Triamino series skeleton hybrid monolithic material, preparation method and QuEChERS pretreatment method

Abstract

The invention discloses a triamino series skeleton hybrid monolithic material, a preparation method and a QuEChERS pretreatment method, the preparation method comprises the following steps: step 1, mixing tetraethoxysilane and diethylenetriamine propyl trimethoxy silane to obtain a prepolymer solution; step 2, performing water bath heating on the pre-polymerized liquid, and cooling to room temperature to obtain a primary product; 3, washing the primary product for multiple times; and step 4, drying the washed preliminary product to obtain the triamino series skeleton hybrid monolithic material. Diethylenetriamine propyl trimethoxy silane is adopted as a silanization reagent for the first time to introduce amino groups, the triamino series skeleton hybrid integral material is synthesized through a one-pot method, preparation is easy, reproducibility is good, cost is low, amino groups on the surface of the material are evenly distributed, the material is loose and porous, the specific surface area is large, the prepared material serves as a QuEChERS reagent, and the specific surface area of the material is larger than that of the QuEChERS reagent. The method can realize extraction and purification of various sleeping and calming medicines, and is high in recovery rate and good in matrix purification effect.

Description

Technical Field

[0001] The present invention relates to the technical field of food residue detection, and in particular to a triamino tandem skeleton hybrid monolithic material, a preparation method and a QuEChERS pretreatment method. Background Art

[0002] Animal-derived foods, as one of the important sources of protein in people's daily diet, play an important role in food safety. At present, many vendors still use hypnotic sedatives in the breeding and transportation of poultry and aquatic products to reduce the damage caused by poultry bumps in order to reduce costs, resulting in the presence of hypnotic sedatives in animal-derived foods. According to the relevant provisions of the National Veterinary Drug Administration Regulations, it is prohibited to detect hypnotic sedatives in animal-derived foods. Hypnotic sedatives mainly include benzodiazepines. There are two major categories: hypnotic drugs and phenothiazines. Both of them usually have the effects of sedation, anti-anxiety, relieving muscle pain and have a certain hypnotic effect. They are often used to treat anxiety disorders, relieve anxiety symptoms and anxiety related to depressive symptoms. Excessive consumption of hypnotic drugs can lead to drug dependence or cognitive impairment, and may also cause fatigue, drowsiness, mild headaches, weakness, dizziness, movement disorders, restlessness, excitement and other adverse reactions, which are very harmful to the human body. Since animal-derived foods are mostly solid samples with complex matrices, they do not meet the requirements of direct instrument detection. Sample pretreatment such as extraction and purification is required before instrumental analysis and detection. Therefore, it is of great significance to develop and establish a fast and efficient sample pretreatment method for the separation and analysis of hypnotic drug residues in animal-derived foods.

[0003] At present, the commonly used sample pretreatment methods mainly include solid phase extraction, liquid-liquid extraction and QuEChERS. Although these traditional methods such as solid phase extraction have the advantages of high selectivity and wide application range, they also have many defects such as cumbersome operation and low extraction efficiency. The solid phase extraction method usually requires a long operation time, including sample pretreatment, column elution, solvent volatilization and concentration. The whole process is relatively cumbersome, requires more operation steps and time, and is time-consuming and laborious; during the solid phase extraction process, the sample needs to go through multiple adsorption, elution and concentration steps, which is easy to cause the loss of the target object and reduce the accuracy and sensitivity of the analysis. Liquid-liquid extraction has problems such as difficulty in selecting the extractant, residual extractant, and excessive use of organic solvent. Although the QuEChERS method has the advantages of convenience, rapidity, simple operation, and high extraction efficiency, most of the existing QuEChERS materials are expensive and costly, and the recovery rates for different residues vary and the applicability is poor. Summary of the invention

[0004] Purpose of the invention: In view of the above shortcomings, the present invention provides a triamino tandem framework hybrid monolithic material, a preparation method and a QuEChERS pretreatment method.

[0005] Technical solution: To solve the above problems, the present invention adopts a triamino tandem skeleton hybrid monolithic material, a preparation method and a QuEChERS pretreatment method, wherein the preparation method comprises the following steps:

[0006] Step 1, tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane are mixed to obtain a prepolymer solution;

[0007] Step 2, heating the prepolymer solution in a water bath, and cooling it to room temperature to obtain a preliminary product;

[0008] Step 3, washing the preliminary product multiple times;

[0009] Step 4: Dry the washed preliminary product to obtain a triamino tandem framework hybrid monolithic material.

[0010] Furthermore, the volume ratio of tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane added in step 1 is 5:1.

[0011] Furthermore, in step 1, tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane are added to a co-solvent and mixed. The co-solvent is prepared by dissolving hexadecyltrimethylammonium bromide in a mixture of anhydrous ethanol and pure water. The amount of hexadecyltrimethylammonium bromide added is 0.4-0.6 g, and the volume ratio of anhydrous ethanol to pure water is 3:1.

[0012] Furthermore, in step 2, the water bath heating temperature is 40-50° C., and the heating time is 4-6 hours.

[0013] Furthermore, step 3 is specifically: using anhydrous ethanol and distilled water to wash the preliminary product repeatedly and alternately.

[0014] Furthermore, the drying in step 4 is specifically as follows: firstly, the preliminary product is filtered, and then the preliminary product is placed in an oven and dried at 60-70°C.

[0015] The present invention also provides a triamino tandem skeleton hybrid integral material prepared by the above preparation method.

[0016] The present invention also provides a QuEChERS pretreatment method using the above-mentioned triamino tandem framework hybrid monolithic material, characterized in that it comprises the following steps:

[0017] Step 1: Place the sample to be tested into a tissue grinding tube, add acetonitrile for vortex oscillation and tissue grinding;

[0018] Step 2, adding anhydrous magnesium sulfate and sodium acetate into the tissue grinding tube, and vortexing again;

[0019] Step 3, centrifuging the tissue grinding tube and extracting the supernatant after centrifugation;

[0020] Step 4, transferring the supernatant to a centrifuge tube containing the triamino tandem framework hybrid monolithic material, vortexing the centrifuge tube and centrifuging again;

[0021] Step 5: Extract the supernatant after centrifugation in step 4 and filter it to obtain the extract to be tested.

[0022] Furthermore, the addition amount of the triamino tandem framework hybrid monolithic material is 20-50% of the mass of the sample to be tested.

[0023] Furthermore, in step 5, the supernatant is filtered using a 0.22 μm organic phase filter membrane.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) For the first time, diethylenetriaminepropyltrimethoxysilane is used as a silanization agent to introduce amino groups, and a triamino tandem skeleton hybrid monolithic material is synthesized by a "one-pot method". The preparation is simple, reproducible, and low-cost. The amino groups on the surface of the material are evenly distributed, loose and porous, and have a large specific surface area. (2) The triamino tandem skeleton hybrid monolithic material is used as a QuEChERS reagent to achieve the extraction and purification of 7 hypnotic sedatives such as oxazepam, lorazepam, diazepam, clonazepam, chlordiazepoxide, nitrazepam, and chlorpromazine in animal-derived foods. The method has a high recovery rate and a good matrix purification effect. There is no significant difference in the recovery effect of different residues, and the applicability is strong. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the overall process of the material preparation method of the present invention;

[0026] Figure 2 This is the Fourier transform infrared spectrum of the material obtained in Example 1;

[0027] Figure 3 This is a scanning electron microscope image of the material obtained in Example 1;

[0028] Figure 4 This is the element mapping diagram of the material obtained in Example 1;

[0029] Figure 5 This is a schematic diagram of the QuEChERS pretreatment process of Example 2. DETAILED DESCRIPTION

[0030] Embodiment 1

[0031] like Figure 1 As shown, a method for preparing a triamino tandem skeleton hybrid monolithic material in this embodiment comprises the following steps:

[0032] Step 1, add 0.44g hexadecyltrimethylammonium bromide (CTAB) to a mixture of 4.5mL anhydrous ethanol and 1.5mL pure water, and vortex ultrasound to completely dissolve CTAB to form a cosolvent. The cosolvent can promote the mutual dissolution of the two silanization reagents, make the two reagents fully mixed and evenly, and improve the uniformity and repeatability of material synthesis; CTAB can dissolve the reactants and increase the specific surface area of ​​the resulting material, and other surfactants can also be used instead. Add 3.3mL tetraethoxysilane (TEOS) and 0.66mL diethylenetriaminopropyltrimethoxysilane (AAAPTMS), vortex ultrasound to mix evenly, and obtain a prepolymer solution. In this step, the addition ratio of TEOS and AAAPTMS is the key influencing factor of the final synthetic material, and the proportion and addition amount of other substances have little effect on the final material performance.

[0033] Step 2: Heat the prepolymer solution in a water bath at 45° C. for 4 hours and cool to room temperature to obtain a preliminary product.

[0034] Step 3: The preliminary product is repeatedly washed alternately with anhydrous ethanol and distilled water to remove unreacted reagents and the template agent CTAB.

[0035] Step 4: first filter the preliminary product, then place the preliminary product in an oven and dry it at 60-70° C. to obtain a triamino tandem framework hybrid monolithic material.

[0036] like Figure 2 The Fourier transform infrared spectrum of the final prepared triamino tandem skeleton hybrid monolithic material is shown in the figure: there is an obvious -1 The characteristic peak of saturated CH stretching vibration at 1473.12 cm -1 The CN stretching vibration peak at 1647.01 cm -1 The NH stretching vibration peak at 100 nm indicates that the amino group from AAAPTMS has been successfully connected to the material skeleton, indicating that the triamino material proposed by this method was successfully prepared. Figure 3 As shown in the SEM image, it can be seen that the surface of the material contains rough small particles, and the overall surface features are loose and porous, indicating that the material has a large specific surface area and a high adsorption capacity for substances. Figure 4 As shown, the material contains Si, O, C, and N elements, and the distribution of each element is relatively uniform, indicating that the amino group distribution uniformity of the proposed material is high, further indicating that the material was successfully prepared.

[0037] Embodiment 2

[0038] like Figure 5 As shown, this embodiment provides an application of the above-mentioned triamino tandem framework hybrid monolithic material in QuEChERS pretreatment in the analysis of hypnotic sedative drugs in animal-derived food, comprising the following steps:

[0039] Step 1. Weigh 1 g of the chicken sample to be tested and put it into a tissue grinding tube. Add 5 mL of acetonitrile, vortex for 5 minutes, and then grind the tissue for 10 minutes.

[0040] Step 2: Add 1.2 g of anhydrous magnesium sulfate and 0.3 g of sodium acetate into the tissue grinding tube and vortex again for 5 min.

[0041] Step 3: Centrifuge the tissue grinding tube and extract the supernatant after centrifugation. At this time, the remaining sedatives and some matrix interfering substances in the sample are extracted into the acetonitrile extract.

[0042] Step 4, transfer the supernatant to a centrifuge tube containing 0.3 g of the triamino tandem framework hybrid monolithic material, vortex the centrifuge tube for 5 minutes and centrifuge again. At this time, the matrix interfering substances in the extract are adsorbed by the triamino framework hybrid monolithic material, and the hypnotic sedative drugs are retained in the acetonitrile extract.

[0043] The amount of triamino tandem skeleton hybrid overall material and the detection method can be adjusted according to one's own experimental conditions. If the signal response of the detection instrument is greatly affected by the matrix, the amount of material can be appropriately increased; if the signal response of the detection instrument is less affected by the matrix, the amount of material can be appropriately reduced.

[0044] Step 5: Extract the supernatant after centrifugation in step 4, and filter the supernatant through a 0.22 μm organic phase filter membrane to obtain an extract to be tested.

[0045] In order to verify the effect of the triamino tandem framework hybrid monolithic material prepared by the present invention, the test extract was detected by ultra-high performance liquid chromatography tandem triple quadrupole ion trap mass spectrometer, and the specific detection ion pairs are shown in Table 1. The contents of 7 kinds of hypnotic sedative drugs such as oxazepam, lorazepam, diazepam, clonazepam, chlordiazepoxide, nitrazepam, and chlorpromazine in the test extract were obtained respectively.

[0046] Table 1 Detection ion table

[0047]

[0048]

[0049] Table 2 lists the experimental results of the extraction and detection of 7 hypnotic sedatives in chicken using the QuEChERS method based on triamino tandem skeleton hybrid monolithic materials. Three spiked amounts were used to investigate this method.

[0050] Table 2 QuEChERS method for triamino tandem framework hybrid monolithic materials for sample determination results

[0051]

[0052] As can be seen from Table 2, the results of the extraction and detection of 7 hypnotic sedatives in chicken using the QuEChERS method based on the triamino tandem skeleton hybrid monolith proposed in this method are ideal. Under the three standard addition amounts of low, medium and high, the recovery rates of the 7 hypnotic sedatives are high, reaching 81.5-103%, with high determination accuracy, and no significant difference in the recovery rates of the 7 drugs, showing good applicability.

[0053] Comparative Example

[0054] The commercial QuEChERS material was used to extract and detect 7 hypnotic sedatives in chicken, and the performance was compared with the material proposed in this method. Except for the different materials used, other operations were consistent with this experimental method. The experimental results of the commercial QuEChERS material are shown in Table 3.

[0055] Table 3 Results of commercial QuEChERS materials used for sample determination

[0056]

[0057] It can be seen that when the commercial QuEChERS material is used to extract and detect 7 hypnotic sedatives in chicken, the recovery rates of different target substances are slightly different. The recovery rates of clonazepam, lorazepam and diazepam reach 65% to 75%, and the recovery rates of chlordiazepoxide, nitrazepam, chlorpromazine and oxazepam are between 30% and 60%. Compared with the commercial QuEChERS material, under the same spiked amount, the overall recovery rate of the QuEChERS method based on the triamino tandem framework hybrid monolithic material proposed in this method is significantly higher, and the recovery rate difference between different target substances is smaller, indicating that the material proposed in this method has better applicability.

[0058] In summary, the "one-pot method" proposed in the present invention is used to prepare a triamino tandem skeleton hybrid monolithic material. The preparation method is simple and has good reproducibility. The amino groups on the surface of the material are evenly distributed, loose and porous, and have a large specific surface area. The QuEChERS method based on the triamino tandem skeleton hybrid monolithic material can be used for the extraction and purification of seven hypnotic sedatives, including oxazepam, lorazepam, diazepam, clonazepam, chlordiazepoxide, nitrazepam, and chlorpromazine, in animal-derived foods. The pretreatment method has low cost, simple operation, high recovery rate, and good accuracy, and can meet the actual analysis and detection of hypnotic sedatives in animal-derived foods.

Claims

1. A method for preparing a triamino tandem skeleton hybrid monolithic material, characterized in that: The following steps are involved: Step 1, tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane are mixed to obtain a prepolymer solution; Step 2, heating the prepolymer solution in a water bath, and cooling it to room temperature to obtain a preliminary product; Step 3, washing the preliminary product multiple times; Step 4: Dry the washed preliminary product to obtain a triamino tandem framework hybrid monolithic material.

2. The preparation method according to claim 1, characterized in that The volume ratio of tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane added in step 1 is 5:

1.

3. The preparation method according to claim 1, characterized in that: In step 1, tetraethoxysilane and diethylenetriaminopropyltrimethoxysilane are added to a co-solvent and mixed. The co-solvent is prepared by dissolving hexadecyltrimethylammonium bromide in a mixture of anhydrous ethanol and pure water. The amount of hexadecyltrimethylammonium bromide added is 0.4-0.6 g, and the volume ratio of anhydrous ethanol to pure water is 3:

1.

4. The preparation method according to claim 1, characterized in that: In step 2, the water bath heating temperature is 40-50° C. and the heating time is 4-6 hours.

5. The preparation method according to claim 1, characterized in that: Step 3 is specifically as follows: the preliminary product is repeatedly washed alternately with anhydrous ethanol and distilled water.

6. The preparation method according to claim 1, characterized in that: The drying in step 4 is specifically as follows: firstly, the preliminary product is filtered, and then the preliminary product is placed in an oven and dried at 60-70°C.

7. A triamino tandem skeleton hybrid monolithic material prepared by the preparation method according to any one of claims 1 to 6.

8. A QuEChERS pretreatment method using the triamino tandem framework hybrid monolithic material of claim 7, characterized in that: The following steps are involved: Step 1: Place the sample to be tested into a tissue grinding tube, add acetonitrile for vortex oscillation and tissue grinding; Step 2, add anhydrous magnesium sulfate and sodium acetate into the tissue grinding tube, and vortex again; Step 3, centrifuging the tissue grinding tube and extracting the supernatant after centrifugation; Step 4, transferring the supernatant to a centrifuge tube containing the triamino tandem framework hybrid monolithic material, vortexing the centrifuge tube and centrifuging again; Step 5: Extract the supernatant after centrifugation in step 4 and filter it to obtain the extract to be tested.

9. The QuEChERS pretreatment method according to claim 8, characterized in that: The addition amount of the triamino tandem framework hybrid monolithic material is 20-50% of the mass of the sample to be tested.

10. The QuEChERS pretreatment method according to claim 8, characterized in that: In step 5, the supernatant is filtered using a 0.22 μm organic phase filter membrane.

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