CN118002086A

CN118002086A - Multi-dimensional layered material and preparation method and application thereof

Info

Publication number: CN118002086A
Application number: CN202410057614.7A
Authority: CN
Inventors: 郭新颖; 张卫兵; 陈�峰; 陆娟
Original assignee: Nantong Center For Disease Control And Prevention
Current assignee: Nantong Center For Disease Control And Prevention
Priority date: 2024-01-15
Filing date: 2024-01-15
Publication date: 2024-05-10

Abstract

The invention belongs to the technical field of analytical chemistry, and particularly relates to a multi-dimensional layered material, a preparation method and application thereof. The preparation method of the multi-dimensional layered material comprises the following steps: (1) Respectively dissolving lithium fluoride and titanium aluminum carbide in hydrochloric acid-water solution, and mixing and reacting the two to obtain Ti ₃C₂; (2) Mixing polyvinylpyrrolidone, sodium hydroxide and hydrazine hydrate, adding the mixture into a mixed solution of Ti ₃C₂ and cobalt salt, and reacting to obtain Ti ₃C₂ -Co; (3) Then reacting the Ti ₃C₂ -Co aqueous solution with the chitosan aqueous solution to obtain Ti ₃C₂ -Co@ chitosan; (4) Finally, reacting Ti ₃C₂ -Co@ chitosan with pyrrole monomer to obtain the multi-dimensional lamellar material. When the multidimensional laminar material prepared by the method is used for extracting a sample, the whole adsorption extraction and enrichment analysis process can be completed only for 2min, and the multidimensional laminar material is a magnetic solid-phase adsorbent with good magnetic separation effect and high recycling efficiency and great potential.

Description

Multi-dimensional layered material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of analytical chemistry, and particularly relates to a multi-dimensional layered material, a preparation method and application thereof.

Background

Triazine herbicide (triazine herbicides) is a high-efficiency, broad-spectrum and low-toxicity herbicide with a stable structure of sym-triazene, which is widely used internationally, can effectively control some weeds which are difficult to remove, and improves the yield and quality of field crops. Meanwhile, triazine herbicide can also generate high-toxicity triazine metabolites such as deethylated atrazine, deisopropylatrazine and deethylatrazine under the action of plant microenvironment, and has great influence on the environment and crops. Because of the complex ingredients of traditional Chinese medicinal materials, efficient enrichment and accurate extraction of target components are key steps for ensuring accurate and reliable results, and different sample pretreatment methods have been reported at present.

The Chinese patent CN104316620A discloses a detection method of trace triazine herbicide, wherein a diluted sample to be detected is used as a liquid to be detected; adding 1-hexyl-3-methylimidazole ferric chloride salt into the liquid to be detected, adding carbonyl iron powder into the liquid to be detected after ultrasonic dispersion, and magnetically separating by using a magnet after shaking to obtain adsorption iron powder; adding secondary distilled water and a weak polar organic reagent into adsorption iron powder, shaking for layering, transferring an upper reagent into a test tube, drying by nitrogen, adding acetonitrile and shaking to obtain a sample injection solution; and measuring the chromatogram of the sample injection solution by using an ultra-fast liquid chromatograph, and quantitatively analyzing the concentration of the triazine herbicide in the sample to be measured according to a regression equation of the chromatographic peak area A and the concentration c of the triazine herbicide.

Another chinese patent CN112946128a discloses a pretreatment method and quantitative detection method for triazine herbicide, the pretreatment method for triazine herbicide: adding a proper amount of hydrochloric acid into a sample to be detected, and uniformly mixing to obtain a sample solution to be detected; adding a sample solution to be detected into an activated spin integrated column solid-phase microextraction device, and centrifuging at 2500r/min for 1min; discarding the solution in the cannula; adding 2mL of acetonitrile/acetic acid solution with the volume ratio of 30:70 into the device, and centrifuging at 1000r/min for 1min; the eluate in the cannula was collected and filtered through a 0.22 μm microporous filter.

However, most of the above methods use commercial solid phase extraction and solid phase microextraction instruments or modified commercial dispersion solid phase extraction materials; when the solid phase extraction pretreatment method is adopted, the sample treatment process needs to undergo the steps of activation, sample loading, leaching, drying, elution and the like, so that the use and the consumption of an organic solvent are huge, the operation is complicated, the time and the labor are consumed, and the environment protection requirement cannot be met; the commercial dispersion solid phase extraction material is a traditional carbon material such as C ₁₈, graphite carbon black and the like, an adsorbent such as neutral alumina or PSA powder and a functionalized iron-based material with simple oxygen-containing functional groups such as carbonyl iron powder and the like, and has the advantages of high pretreatment speed, low selectivity, poor specificity, few detectable components, incapability of being fully recycled after disposable consumption and environmental pollution.

Therefore, the combined action of the rapid dispersion solid phase extraction technology and the novel nano adsorbent which has strong specificity, high enrichment degree and recycling can provide a novel method and a novel thought for a laboratory and a detection mechanism in the triazine herbicide and metabolite residue analysis technology thereof, and the establishment of a rapid, efficient, multi-component and high-throughput online screening and quantitative detection technology for the novel technology for the analysis of the triazine herbicide and the metabolite residue of the traditional Chinese medicine has important significance.

Disclosure of Invention

Aiming at the problems existing in the prior art, the invention provides a multi-dimensional layered material, and a preparation method and application thereof. The novel layered magnetic nano material with excellent adsorption performance can form strong intermolecular acting force and pi-pi bonding effect with triazine organic compounds with a sym-triazene structure, and is used for rapid analysis of triazine herbicides and metabolite residues of the triazine herbicides.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

the raw materials of the multi-dimensional layered material comprise lithium fluoride, cobalt salt, titanium aluminum carbide, polyvinylpyrrolidone and chitosan.

Preferably, the particle size of the multi-dimensional layered material is 50-80nm.

Preferably, the cobalt salt is selected from one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate and cobalt chloride hexaamide.

Preferably, the molar ratio of the lithium fluoride, the cobalt salt, the titanium aluminum carbide, the polyvinylpyrrolidone and the chitosan is 58-77:4.4-5.4:5.1-6.2:0.56-1.4:4.5-5.4.

The invention also provides a preparation method of the multi-dimensional layered material, which comprises the following steps:

(1) Respectively dissolving lithium fluoride and titanium aluminum carbide in hydrochloric acid-water solution, and mixing and reacting the two to obtain Ti ₃C₂;

(2) Mixing polyvinylpyrrolidone, sodium hydroxide and hydrazine hydrate, adding the mixture into a mixed solution of Ti ₃C₂ and cobalt salt, and reacting to obtain Ti ₃C₂ -Co;

(3) Then reacting the Ti ₃C₂ -Co aqueous solution with the chitosan aqueous solution to obtain Ti ₃C₂ -Co@ chitosan;

(4) Finally, reacting Ti ₃C₂ -Co@ chitosan with pyrrole monomer to obtain the multi-dimensional lamellar material.

Preferably, in the step (1), the mass volume ratio of the lithium fluoride to the hydrochloric acid-water solution is 1.5-2g:15-20mL, stirring is needed when the lithium fluoride is dissolved in the hydrochloric acid-water solution, the stirring speed is 100-400r/min, and the stirring time is 10-60min.

Preferably, in the step (1), the mass volume ratio of the titanium aluminum carbide to the hydrochloric acid-water solution is 1-1.2 g/5 mL, ultrasound is needed when the titanium aluminum carbide is dissolved in the hydrochloric acid-water solution, the power of the ultrasound is 60-200W, and the time of the ultrasound is 8-15min.

Preferably, in the step (1), the volume ratio of hydrochloric acid to water in the hydrochloric acid-water solution is 3-5:1, the temperature of the reaction is 25-35 ℃, the reaction is stirred, water is washed to pH=7 after the reaction, and the reaction is freeze-dried under the conditions of filtration, ice bath and nitrogen.

Preferably, the stirring speed is 100-400r/min, the stirring time is 24-30h, the freeze-drying temperature is-18-4 ℃, and the freeze-drying time is 0.5-120min.

Preferably, the mass-volume ratio of polyvinylpyrrolidone, sodium hydroxide and hydrazine hydrate in the step (2) is 0.1-0.25g:0.12-0.4g:30-40mL, and the mixing is carried out by stirring and ultrasonic treatment.

Preferably, the stirring speed is 100-400r/min, the stirring time is 30-120min, the ultrasonic power is 60-200W, and the ultrasonic time is 10-30min.

Preferably, the cobalt salt in the step (2) needs to be dissolved in ethylene glycol, and the mass volume ratio of the cobalt salt to the ethylene glycol is 1-2 g/15-20 mL.

Preferably, ti ₃C₂ is dissolved in water and is subjected to ultrasonic treatment, the mass-volume ratio of Ti ₃C₂ to water is 1-1.5g:20-50mL, the ultrasonic power is 60-200W, and the ultrasonic treatment time is 90-120min.

Preferably, the dropping speed of the addition in the step (2) is 2-5 drops/10 seconds, the temperature of the reaction is 25-35 ℃, the reaction is carried out by ultrasonic, and the filtration, washing and drying are carried out after the reaction.

Preferably, the power of the ultrasonic wave is 60-200W, the ultrasonic wave time is 10-20min, the washed solution comprises water and ethanol, the washing times are 3-6 times, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

Preferably, in the step (3), the mass fraction of the Ti ₃C₂ -Co aqueous solution is 1-2%, the mass fraction of the chitosan aqueous solution is 0.5-1%, and the volume ratio of the Ti ₃C₂ -Co aqueous solution to the chitosan aqueous solution is 1:1-2.

Preferably, the temperature of the reaction in the step (3) is 25-35 ℃, stirring is carried out during the reaction, and the reaction is washed with water, centrifuged and dried.

Preferably, the stirring speed is 100-400r/min, the stirring time is 30-90min, the times of water washing and centrifugation are 3-5 times, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

Preferably, the temperature of the reaction in step (4) is 25-35 ℃ and the reaction time is 24-30h.

Preferably, the Ti ₃C₂ -Co@ chitosan and pyrrole monomer before the reaction in the step (4) are mixed with aqueous hydrochloric acid and subjected to ultrasonic treatment, and ammonium persulfate solution is added during the reaction, and filtering, washing, drying and grinding are performed after the reaction.

Preferably, the volume ratio of hydrochloric acid to water in the hydrochloric acid-water solution is 1:4-1:5, the concentration of the ammonium persulfate solution is 0.04-0.05mol/L, and the mass volume ratio of the Ti ₃C₂ -Co@ chitosan, the pyrrole monomer, the hydrochloric acid-water solution and the ammonium persulfate solution is 1-1.2g:8-14mL:100-150mL:20mL.

Preferably, the power of the ultrasonic wave is 60-200W, the ultrasonic wave time is 10-20min, the washed solution comprises water and ethanol, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

The invention also provides application of the multi-dimensional layered material in analysis and detection of triazine herbicides and metabolites thereof.

Compared with the prior art, the invention has the beneficial effects that:

(1) When the multi-dimensional layered material prepared by the method is used for extracting a sample, the time consumption of the extraction process is greatly shortened because the layered magnetic material has a shorter diffusion distance, and the whole-course adsorption extraction and enrichment analysis process can be completed in 2min, so that the multi-dimensional layered material is a magnetic solid-phase adsorbent with good magnetic separation effect and high recycling efficiency and great potential.

(2) The multi-dimensional layered material prepared by the method is used for rapid and efficient extraction and enrichment of triazine herbicides, and can be combined with a high-performance liquid chromatography technology.

(3) The method can complete high-flux multi-component simultaneous on-line rapid screening and quantitative determination of 22 triazine herbicides and metabolites thereof, is extremely suitable for analysis of residue of triazine herbicides and metabolites thereof, and has important significance for quality safety detection and control of Chinese medicinal materials.

(4) The multi-dimensional layered material prepared by room temperature contains Co element and chitosan, so that the material has excellent ferromagnetism and further improves the adsorption performance.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) image of Ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

FIG. 2 is a Scanning Electron Microscope (SEM) image of Ti ₃C₂ -Co prepared in comparative example 2.

FIG. 3 is a high performance liquid chromatogram of 22 triazine herbicides and their metabolites (wherein numbers 1-22 represent respectively 1. Deisoxyatrazine, 2. Oxaziridone, 3. Deithylatrazine, 4. West Ma Tong, 5. Hexazinone, 6. Simazine, 7. Deithylatrazine, 8. Atrathrough, 9. Oxaziridone, 10. Simetryn, 11. Atrazine, 12. Zhong Dingtong, 13. Plowing, 14. Terbutamid, 15. Atrazine, 16. Promethazine, 17. Terbutryn, 18. Prometryn, 19. Terbutryn, 20. Atrazine, 21. Isovaleric, 22. Prometryn).

Fig. 4 is a high performance liquid chromatogram of whole herb Chinese herbal medicine sample humifuse euphorbia herb in different pretreatment methods.

FIG. 5 is a high performance liquid chromatogram of the detection of the component deethylatrazine by 5 methods for a sample humifuse euphorbia herb.

FIG. 6 shows high performance liquid chromatograms of flos Chrysanthemi samples of flowers and Chinese medicinal materials in different pretreatment methods.

FIG. 7 is a high performance liquid chromatogram of the detection of the component prometryn in the sample chrysanthemum in 5 methods.

FIG. 8 shows high performance liquid chromatograms of radix astragali samples of root and rhizome Chinese medicinal materials in different pretreatment methods.

FIG. 9 is a high performance liquid chromatogram of the 5 methods for detecting the components metribuzin and prometryn when the astragalus root is sampled.

FIG. 10 shows high performance liquid chromatograms of Ganoderma lucidum samples of fungus Chinese medicinal materials in different pretreatment methods.

FIG. 11 shows high performance liquid chromatograms of 5 methods without component detection for Ganoderma lucidum samples.

FIG. 12 is a high performance liquid chromatogram of fruit seed type Chinese herbal medicine sample Gordon euryales in different pretreatment methods.

FIG. 13 is a high performance liquid chromatogram of real-time 5 methods of detecting no component of the sample Gordon euryale seed.

(In FIGS. 4-13, numbers 1-5 represent respectively: 1. Direct extraction method; 2.PSA+C ₁₈ dispersion solid phase extraction; 3.Ti ₃C₂ -Co magnetic solid phase extraction; 4.Ti ₃C₂ -Co@ chitosan magnetic solid phase extraction; 5. Ti ₃C₂ -Co@ chitosan@PPy. This method).

Detailed Description

It is worth noting that the raw materials used in the invention are all common commercial products, wherein polyvinylpyrrolidone (molecular weight 8000) has a product number of P110608, and chitosan (molecular weight about 100 ten thousand) has a product number of C434553, which are all purchased from Aba Ding Shiji company; absolute ethanol, ethylene glycol, hydrochloric acid, sodium hydroxide, pyrrole, hydrazine hydrate and Ammonium Persulfate (APS) are all analytically pure and all purchased from the national pharmaceutical group reagent company; c ₁₈ (40-63 μm), graphite carbon black (200-400 mesh), neutral alumina (Al-N, 100-300 mesh) and PSA (ethylenediamine-N-propyl, 40-63 μm, 60A) were all purchased from Shanghai Annotation reagent company; west Ma Tong, simazine, atrazine, metribuzin, atrazine, zhong Dingtong, plodin, terbutamid, ametryn, plodin, terbutryn, prometryn, terbutryn, bentazon, isovaleric, ipratropium, deisopropyl atrazine, deethyl atrazine and deethyl atrazine are all available from Shanghai's spectroscopy reagent company; oxaziclomefone and cyazone were purchased from Sigma reagent limited.

Example 1

A multi-dimensional layered material (Ti ₃C₂ -Co@ chitosan @ PPy) and a preparation method thereof comprise the following steps:

(1) Preparation of Ti ₃C₂:

First, 1.5g of LiF was dissolved in 15mL of 5:1 by volume hydrochloric acid-water solution, placed in a round-bottomed flask, and stirred continuously at 100r/min under a stirrer for 60min until uniform, and the obtained solution was named liquid No. 1.

Then 1.0g of Ti ₃AlC₂ powder was weighed and dissolved in 5.0mL of 5:1 by volume hydrochloric acid-water solution, and dispersed by 60W ultrasound for 15min until a uniform dispersion state was presented, designated liquid No. 2. Immediately, the liquid No. 2 was poured into the liquid No.1 in its entirety, stirred continuously at 100r/min for 60min at 25℃and reacted sufficiently for 24 hours.

And finally, after the reaction is finished, washing the suspension after the reaction by using pure water to remove excessive acid, collecting precipitate by a filtering and centrifuging method, washing the product by using pure water to neutral pH=7, and freeze-drying at-18 ℃ for 0.5min in an ice bath and nitrogen-filled state to obtain Ti ₃C₂ powder.

(2) Preparation of Ti ₃C₂ -Co:

Firstly, 0.10g of polyvinylpyrrolidone and 0.12g of sodium hydroxide are weighed and dissolved in 30mL of hydrazine hydrate, continuously stirred for 30min at 400r/min until uniform, and treated by 200W ultrasonic for 10min to prepare a uniformly mixed solution, and the uniformly mixed solution is marked as solution A; then 1.29g of cobalt nitrate hexahydrate was weighed and dissolved in 15mL of ethylene glycol to prepare a cobalt ion-containing alcohol solution, designated as solution B; then, 1.0g of Ti ₃C₂ powder was weighed into 20mL of an aqueous solution, and sonicated at 200W for 90min to obtain a uniform dispersion, which was designated as solution C.

The solution B and the solution C were mixed uniformly and denoted as solution M.

The mixed solution M was added to the solution A at a dropping rate of 2 drops/10 seconds at 25℃and then continuously stirred at 400rpm for 30 minutes, and was subjected to ultrasonic treatment at 200W for 10 minutes to allow the reaction to proceed sufficiently. Taking out the precipitate after the reaction is completed, washing the precipitate with pure water and ethanol for 3 times respectively, and vacuum drying the precipitate for 24 hours at 60 ℃ to obtain the magnetic Ti ₃C₂ -Co powder.

(3) Preparation of Ti ₃C₂ -Co@ chitosan:

20mL of 0.5% chitosan aqueous solution and 20mL of 1.0% Ti ₃C₂ -Co aqueous solution are continuously stirred at 100rpm for 90min to be uniform at 25 ℃, deionized water is added for washing and centrifugation for 3 times, and the mixture is dried at 60 ℃ for 24h to obtain Ti ₃C₂ -Co@ chitosan.

(4) Preparation of Ti ₃C₂ -Co@ chitosan @ PPy:

1.0g of magnetic Ti ₃C₂ -Co@ chitosan powder and 8mL of pyrrole monomer were weighed out respectively at 25℃and dissolved in 100mL of 1.0mol/L aqueous hydrochloric acid solution (volume ratio 1:4), and sonicated at 60W for 20min

Dispersing uniformly, slowly dropwise adding 20mL of 0.04mol/L ammonium persulfate solution into a round-bottom flask under the acidic condition while stirring, reacting for 24 hours, filtering to separate a sample, repeatedly cleaning with pure water and ethanol for 3 times, drying at 60 ℃ for 24 hours, and grinding to obtain the magnetic Ti ₃C₂ -Co@ chitosan@PPy.

Example 2

(1) Preparation of Ti ₃C₂:

First, 2.0g of LiF was dissolved in 20mL of a 3:1 volume ratio hydrochloric acid-water solution, placed in a round bottom flask, and stirred continuously at 400rpm under a stirrer for 10min until uniform, and the obtained solution was named liquid No. 1.

Then 1.2g of Ti ₃AlC₂ powder was weighed and dissolved in 5.0mL of hydrochloric acid-water solution with a volume ratio of 3:1, and dispersed by 200W ultrasound for 10min until a uniform dispersion state was presented, designated liquid No. 2. Immediately, the liquid No. 2 was poured entirely into the liquid No.1, stirred continuously at 400rpm for 10min at 35℃and reacted for 30 hours.

And finally, after the reaction is finished, washing the suspension after the reaction by using pure water to remove excessive acid, collecting precipitate by a filtering and centrifuging method, washing the product by using the pure water to neutral pH=7, and freeze-drying the product at 4 ℃ for 120min in an ice bath and nitrogen-filled state to obtain Ti ₃C₂ powder.

(2) Preparation of Ti ₃C₂ -Co:

Firstly, weighing 0.25g of polyvinylpyrrolidone and 0.40g of sodium hydroxide, dissolving in 40mL of hydrazine hydrate, continuously stirring for 120min to uniformity at 100r/min, and performing ultrasonic treatment at 60W for 30min to prepare a uniformly mixed solution, and marking the uniformly mixed solution as a solution A; 1.29g of hexaminocobaltous chloride is weighed again and dissolved in 20mL of glycol to prepare an alcohol solution containing cobalt ions, which is marked as solution B; then, 1.5g of Ti ₃C₂ powder was weighed into 50mL of an aqueous solution, and sonicated at 60W for 120min to obtain a uniform dispersion, which was designated as solution C.

The mixed solution M was added to the solution A at a dropping rate of 5 drops/10 seconds at 35℃and then continuously stirred at 100rpm for 120 minutes, and was subjected to ultrasonic treatment at 60W for 20 minutes to allow the reaction to proceed sufficiently. And taking out the precipitate after the reaction is completed, washing the precipitate with pure water and ethanol for 6 times respectively, and vacuum drying the precipitate at 70 ℃ for 22 hours to obtain the magnetic Ti ₃C₂ -Co powder.

(3) Preparation of Ti ₃C₂ -Co@ chitosan:

40mL of 1.0% chitosan aqueous solution and 20mL of 2.0% Ti ₃C₂ -Co aqueous solution are continuously stirred at 400rpm for 30min to be uniform at 35 ℃, washed with deionized water and centrifuged for 5 times, and dried at 70 ℃ for 22h to obtain Ti ₃C₂ -Co@ chitosan.

(4) Preparation of Ti ₃C₂ -Co@ chitosan @ PPy:

1.2g of magnetic Ti ₃C₂ -Co@ chitosan powder and 14mL of pyrrole monomer are respectively weighed at 35 ℃ and dissolved in 150mL of 1.25mol/L hydrochloric acid aqueous solution (volume ratio is 1:5), and are uniformly dispersed by 200W ultrasonic treatment for 10min, 20mL of 0.05mol/L ammonium persulfate solution is slowly added dropwise under the acidic condition while stirring in a round bottom flask, the reaction is carried out for 30h, a sample is separated by suction filtration, the sample is repeatedly washed by pure water and ethanol for 5 times, the drying is carried out at 70 ℃ for 22h, and the magnetic Ti ₃C₂ -Co@ chitosan@PPy is obtained by grinding.

Comparative example 1

The material was psa+c ₁₈.

Comparative example 2

A multi-dimensional layered material (Ti ₃C₂ -Co) is prepared by the following steps:

(1) Preparation of Ti ₃C₂:

(2) Preparation of Ti ₃C₂ -Co:

Comparative example 3

A multi-dimensional lamellar material (Ti ₃C₂ -Co@ chitosan) and a preparation method thereof comprise the following steps:

(1) Preparation of Ti ₃C₂:

(2) Preparation of Ti ₃C₂ -Co:

(3) Preparation of Ti ₃C₂ -Co@ chitosan:

Continuously stirring 0.5% chitosan water solution (molecular weight about 100 ten thousand) and 1.0% Ti ₃C₂ -Co water solution at 100rpm for 90min at 25deg.C until uniform, adding deionized water, washing and centrifuging for 3 times, and drying at 60deg.C for 24 hr to obtain Ti ₃C₂ -Co@ chitosan

The multi-dimensional layered material (magnetic Ti ₃C₂ -Co@ chitosan@PPy) prepared in example 1 is shown in FIG. 1, and the particle size of Ti ₃C₂ -Co@ chitosan@PPy nano particles coated by chitosan and polypyrrole is smaller and only 50-80nm can be seen in FIG. 1.

The scanning electron microscope diagram of the Ti ₃C₂ -Co material prepared in comparative example 2 is shown in fig. 2, and fig. 2 shows that the Ti ₃C₂ -Co nano material has an obvious lamellar structure under a scanning electron microscope, and the addition of cobalt element enables the material to show excellent magnetic performance.

Application example quantitative determination

The multi-dimensional layered material is applied to the measurement of 22 triazines and metabolites thereof in 109 traditional Chinese medicinal materials of 4 kinds.

(1) All grass 20: herba Euphorbiae Humifusae, herba Lysimachiae, herba Sedi, herba Leonuri, herba Eleusines Indicae, herba plantaginis, medulla Junci, herba Solani Nigri, herba Pteridis Multifidae, herba Houttuyniae, spica Prunellae, herba Hyperici Japonici, herba Scutellariae Barbatae, herba Artemisiae Annuae, herba Euphorbiae Helioscopiae, herba Acalyphae, herba Andrographitis, caulis Lonicerae, herba Gynostemmatis, and herba Epimedii;

(2) 14 kinds of flowers: flos Chrysanthemi, flos Rosae chinensis, flos Lonicerae, flos Celosiae Cristatae, flos moutan, flos Farfarae, flos Lilii Viriduli, flos Albiziae, flos Sophorae Immaturus, flos Carthami, flos Puerariae Lobatae, flos Magnoliae officinalis, stigma Maydis, and stamen Nelumbinis;

(3) Root and rhizome 48: astragalus root, tendril-leaved fritillary bulb, angelica, pseudo-ginseng, yam, turmeric, bupleurum root, large-leaf gentian root, white atractylodes rhizome, red sage root, pilose asiabell root, costustoot, baikal skullcap root, common burreed rhizome, rehmannia root, coptis root, morinda root, india madder root, platycodon root, himalayan teasel root, rhizoma atractylodis, largehead atractylodes rhizome, rhubarb, giant knotweed rhizome, tuber fleeceflower root, twotooth achyranthes root, common monkshood daughter root, white paeony root, tetrandra root, rhizoma corydalis, indigowoad root, kudzuvine root, liquorice, ephedra, dwarf lilyturf tuber, asparagus root, szechuan lovage rhizome, manchurian wildginger, thinleaf milkwort root-bark, nutgrass galingale rhizome, rhizoma kaempferiae, pinellia tuber, ramie root, giant knotweed rhizome, pubescent holly root, paris rhizome and medicinal cyathula root;

(4) Fungus 5: ganoderma lucidum, poria cocos, tremella, perilla seed and smilax glabra;

(5) Fruit seed class 22: semen euryales, lotus seed, medlar, peach kernel, hawthorn, gardenia, fructus quisqualis, cardamom, semen cuscutae, raspberry, plantain seed, mulberry, castor seed, almond, cowherb seed, wild jujube seed, chinese honeylocust fruit, momordica grosvenori, arborvitae seed, citron, long pepper and malt.

The measuring method comprises the following steps:

(1) Sample treatment: crushing the dried sample by a crusher, sieving with a 40-mesh sieve, and sealing and preserving at normal temperature;

(2) Extracting: 10.0g (accurate to 0.001 g) of the traditional Chinese medicine powder is weighed into a 50mL centrifuge tube, 20mL of acetonitrile solution is added, mixed and vibrated for 20min at 5000rpm, water bath is carried out at 30 ℃,70W ultrasonic is carried out for 10min, and centrifugation is carried out for 5min at 4000 r/min. Repeatedly extracting for 2 times, mixing the two supernatants, concentrating at 35deg.C under nitrogen blowing, dissolving the residue with acetone, and keeping volume to 10mL.

(3) Purifying: transferring 1.0mL of the liquid to be purified into a centrifuge tube, adding 10mg of the multi-dimensional layered material prepared in the example 1 and the comparative examples 1-3 into the centrifuge tube, performing ultrasonic dispersion for 1min, performing vortex shaking for 2min, performing solid-liquid two-phase magnetic attraction separation, removing the supernatant, and retaining the magnetic nanoparticles containing the target components. Accurately removing 2mL of acetone, shaking for 2min by vortex, completely eluting the target component from the nano particles, collecting eluent, filtering by a 0.22 mu m filter membrane, and carrying out reagent blank test in the experimental process.

Wherein, the multi-dimensional layered material prepared in example 1 can be reused 15-20 times without reducing the specific adsorption effect after repeated washing with acetone and pure water.

1. Preparation of standard solution

1.1.22 Triazine herbicides and metabolite standard solutions (1000 μg/mL) were respectively prepared: west Ma Tong, simazine, atrazine, metribuzin, atrazine, zhong Dingtong, plodin, terbutamid, ametryn, plodin, terbutryn, prometryn, terbutryn, bentazon, isovalerate, isoprotuzin, deisopropyl atrazine, deethyl terbutryn, oxazin and hexazinone.

1.2 Preparation of a Mixed Standard stock solution (40. Mu.g/mL): and respectively taking 40 mu L from the standard solutions of 22 triazine herbicides and metabolites thereof, placing the solutions in a brown sample injection bottle, and using acetonitrile to fix the volume to 1.0mL to prepare the mixed standard stock solution of the triazine herbicides and metabolites thereof with the mass concentration of 40 mu g/mL.

1.3 Configuration of mixed standard working solution: the 40 mug/mL mixed standard stock solution is diluted step by step to prepare a series of mixed standard working solutions with mass concentrations of 0.1, 0.2, 0.4, 0.5, 1.0, 2.0, 4.0, 5.0, 10.0 and 20 mug/mL respectively, and the mother solution is returned to room temperature and is uniformly mixed by vortex before each dilution or preparation.

2. Drawing of a Standard Curve

And (3) injecting the standard solution series into a liquid chromatograph, sequentially sampling and detecting from low concentration to high concentration, and carrying out linear regression analysis by taking the peak area of the chromatographic peak of each compound component as an ordinate and the marked concentration of each component as an abscissa to obtain a standard curve regression equation.

Wherein, the liquid chromatography detection conditions are as follows:

chromatographic column: athena C ₁₈ hydrophobic column (250 mm. Times.4.6 mm,5 μm).

Column temperature: 35 ℃.

Detection wavelength: 222nm.

Sample injection amount: 5.0. Mu.L.

Flow rate: 1.0mL/min.

Mobile phase: linear gradient elution was performed with water (phase a) and acetonitrile (phase B) as mobile phases.

Gradient elution procedure: 0-5min,0% B-30% B;5-15min,30% B to 35% B;15-25min,35% B to 45% B;25-35min,45% B to 55% B;35-40min,55% B.fwdarw.25% B.

The high performance liquid chromatograms of the 22 triazine herbicides and metabolites thereof are shown in fig. 3, and numerals 1 to 22 in fig. 3 respectively represent: 1. the composition comprises 3 parts of deisoxazine, 2 parts of oxaziridone, 4 parts of atrazine, ma Tong parts of cymoxanil, 6 parts of simazine, 7 parts of deitobuthylazine, 8 parts of atraotype, 9 parts of oxaziridone, 10 parts of simetryn, 11 parts of atrazine, 12 parts of Zhong Dingtong, 13 parts of ploidy, 14 parts of terbutryn, 15 parts of terbutryn, 16 parts of prometryn, 17 parts of terbutryn, 18 parts of prometryn, 19 parts of terbutryn, 20 parts of atrazine, 21 parts of isotebuzin and 22 parts of prometryn.

The results of the peak time, standard curve, linear range and correlation coefficient of 22 triazine herbicides and metabolites thereof are shown in table 1, and the detection limit, quantitative limit, recovery rate and relative standard deviation of 22 triazine herbicides and metabolites thereof are shown in table 2.

From the results in tables 1-2, the linear range of the method can be found: 0.1-20 mug/mL, detection limit range: 0.2-1.0 mug/kg, quantitative limit range: 0.7-3.3 mug/kg, recovery range: 92.8-99.6%, relative standard deviation range: 1.2-3.8%, and the correlation coefficient R ² is 0.9999, the method has high recovery rate, good precision, low detection limit and good linear relation.

TABLE 1 Peak time, standard Curve and Linear Range for 22 triazine herbicides and metabolites thereof

TABLE 2 detection limits, quantitative limits, recovery rates and relative standard deviations of 22 triazine herbicides and metabolites thereof

3. Determination of representative sample solutions

3.1 The method (Ti ₃C₂ -Co@ chitosan@PPy magnetic solid phase extraction prepared in example 1) and other pretreatment methods (direct extraction method; PSA+C ₁₈ prepared in comparative example 1 is subjected to dispersion solid phase extraction, ti ₃C₂ -Co prepared in comparative example 2 is subjected to magnetic solid phase extraction, ti ₃C₂ -Co@ chitosan prepared in comparative example 3 is subjected to magnetic solid phase extraction), and the content of 22 triazine herbicides and metabolites thereof in the whole herb traditional Chinese medicinal material sample humifuse euphorbia herb is detected by a high performance liquid chromatography, wherein the direct extraction method refers to pretreatment steps such as extraction, enrichment, analysis, concentration and the like of the sample are not performed.

The result of the high performance liquid chromatography superposition chart is shown in fig. 4, and the high performance liquid chromatography superposition chart is sequentially as follows from top to bottom in fig. 4: 1. a direct extraction method; 2. performing dispersion solid phase extraction on the PSA+C ₁₈ prepared in comparative example 1; 3. performing magnetic solid phase extraction on Ti ₃C₂ -Co prepared in comparative example 2; 4. performing magnetic solid-phase extraction on the Ti ₃C₂ -Co@ chitosan prepared in comparative example 3; 5. ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

Wherein the component deethylatrazine is detected, as shown in figure 5, the mass concentrations obtained by methods 1-5 are respectively: 5.02. Mu.g/kg, 5.12. Mu.g/kg, 5.20. Mu.g/kg, 5.17. Mu.g/kg, 5.25. Mu.g/kg.

3.2 Using the method and other pretreatment methods, detecting the content of 22 triazine herbicides and metabolites thereof in the flower traditional Chinese medicine sample chrysanthemum by a high performance liquid chromatograph.

The result of the high performance liquid chromatography superposition chart is shown in fig. 6, and the following steps are sequentially carried out from top to bottom in fig. 6: 1. a direct extraction method; 2. performing dispersion solid phase extraction on the PSA+C ₁₈ prepared in comparative example 1; 3. performing magnetic solid phase extraction on Ti ₃C₂ -Co prepared in comparative example 2; 4. performing magnetic solid-phase extraction on the Ti ₃C₂ -Co@ chitosan prepared in comparative example 3; 5. ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

Wherein the prometryn component is detected, as shown in FIG. 7, the mass concentrations obtained by methods 1-5 are respectively: 7.90. Mu.g/kg, 7.96. Mu.g/kg, 7.04. Mu.g/kg, 7.23. Mu.g/kg, 8.02. Mu.g/kg.

3.3 Using the method and other pretreatment methods, detecting the contents of 22 triazine herbicides and metabolites thereof in root and rhizome Chinese medicinal material samples astragalus by a high performance liquid chromatography.

The result of the high performance liquid chromatography superposition chart is shown in fig. 8, and the following steps are sequentially carried out from top to bottom in fig. 8: 1. a direct extraction method; 2. performing dispersion solid phase extraction on the PSA+C ₁₈ prepared in comparative example 1; 3. performing magnetic solid phase extraction on Ti ₃C₂ -Co prepared in comparative example 2; 4. performing magnetic solid-phase extraction on the Ti ₃C₂ -Co@ chitosan prepared in comparative example 3; 5. ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

Wherein the components of the metribuzin and the prometryn are detected, as shown in figure 9, the mass concentrations of the metribuzin obtained by the methods 1-5 are respectively as follows: 9.93. Mu.g/kg, 10.37. Mu.g/kg, 10.70. Mu.g/kg, 7.76. Mu.g/kg, 11.22. Mu.g/kg. The mass concentrations of the prometryns obtained by the methods 1 to 5 are respectively as follows: 2.83. Mu.g/kg, 2.47. Mu.g/kg, 3.34. Mu.g/kg, 3.37. Mu.g/kg, 4.79. Mu.g/kg.

3.4 Using the method and other pretreatment methods, detecting the content of 22 triazine herbicides and metabolites thereof in the fungus traditional Chinese medicine sample ganoderma lucidum by a high performance liquid chromatograph.

The result of the high performance liquid chromatography superposition chart is shown in fig. 10, and the following steps are sequentially carried out from top to bottom in fig. 10: 1. a direct extraction method; 2. performing dispersion solid phase extraction on the PSA+C ₁₈ prepared in comparative example 1; 3. performing magnetic solid phase extraction on Ti ₃C₂ -Co prepared in comparative example 2; 4. performing magnetic solid-phase extraction on the Ti ₃C₂ -Co@ chitosan prepared in comparative example 3; 5. ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

No target component was detected, and the sample detection rate was 0%, as shown in FIG. 11.

3.5 Using the method and other pretreatment methods, detecting the content of 22 triazine herbicides and metabolites thereof in the fruit seed type Chinese medicinal material sample gorgon fruit by a high performance liquid chromatography.

The result of the high performance liquid chromatography superposition chart is shown in fig. 12, and the following steps are sequentially carried out from top to bottom in fig. 12: 1. a direct extraction method; 2. performing dispersion solid phase extraction on the PSA+C ₁₈ prepared in comparative example 1; 3. performing magnetic solid phase extraction on Ti ₃C₂ -Co prepared in comparative example 2; 4. performing magnetic solid-phase extraction on the Ti ₃C₂ -Co@ chitosan prepared in comparative example 3; 5. ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1.

No target component was detected, and the sample detection rate was 0%, as shown in FIG. 13.

As can be seen from figures 4-13, the multi-dimensional layered material prepared by the invention has the detection effect of detecting the content of 22 triazine herbicides and metabolites thereof, which is obviously better than that of the direct extraction method and comparative examples 1-3.

4. Recovery and precision testing

And (3) recovery rate test: respectively adding three different standard adding concentrations of low, medium and high of theoretical mass concentration of 2.0 mug/kg, 5.0 mug/kg and 20 mug/kg into the sample extracting solution, carrying out sample treatment and on-machine test according to the extracting steps, carrying out parallel measurement on each sample for 7 times (n=7), calculating to obtain the actual mass concentration, wherein the average recovery rate under each mass concentration is 90-110%, and the Relative Standard Deviation (RSD) of 7 recovery rate data is less than 10%.

Wherein, the calculation formula of the recovery (%) is as follows:

Percent recovery = (actual mass concentration-mass concentration of measured component contained in sample)/theoretical mass concentration×100%

And (3) precision testing: the relative standard deviation is commonly used to represent the relative value of the standard deviation of single measurement to the average value of measurement, and the actual mass concentration obtained by parallel measurement of each sample is substituted into a formula for calculation.

Wherein, the calculation formulas of the Standard Deviation (SD) and the Relative Standard Deviation (RSD) are as follows:

relative Standard Deviation (RSD) =standard deviation (SD)/arithmetic mean of measurement results

The average recovery rate calculated for each of the samples measured in parallel and 7 times in succession, and the relative standard deviation RSD, and the sample-labeled recovery ranges for the 5 methods and the relative standard deviation are summarized in table 3.

TABLE 3 sample addition recovery ranges and relative standard deviations

As is clear from the results of Table 3, the pretreatment of Ti ₃C₂ -Co@ chitosan @ PPy prepared in example 1 of the present invention was applied, and the contents of 22 triazine herbicides and their metabolites in the samples were detected by a high performance liquid chromatography, and the average recovery rate and the relative standard deviation RSD were superior to those of the direct extraction method and comparative examples 1-3.

Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. The multi-dimensional layered material is characterized in that raw materials of the multi-dimensional layered material comprise lithium fluoride, cobalt salt, titanium aluminum carbide, polyvinylpyrrolidone and chitosan.

2. The multi-dimensional layered material of claim 1, wherein the particle size of the multi-dimensional layered material is 50-80nm.

3. The multi-dimensional layered material of claim 1, wherein the cobalt salt is selected from one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, and cobalt chloride hexaamide.

4. The multi-dimensional layered material of claim 1, wherein the molar ratio of lithium fluoride, cobalt salt, titanium aluminum carbide, polyvinylpyrrolidone, and chitosan is 58-77:4.4-5.4:5.1-6.2:0.56-1.4:4.5-5.4.

5. A method of preparing a multi-dimensional layered material according to any one of claims 1 to 4, comprising the steps of:

(4) And finally, reacting Ti ₃C₂ -Co@ chitosan with pyrrole to obtain the multi-dimensional lamellar material.

6. The preparation method according to claim 5, wherein in the step (1), the mass-volume ratio of the lithium fluoride to the hydrochloric acid-water solution is 1.5-2g:15-20mL, stirring is required when the lithium fluoride is dissolved in the hydrochloric acid-water solution, the stirring rotating speed is 100-400r/min, and the stirring time is 10-60min; in the step (1), the mass volume ratio of the titanium aluminum carbide to the hydrochloric acid-water solution is 1-1.2g to 5mL, the titanium aluminum carbide is required to be ultrasonically dissolved in the hydrochloric acid-water solution, the ultrasonic power is 60-200W, and the ultrasonic time is 8-15min; in the step (1), the volume ratio of hydrochloric acid to water in the hydrochloric acid-water solution is 3-5:1, the reaction temperature is 25-35 ℃, stirring is carried out during the reaction, water washing is carried out after the reaction until the pH=7, filtering, ice bath and nitrogen are carried out, the stirring speed is 100-400r/min, the stirring time is 24-30h, the freeze drying temperature is-18-4 ℃, and the freeze drying time is 0.5-120min.

7. The preparation method according to claim 5, wherein the mass-to-volume ratio of polyvinylpyrrolidone, sodium hydroxide and hydrazine hydrate in the step (2) is 0.1-0.25g:0.12-0.4g:30-40mL, stirring and ultrasonic are carried out during mixing, the stirring rotating speed is 100-400r/min, the stirring time is 30-120min, the ultrasonic power is 60-200W, and the ultrasonic time is 10-30min; in the step (2), the cobalt salt needs to be dissolved in glycol, the mass volume ratio of the cobalt salt to the glycol is 1-2g:15-20mL, the Ti ₃C₂ needs to be dissolved in water and is subjected to ultrasonic treatment, the mass volume ratio of the Ti ₃C₂ to the water is 1-1.5g:20-50mL, the power of the ultrasonic treatment is 60-200W, and the ultrasonic treatment time is 90-120min; the dropping speed of the addition in the step (2) is 2-5 drops/10 seconds, the reaction temperature is 25-35 ℃, the reaction is carried out by ultrasonic, filtration, washing and drying are carried out after the reaction, the ultrasonic power is 60-200W, the ultrasonic time is 10-20min, the washing solution comprises water and ethanol, the washing times are 3-6 times, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

8. The preparation method according to claim 5, wherein in the step (3), the mass fraction of the Ti ₃C₂ -Co aqueous solution is 1-2%, the mass fraction of the chitosan aqueous solution is 0.5-1%, and the volume ratio of the Ti ₃C₂ -Co aqueous solution to the chitosan aqueous solution is 1:1-2; the temperature of the reaction in the step (3) is 25-35 ℃, stirring is carried out during the reaction, washing, centrifuging and drying are carried out after the reaction, the stirring speed is 100-400r/min, the stirring time is 30-90min, the times of washing and centrifuging are 3-5, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

9. The process according to claim 5, wherein the temperature of the reaction in step (4) is 25 to 35℃and the reaction time is 24 to 30 hours; mixing Ti ₃C₂ -Co@ chitosan and pyrrole before reaction in the step (4) with aqueous hydrochloric acid solution and carrying out ultrasonic treatment, adding ammonium persulfate solution during reaction, filtering, washing, drying and grinding, wherein the volume ratio of hydrochloric acid to water in the aqueous hydrochloric acid solution is 1:4-5, the concentration of the ammonium persulfate solution is 0.04-0.05mol/L, the mass-volume ratio of Ti ₃C₂ -Co@ chitosan, pyrrole, aqueous hydrochloric acid solution and ammonium persulfate solution is 1-1.2g:8-14mL:100-150mL:20mL, the power of ultrasonic treatment is 60-200W, the ultrasonic treatment time is 10-20min, the washed solution comprises water and ethanol, the drying temperature is 60-80 ℃, and the drying time is 22-24h.

10. Use of the multi-dimensional layered material according to any one of claims 1-4 or the multi-dimensional layered material obtained by the preparation method according to any one of claims 5-9 for the analytical detection of triazine herbicides and metabolites thereof, which are Chinese medicinal materials.