., ltd (1000. Mu.g/mL) and stored at-20 ℃.
Preparation method of multi-wall carbon nano tube @ silicon dioxide @ polyaniline in basic embodiment
The method comprises the following steps:
(1) The preparation method of the MWCNTs@SiO 2 comprises the following steps:
Adding 2.0-3.0g of multi-wall carbon nano tube into a 250mL beaker, adding 70-100mL of mixed solution of cyclohexane, normal hexanol and Triton X-100, performing ultrasonic dispersion for 10-20min, sequentially adding 4.5-5.0mL of HPTS, 1.0-1.2mL of TEOS and 1.0-1.5mL of concentrated ammonia water under magnetic stirring, uniformly stirring, and performing hydrolysis polymerization at room temperature for 12-16h; after the reaction is finished, acetone demulsifies, centrifugal separation is carried out at the rotating speed of 5000-8000 r/min, supernatant is removed, ethanol and pure water are used for circulating and cleaning for 3-5 times to remove surfactant until the surfactant is neutral, and vacuum drying is carried out at the temperature of 40-60 ℃ to obtain the multi-wall carbon nano tube@silicon dioxide composite material;
(2) The preparation method of the MWCNTs@SiO 2 @PANI comprises the following steps:
Adding 5.0-15.0mL of ethanol into a round-bottom three-neck flask, introducing nitrogen to remove oxygen for 10-15min, adding 1.0-2.0g of the multi-wall carbon nano tube @ silicon dioxide composite material prepared in the step 1, performing short-term ultrasonic homogenization for 30 seconds, firstly adding 50-80mL of ultrapure water containing 0.05-0.15mol of hydrochloric acid, then adding 1.0-1.5g of dodecyl alcohol polyoxyethylene ether sulfuric acid, rapidly stirring at a constant temperature for 10-20min, then adding 2.2-8.8mL of aniline, dropwise adding 0.04-0.15mol of ammonium persulfate aqueous solution, controlling the reaction temperature in an ice bath state (0-4 ℃), and performing high-speed stirring reaction for 10-20h; and demulsifying the product by using acetone, filtering the emulsion by using a G3/G4 funnel, centrifuging, repeatedly washing the emulsion to be neutral by using ethanol-water, and freeze-drying the emulsion by using a freeze dryer to obtain the MWCNTs@SiO 2 @PANI polymer.
The volume ratio of the mixed solution of cyclohexane, n-hexanol and Triton X-100 in the step (1) is 2-5:1-1.5:1.
The volume ratio of HPTS, TEOS and concentrated ammonia water in the step (1) is 4.5-5:1-1.2:1-1.5.
The pipe diameter of the multi-wall carbon nano-pipe @ silicon dioxide composite material in the step (1) is 50nm.
The speed of dropwise adding the ammonium persulfate aqueous solution in the step (2) is 20-30 drops/min.
Example 1 high throughput detection method of carbamates and their thio-products in complex matrix dry samples comprising the steps of:
S1, preparing carbamate and thio standard solution thereof
S1-1, standard intermediate solution for preparing carbamate and thioxo thereof: respectively transferring 20 mu L of single standard solution of carbamate and thio-compound thereof, and using acetonitrile to fix the volume to 1mL to prepare 20 mu g/mL standard intermediate solution;
s1-2, preparing standard working solution of carbamate and thioxo thereof: gradually diluting the standard intermediate liquid of the carbamate and the thio-compounds thereof obtained in the step S1-1 by a plurality of times to obtain standard working liquids with the serial concentrations of 0.1,0.5,1.0,5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively;
S2, preparation of sample solution to be tested
S2-1, sample preparation: weighing solid sample, slicing, grinding, pulverizing, sieving with 0.5mm sample sieve, mixing, homogenizing by four-way method, and sealing at-20deg.C;
S2-2, extracting: weighing 2.0g of sample in a sample tube, adding 10mL of water-acetonitrile mixed solution, vibrating and extracting for 20min, then adding 1.0g of sodium chloride and 3.0g of anhydrous magnesium sulfate at one time, vibrating for 1min, centrifuging for 5min at 4000r/min, and taking supernatant for later use.
S2-3, purifying: removing 1.0mL of supernatant, firstly adding 0.20g of anhydrous magnesium sulfate water scavenger, and centrifuging to extract the supernatant; then adding 0.04g of MWCNTs@SiO 2 @PANI adsorbent, vigorously swirling for 1min, fully dispersing and purifying, centrifuging at 4000r/min for 5min, and sucking the supernatant to pass through a 0.22 mu m microporous filter membrane to obtain a sample solution to be detected;
S3, drawing a standard curve
Injecting the standard solution series into a liquid chromatograph-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of carbamate and thio-compounds thereof as an ordinate and the concentration of the corresponding carbamate and thio-compounds thereof as an abscissa;
S4, analysis and detection
And (3) measuring the sample solution to be measured configured in the step (S2) and the standard solution configured in the step (S1) on a machine, and calculating the concentration of carbamate and thio-compounds in the sample solution to be measured according to a standard curve by an external standard method.
Example 2 high throughput detection method of carbamates and their thio-products in complex matrix dry samples comprising the steps of:
S1, preparing carbamate and thio standard solution thereof
S1-1, standard intermediate solution for preparing carbamate and thioxo thereof: respectively transferring 20 mu L of single standard solution of carbamate and thio-compound thereof, and using acetonitrile to fix the volume to 1mL to prepare 20 mu g/mL standard intermediate solution;
s1-2, preparing standard working solution of carbamate and thioxo thereof: gradually diluting the standard intermediate liquid of the carbamate and the thio-compounds thereof obtained in the step S1-1 by a plurality of times to obtain standard working liquids with the serial concentrations of 0.1,0.5,1.0,5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively;
S2, preparation of sample solution to be tested
S2-1, sample preparation: weighing solid sample, slicing, grinding, pulverizing, sieving with 0.5mm sample sieve, mixing, homogenizing by four-way method, and sealing at-18deg.C;
S2-2, extracting: weighing 5.0g of sample in a sample tube, adding 40mL of water-acetonitrile mixed solution, vibrating and extracting for 30min, then adding 2.0g of sodium chloride and 5.0g of anhydrous magnesium sulfate at one time, vibrating for 2min, centrifuging for 10min at 600 r/min, and taking supernatant for later use.
S2-3, purifying: transferring 2.0mL of supernatant, firstly adding 0.40g of anhydrous magnesium sulfate water scavenger, and centrifugally extracting the supernatant; then adding 0.08g of MWCNTs@SiO 2 @PANI extraction adsorbent, vigorously swirling for 2min, fully dispersing and purifying, centrifuging for 10min at 6000r/min, and sucking the supernatant to pass through a 0.22 mu m microporous filter membrane to obtain a sample solution to be detected;
S3, drawing a standard curve
Injecting the standard solution series into a liquid chromatograph-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of carbamate and thio-compounds thereof as an ordinate and the concentration of the corresponding carbamate and thio-compounds thereof as an abscissa;
S4, analysis and detection
And (3) measuring the sample solution to be measured configured in the step (S2) and the standard solution configured in the step (S1) on a machine, and calculating the concentration of carbamate and thio-compounds in the sample solution to be measured according to a standard curve by an external standard method.
The detection conditions for examples 1-2 were:
Instrument: agilent 1260 high performance liquid chromatograph tandem 6460 triple quadrupole mass spectrometer;
Liquid chromatography conditions:
Chromatographic column: agilent ZORBAX SB-C 18 (2.1 x 100mm x 3.5 μm);
flow rate: 0.4mL/min;
column temperature: 40 ℃;
Sample injection amount: 5. Mu.L;
Mobile phase: a is 0.1% formic acid water solution, B is acetonitrile;
Gradient elution procedure: 0-1min,5% B;1-5min,5% -60% B;5-20min,60% -100% B;20-25min,100% B;25-26min,100% -5% B;26-35min,5% B;
Mass spectrometry conditions:
scanning mode: positive ion scan (esi+);
spray voltage: 4000V;
Atomization gas pressure GS1:45psi;
Ion source: ESI;
Mass spectrometry scanning mode: MRM;
heating air temperature: 350 ℃;
Ion source temperature: 100 ℃;
desolventizing gas: 10L/min.
Residence time: 25ms.
Table 1 shows retention times, quantitative ion and collision energies for 28 carbamates and their thio-products
Note that: carbamates No. 1-19, thiocarbamates No. 20-28, deuterated internal standard No. 29 comparative example 1:
the direct injection method was carried out without adding MWCNTs@SiO 2 @PANI adsorbent, otherwise the same as in example 1. Comparative example 2:
The pretreatment of PSA dispersion solid phase extraction method was carried out by replacing the MWCNTs@SiO 2 @PANI adsorbent with 0.04gPSA, otherwise the same as in example 1.
Comparative example 3:
Pretreatment by a C 18 dispersion solid phase extraction method is carried out, and the MWCNTs@SiO 2 @PANI adsorbent is replaced by 0.04gC 18, and the same as in example 1 is carried out.
Comparative example 4:
PSA+C 18 dispersed solid phase extraction pretreatment the MWCNTs@SiO 2 @PANI adsorbent was replaced with 0.04g of PSA+C 18, otherwise as in example 1.
Effect verification
1. Determination of the content of carbamates and their thio-compounds in the samples:
Sample solutions to be tested were prepared by the methods of examples 1-2 and comparative examples 1-4, respectively: namely sample solutions of Chinese medicinal materials honeysuckle, tea and mushroom are respectively marked as a sample 1 (marked as a sample 1-1, a sample 1-2, a sample 1-3, a sample 1-4, a sample 1-5 and a sample 1-6 according to different groups); sample 2 (labeled as sample 2-1, sample 2-2, sample 2-3, sample 2-4, sample 2-5, and sample 2-6 according to the different groupings) and sample 3 (labeled as sample 3-1, sample 3-2, sample 3-3, sample 3-4, sample 3-5, and sample 3-6 according to the different groupings) and the content of carbamates and their thio-compounds in sample 1, sample 2, and sample 3 were determined.
The calculation formula is as follows:
Wherein,
X is the content of carbamate and thioxo thereof in the sample, the unit is microgram per kilogram (mug/kg), C is the concentration of a certain component in the liquid to be tested obtained by substituting the standard curve, the unit is nanograms per milliliter (ng/mL), V is the final constant volume of the liquid to be tested in the sample, the unit is milliliter (mL), 1000 is the conversion multiple, m is the sample weighing mass of the sample, the unit is grams (g), and f is the dilution multiple.
The specific detection results are shown in the following table 2:
TABLE 2
Table 2 above shows the results of measuring the contents of the urethane and its thio compounds in sample 1, which shows that the target components carbofuran and 3-hydroxy carbofuran are detected in sample 1 based on the detection data in Table 2; and calculating the concentration thereof; whereas no relevant target components were detected in sample 2 and sample 3.
It can also be seen from fig. 7-11:
Fig. 7 and fig. 8 are ion flow chromatographic test charts of the traditional Chinese medicine honeysuckle in positive samples, and according to fig. 7a-e and fig. 8a-e, combined with qualitative and quantitative ion pair identification of target components, the result shows that 2 target components of carbofuran and 3-hydroxy carbofuran are detected in the honeysuckle samples, and the detected concentration of the 2 target components is calculated according to the peak area of the spectrum and the corresponding mass concentration.
Figures 9-11 are total ion flow diagrams of honeysuckle, tea and mushroom under different pretreatment conditions, respectively. As can be seen from FIGS. 10-11, tea leaves and mushrooms are not detected with any target components, and are attached to sample charts for reference.
2. Detection of linear range, detection limit and quantification limit
The 28 carbamates and their thio-products were analyzed and tested, and the specific test results are shown in Table 3 below.
TABLE 3 Table 3
From the test results of table 2 above, it can be derived that: the curve range of detection is 1.0-500 mug/L, the detection Limit (LOD) range of 28 components is 0.15-20 mug/kg, the quantitative Limit (LOQ) range is 0.50-67 mug/kg, and the correlation coefficient (R 2) is 0.9986-0.9999.
3. Method recovery and precision
The mixed standard solution of the carbamate and the thio-compounds is added into the representative sample, the addition amounts of the carbamate and the thio-compounds are respectively 10, 50 and 200 mug/kg, each sample is measured in parallel and is measured for 6 times continuously, the average recovery rate of 28 carbamate and the thio-compounds is calculated to be 89.8 percent to 99.1 percent, and the relative standard deviation RSD (%) is 1.7 percent to 4.5 percent.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will be able to implement the invention as described in the specification and above; however, those skilled in the art should not depart from the scope of the invention, and make various changes, modifications and adaptations of the invention using the principles disclosed above; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (11)
1. A high-throughput detection method for carbamates and thio-compounds thereof is characterized in that: the method comprises the following steps:
S1, preparing carbamate and a thio-compound standard solution thereof;
s2, preparing a sample solution to be detected, wherein the sample is prepared from traditional Chinese medicinal materials, tea and mushroom;
S2-1, sample preparation: weighing solid sample, slicing, grinding, pulverizing, sieving with 0.5 mm sample sieve, mixing, homogenizing by four-way method, and sealing at-20deg.C to-18deg.C;
S2-2, extracting: weighing a 2.0 g sample in a sample tube, adding 15-25: 25 mL water-acetonitrile mixed solution, vibrating and extracting 20-30: 30min, then adding 1.0-2.0: 2.0 g sodium chloride and 3.0-5.0: 5.0 g anhydrous magnesium sulfate at a time, vibrating for 1-2 min, centrifuging for 5-10: 10 min at 4000-6000: 6000 r/min, and taking supernatant for later use;
S2-3, purifying: removing 1.0-2.0 mL supernatant, adding 0.20-0.40g anhydrous magnesium sulfate water scavenger, centrifuging and extracting supernatant; then adding 0.04-0.08 g MWCNTs@SiO 2 @PANI adsorbent, vigorously swirling 1-2 min, fully dispersing and purifying, centrifuging at 4000-6000 r/min for 5-10 min, and sucking the supernatant to pass through a 0.22 μm microporous filter membrane to obtain a sample solution to be detected;
the preparation method of the MWCNTs@SiO 2 @PANI adsorbent comprises the following steps:
(1) Preparation of MWCNTs@SiO 2
Adding a mixed solution of cyclohexane, n-hexanol and Triton X-100 into the multiwall carbon nanotube, stirring and dispersing, sequentially adding HPTS, TEOS and concentrated ammonia water, stirring uniformly to carry out hydrolysis polymerization reaction, demulsifying acetone after the reaction is finished, centrifuging, discarding supernatant, cleaning and removing surfactant until the mixture is neutral, and vacuum drying to obtain the multiwall carbon nanotube@silicon dioxide composite material;
(2) Preparation of MWCNTs@SiO 2 @PANI
Adding the multi-wall carbon nano tube @ silicon dioxide composite material prepared in the step (1) after introducing nitrogen into ethanol for deoxidization, adding ultrapure water of hydrochloric acid after uniform dispersion, adding dodecyl alcohol polyoxyethylene ether sulfuric acid, stirring at a high speed, adding aniline, dropwise adding ammonium persulfate aqueous solution dropwise, stirring at a high speed for reaction in an ice bath state, demulsifying the product after the reaction is finished, filtering the product by using acetone, centrifuging, repeatedly washing the emulsion to be neutral by using ethanol-water, and freeze-drying by using a freeze dryer to obtain MWCNTs@SiO 2 @PANI polymer;
S3, drawing a standard curve
Injecting a series of standard solutions into a liquid chromatograph-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of carbamate and thio-compounds thereof as an ordinate and the concentration of the corresponding carbamate and thio-compounds thereof as an abscissa;
S4, analysis and detection
The sample solution to be detected which is configured in the step S2 and the standard solution which is configured in the step S1 are measured on a machine, and the concentration of carbamate and thio-compounds in the sample solution to be detected is calculated according to a standard curve by an external standard method;
The carbamate and the thio-compound thereof are selected from methomyl oxime, methomyl, pirimicarb, 3-hydroxy carbofuran, propoxur, carbofuran, oxadiazon, carbaryl, isoprocarb, 2,3, 5-mixed carbofuran, chlorfenacarb, fenobucarb, brazzein, thiodicarb, indoxacarb, benfuracarb, methiocarb, fenoxycarb, bufenoxycarb, avenanthramide, prosulfocarb, carboxin, dicamba, methoprene, molinate and gramineous.
2. The high throughput assay of claim 1, wherein: the volume ratio of water to acetonitrile in the water-acetonitrile mixed solution in the step S2-2 is 1-2:2-3.
3. The high throughput assay of claim 1, wherein: the acetonitrile described in step S2-2 contains 1% acetic acid.
4. The high throughput assay of claim 1, wherein: the mass ratio of the sodium chloride to the anhydrous magnesium sulfate in the step S2-2 is 1-2:3-5.
5. The high throughput assay of claim 1, wherein: the mass ratio of the anhydrous magnesium sulfate water scavenger to the MWCNTs@SiO 2 @PANI adsorbent in the step S2-3 is 5-10:1-2.
6. The high throughput assay of claim 1, wherein: the preparation of the standard solution of carbamate and thio thereof in step S1 comprises the following steps:
s1-1, standard intermediate solution for preparing carbamate and thioxo thereof: respectively transferring 20 mu L of single standard solution of carbamate and thio-compound thereof, and using acetonitrile to fix the volume to 1 mL to prepare 20 mu g/mL standard intermediate solution;
S1-2, preparing standard working solution of carbamate and thioxo thereof: and (3) gradually diluting the standard intermediate liquid of the carbamate and the thio-compound thereof obtained in the step S1-1 by a plurality of times to obtain standard working liquids with the serial concentrations of 0.1,0.5,1.0,5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0 ng/mL respectively.
7. The high throughput assay of claim 1, wherein: the chromatographic conditions in step S3 are:
Liquid chromatography conditions:
Instrument: agilent 1260 high performance liquid chromatograph tandem 6460 triple quadrupole mass spectrometer;
Chromatographic column: agilent ZORBAX SB-C 18, 2.1 x 100mm x 3.5 μm;
flow rate: 0.4mL/min;
column temperature: 40 ℃;
sample injection amount: 5 mu L;
mobile phase: a is 0.1% formic acid water solution, B is acetonitrile;
Gradient elution procedure ：0-1min, 5% B; 1-5min, 5%-60%B; 5-20min, 60%-100% B; 20-25min, 100% B; 25-26min, 100%-5% B; 26-35min, 5% B;
Mass spectrometry conditions:
scanning mode: positive ion scan, esi+;
spray voltage: 4000V;
Atomization gas pressure GS1:45psi;
Ion source: ESI;
mass spectrometry scanning mode: MRM;
heating air temperature: 350 ℃;
ion source temperature: 100. the temperature is lower than the temperature;
desolventizing gas: 10 L/min;
Residence time: 25ms.
8. The high throughput assay of claim 1, wherein: the volume ratio of HPTS, TEOS and concentrated ammonia water in the step (1) is 4.5-5:1-1.2:1-1.5.
9. The high throughput assay of claim 1, wherein: the pipe diameter of the multi-wall carbon nano-pipe@silicon dioxide composite material in the step (1) is 50 nm.
10. The high throughput assay of claim 1, wherein: the speed of dropwise adding the ammonium persulfate aqueous solution in the step (2) is 20-30 drops/min.
11. The high throughput assay according to any one of claims 8-10 wherein: the MWCNTs@SiO 2 @PANI adsorbent described in step S2-3 is prepared by the following method:
(1) The preparation method of the MWCNTs@SiO 2 comprises the following steps:
Adding 2.0-3.0g of multi-wall carbon nano tube into a 250 mL beaker, adding 70-100 mL cyclohexane, normal hexanol and Triton X-100 mixed solution, performing ultrasonic dispersion for 10-20min, sequentially adding 4.5-5.0 mL HPTS, 1.0-1.2 mL TEOS and 1.0-1.5 mL concentrated ammonia water under magnetic stirring, stirring uniformly, and performing reaction at the room temperature for hydrolysis polymerization for 12-16 h; after the reaction is finished, acetone demulsifies, centrifugal separation is carried out at the rotating speed of 5000-8000 r/min, supernatant is removed, ethanol and pure water are used for circulating and cleaning for 3-5 times to remove surfactant until the surfactant is neutral, and vacuum drying is carried out at the temperature of 40-60 ℃ to obtain the multi-wall carbon nano tube@silicon dioxide composite material;
(2) The preparation method of the MWCNTs@SiO 2 @PANI comprises the following steps:
Adding 5.0-15.0 mL ethanol, introducing nitrogen to deoxidize 10-15 min, adding 1.0-2.0 g multi-wall carbon nano tube @ silicon dioxide composite material prepared in step 1, carrying out short-term ultrasonic homogenization for 30 seconds, firstly adding 50-80 mL ultrapure water containing 0.05-0.15 mol hydrochloric acid, then adding 1.0-1.5 g dodecyl alcohol polyoxyethylene ether sulfuric acid, stirring rapidly at constant temperature with a magnet at high speed for 10-20 min, then adding 2.2-8.8 mL aniline, dropwise adding 0.04-0.15 mol ammonium persulfate aqueous solution dropwise, controlling the reaction temperature in an ice bath state at 0-4 ℃, and stirring at high speed for reacting for 10-20 h; and demulsifying the product by using acetone, filtering the emulsion by using a G3/G4 funnel, centrifuging, repeatedly washing the emulsion to be neutral by using ethanol-water, and freeze-drying the emulsion by using a freeze dryer to obtain the MWCNTs@SiO 2 @PANI polymer.
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