阅读说明：本技术 一种喹诺酮类药物通过型固相萃取柱的制备方法 (Preparation method of quinolone drug pass-through solid-phase extraction column ) 是由 张水锋 盛华栋 叶明立 潘项捷 冯婷婷 施元旭 于 2021-06-26 设计创作，主要内容包括：本发明涉及固相萃取柱的制备技术,旨在提供一种喹诺酮类药物通过型固相萃取柱的制备方法。包括：将螺旋状COFs复合材料与适量纯有机溶剂混合,超声处理至分散均匀；将预处理后的材料填充至聚丙烯材质的固相萃取柱中,两端分别用筛板封堵；将传统固相萃取吸附剂与适量纯有机溶剂混合,超声处理至分散均匀后；将预处理后的材料继续填充至固相萃取柱中,端部用筛板封堵后作为进样端；用纯有机溶剂上柱清洗后,以惰性气体吹扫除去残留有机溶剂后真空干燥,制得喹诺酮类药物通过型固相萃取柱。本发明具有制备工艺简单、对食品杂质截留能力强、净化效果好等优点。可显著降低质谱检测过程中的基质干扰效应,有效提改善质谱检测响应信号,有效提高灵敏度。(The invention relates to a preparation technology of a solid phase extraction column, and aims to provide a preparation method of a quinolone drug pass type solid phase extraction column. The method comprises the following steps: mixing the spiral COFs composite material with a proper amount of pure organic solvent, and carrying out ultrasonic treatment until the mixture is uniformly dispersed; filling the pretreated material into a solid phase extraction column made of polypropylene, and respectively plugging two ends of the solid phase extraction column with sieve plates; mixing a traditional solid phase extraction adsorbent with a proper amount of pure organic solvent, and performing ultrasonic treatment until the mixture is uniformly dispersed; continuously filling the pretreated material into a solid-phase extraction column, and plugging the end part by using a sieve plate to be used as a sample introduction end; and (3) cleaning the quinolone drug passing solid phase extraction column by using a pure organic solvent, removing residual organic solvent by purging with inert gas, and drying in vacuum to obtain the quinolone drug passing solid phase extraction column. The invention has the advantages of simple preparation process, strong food impurity interception capability, good purification effect and the like. The matrix interference effect in the mass spectrum detection process can be obviously reduced, the mass spectrum detection response signal can be effectively improved, and the sensitivity can be effectively improved.)

1. A preparation method of a quinolone drug pass-type solid phase extraction column is characterized by comprising the following steps:

(1) mixing the spiral COFs composite material with a proper amount of pure organic solvent, and carrying out ultrasonic treatment until the mixture is uniformly dispersed; filling the pretreated material into a solid phase extraction column made of polypropylene, and respectively plugging two ends of the solid phase extraction column with sieve plates;

(2) mixing a traditional solid phase extraction adsorbent with a proper amount of pure organic solvent, and performing ultrasonic treatment until the mixture is uniformly dispersed; continuously filling the pretreated material into the solid-phase extraction column in the step (1), and plugging the end part by using a sieve plate to be used as a sample introduction end;

(3) cleaning the quinolone drug pass-through solid phase extraction column by using a pure organic solvent, removing residual organic solvent by purging with inert gas, and drying in vacuum to obtain the quinolone drug pass-through solid phase extraction column;

the spiral COFs composite material is prepared by the following steps:

(1.1) taking 1,3, 5-tri (p-formylphenyl) benzene, tetraethylenepentamine, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the proportion of 0.4 mmol: 1.2 mmol: 8 mL: 6mL, adding into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min;

(1.2) transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: 0 → 6h, 40 → 80 ℃; 6 → 8h, 80 → 90 ℃, and keeping for 16 h; 24h → 30h, 90 → 60 ℃; 30h → 36h, 60 → 100 ℃, and keeping for 12 h; 48h → 54h, 100 → 60 ℃; 54h → 60h, 60 → 120 ℃ and keeping for 12 h; heating reaction is carried out according to the temperature-rising program;

(1.3) after the reaction is finished, naturally cooling to room temperature; and (3) carrying out vacuum filtration, collecting filter residues, washing with a pure organic solvent, and carrying out vacuum drying at 60 ℃ for 12h to obtain the spiral COFs composite material growing in an unlimited order.

2. The preparation method according to claim 1, wherein the mass ratio of the spiral COFs composite material to the traditional solid phase extraction adsorbent is 1: 2-1: 10.

3. The preparation method according to claim 1, wherein in the step (1), the ratio of the usage amount of the helical COFs composite material to the pure organic solvent is 50-300 mg: 5-20 mL, and the ultrasonic treatment is performed for 5-30 min after the helical COFs composite material and the pure organic solvent are shaken for 10 min.

4. The preparation method according to claim 1, wherein in the step (2), the ratio of the traditional solid phase extraction adsorbent to the pure organic solvent is 100-600 mg: 5-20 mL, and the ultrasonic treatment is performed for 5-30 min after the mixture is shaken for 10 min.

5. The method according to claim 1, wherein in the step (3), the vacuum drying conditions are as follows: 30-90 ℃ for 1-24 hours.

6. The method according to claim 1, wherein the pure organic solvent is any one of dimethyl sulfoxide, methanol, ethanol, acetonitrile, acetone, and dichloromethane.

7. The method of claim 1, wherein the conventional solid phase extraction adsorbent is C₁₈Any one of ion exchange resin, modified silica, alumina or PSA.

8. The method according to any one of claims 1 to 7, wherein the solid phase extraction column is a syringe outer cylinder having a radial dimension of 1.0 to 2.5 cm.

9. A method for using a quinolone drug pass-through solid-phase extraction column obtained by the preparation method according to any one of claims 1 to 7, comprising:

(1) the solid phase extraction column is vertically fixed on a frame, and a container is arranged below the outlet end at the bottom of the solid phase extraction column and is used for receiving and separating a sample;

(2) injecting a mixed liquid of water and acetonitrile into a sample introduction end of a solid phase extraction column, and sequentially flowing through a traditional solid phase extraction adsorbent and a spiral COFs composite material to realize activation of the solid phase extraction column;

(3) injecting the sample extracting solution into the sample introduction end of the solid phase extraction column, and enabling the sample extracting solution to sequentially flow through the traditional solid phase extraction adsorbent and the spiral COFs composite material to realize adsorption and interception of a sample matrix.

Technical Field

The invention relates to a preparation method of a solid phase extraction column, in particular to a preparation method of a quinolone drug pass type solid phase extraction column.

Background

Quinolone drugs are used as a class of broad-spectrum antibiotics for the prevention and treatment of infectious diseases, and are used in large quantities in animal husbandry. However, trace carbostyril drugs left in livestock, aquatic products and egg products potentially promote the formation of drug-resistant bacteria and even super multi-drug-resistant bacteria, thereby bringing harm to the human endocrine system. In view of this, rapid determination of residual quinolone drug in food has become an important issue for monitoring chemical pollutants in food.

Because the matrix of the sample of the residual quinolone drugs is complex, various and low in content (pg level), the enrichment and purification technology of the sample becomes important for monitoring the food chemical pollutants. At present, the sample pretreatment method of the quinolone drug residues comprises the following steps: liquid-liquid extraction and solid-phase extraction. Solid phase extractionExtraction has the advantages of less consumption of organic solvent and easy automation compared with liquid-liquid extraction. However, the traditional solid phase extraction column mostly adopts C₁₈The particles such as ion exchange resin, aluminum oxide and the like are used as fillers, the effect of separating and purifying the residual carbostyril drugs is poor, the matrix effect is strong, and the recovery rate is generally 70% or even lower. With C₁₈The small column can only remove part of non-polar lipid substances, while most of vegetables and fruits are water-soluble polar substances, so that separation and purification are difficult to realize.

Therefore, the novel solid phase extraction column is developed and applied to one-step purification of quinolone drug residues in food samples, and the novel solid phase extraction column has a wide application prospect and certain challenges.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects of the prior art and provides a preparation method of a quinolone drug pass-type solid phase extraction column.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the preparation method of the quinolone drug pass-through solid phase extraction column comprises the following steps:

(1) mixing the spiral COFs composite material with a proper amount of pure organic solvent, and carrying out ultrasonic treatment until the mixture is uniformly dispersed; filling the pretreated material into a solid phase extraction column made of polypropylene, and respectively plugging two ends of the solid phase extraction column with sieve plates;

(2) mixing a traditional solid phase extraction adsorbent with a proper amount of pure organic solvent, and performing ultrasonic treatment until the mixture is uniformly dispersed; continuously filling the pretreated material into the solid-phase extraction column in the step (1), and plugging the end part by using a sieve plate to be used as a sample introduction end;

(3) cleaning the quinolone drug pass-through solid phase extraction column by using a pure organic solvent, removing residual organic solvent by purging with inert gas, and drying in vacuum to obtain the quinolone drug pass-through solid phase extraction column;

the spiral COFs composite material is prepared by the following steps:

(1.1) taking 1,3, 5-tri (p-formylphenyl) benzene, tetraethylenepentamine, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the proportion of 0.4 mmol: 1.2 mmol: 8 mL: 6mL, adding into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min;

(1.2) transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: 0 → 6h, 40 → 80 ℃; 6 → 8h, 80 → 90 ℃, and keeping for 16 h; 24h → 30h, 90 → 60 ℃; 30h → 36h, 60 → 100 ℃, and keeping for 12 h; 48h → 54h, 100 → 60 ℃; 54h → 60h, 60 → 120 ℃ and keeping for 12 h; heating reaction is carried out according to the temperature-rising program;

(1.3) after the reaction is finished, naturally cooling to room temperature; and (3) carrying out vacuum filtration, collecting filter residues, washing with a pure organic solvent, and carrying out vacuum drying at 60 ℃ for 12h to obtain the spiral COFs composite material growing in an unlimited order.

Preferably, the mass ratio of the spiral COFs composite material to the traditional solid phase extraction adsorbent is 1: 2-1: 10.

Preferably, in the step (1), the ratio of the usage amount of the spiral COFs composite material to the pure organic solvent is 50-300 mg: 5-20 mL, and the spiral COFs composite material is shaken for 10min and then subjected to ultrasonic treatment for 5-30 min.

Preferably, in the step (2), the ratio of the traditional solid phase extraction adsorbent to the pure organic solvent is 100-600 mg: 5-20 mL, and the ultrasonic treatment is carried out for 5-30 min after the mixture is shaken for 10 min.

Preferably, in the step (3), the vacuum drying conditions are as follows: 30-90 ℃ for 1-24 hours.

Preferably, the pure organic solvent is any one of dimethyl sulfoxide, methanol, ethanol, acetonitrile, acetone and dichloromethane.

Preferably, the conventional solid phase extraction adsorbent is C₁₈One of ion exchange resin, modified silica, alumina or PSA.

Preferably, the solid phase extraction column is an outer syringe cylinder with the radial dimension of 1.0-2.5 cm.

The invention further provides a using method of the quinolone drug pass-type solid phase extraction column, which comprises the following steps:

(1) the solid phase extraction column is vertically fixed on a frame, and a container is arranged below the outlet end at the bottom of the solid phase extraction column and is used for receiving and separating a sample;

(2) injecting a mixed liquid of water and acetonitrile into a sample introduction end of a solid phase extraction column, and sequentially flowing through a traditional solid phase extraction adsorbent and a spiral COFs composite material to realize activation of the solid phase extraction column;

(3) injecting the sample extracting solution into the sample introduction end of the solid phase extraction column, and enabling the sample extracting solution to sequentially flow through the traditional solid phase extraction adsorbent and the spiral COFs composite material to realize adsorption and interception of a sample matrix.

Description of the inventive principles:

the invention adopts covalent organic framework materials (COFs) as the passing solid phase extraction filler for purifying the residual carbostyril in food samples. The filler has strong adsorption capacity on interfering matrixes in food samples, quinolone drug residues can completely pass through the filler, the purification purpose is achieved, and the collected purified test solution can be directly used for analysis of instruments. The passing type solid phase extraction column can replace the traditional C₁₈The isocrystan extraction column solves the problems of complex and tedious pretreatment and low recovery rate. Compared with other solid phase extraction fillers such as C, the through type solid phase extraction column prepared by the invention is used for detecting quinolone drugs₁₈The method has the advantages of more thorough elimination of matrix interference effect and improvement of detection sensitivity.

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

1. the spiral COFs composite material obtained by using a specific preparation technology can efficiently adsorb and retain complex matrixes such as grease, sugar, pigment and the like in a food sample, so that the influence of matrix effect on the qualitative and quantitative effects of quinolone medicines is reduced.

2. The invention adopts two-section type filler arrangement, the traditional solid phase extraction adsorbent is in front, and the spiral COFs composite material is behind; the arrangement mode can realize further purification of the sample matrix on the basis that the traditional adsorbent adsorbs and intercepts complex matrixes such as grease, sugar, pigment and the like in the food sample.

3. The quinolone medicine pass solid phase extraction column prepared by the invention has the advantages of simple preparation process, strong food impurity interception capability, good purification effect and the like.

4. Compared with other solid phase extraction fillers such as C, the through type solid phase extraction column prepared by the invention₁₈The adsorption capacity to food substrates is larger, the quinolone drugs are hardly adsorbed, and the substrate interference effect in the mass spectrum detection process can be obviously reduced. The mass spectrum detection response signal can be effectively improved, so that the peak shape of the chromatographic peak of the target object is more symmetrical and sharp, the background base line is lower and flatter, and the sensitivity is effectively improved.

Drawings

FIG. 1 is an LC-MS/MS spectrum of residual quinolone drugs in a food product purified with a spiral COFs filler according to example one of the present invention.

FIG. 2 is an LC-MS/MS spectrum of residual quinolone drugs in a food product not purified with the helical COFs filler according to example one of the present invention.

FIG. 3 is a schematic diagram of the use of a quinolone drug pass-through solid phase extraction column.

Reference numbers in the figures: 1 a sample matrix; 2 a quinolone drug; 3, a sieve plate; 4, traditional adsorption packing; 5 spiral COFs adsorbing filler.

Detailed Description

The following further describes the present invention with reference to the drawings and the following embodiments, so as to make the advantages and benefits of the present invention more prominent, but the present invention is not limited to the following embodiments.

1. The preparation method of the quinolone drug pass-type solid phase extraction column provided by the invention comprises the following steps:

(1) mixing the spiral COFs composite material with a proper amount of pure organic solvent, and carrying out ultrasonic treatment until the mixture is uniformly dispersed; filling the pretreated material into a solid phase extraction column made of polypropylene, and respectively plugging two ends of the solid phase extraction column with sieve plates;

the solid phase extraction column is an outer barrel of the injector with the radial dimension of 1.0-2.5 cm. The dosage ratio of the spiral COFs composite material to the pure organic solvent is 50-300 mg: 5-20 mL, and the ultrasonic treatment is carried out for 5-30 min after the materials are shaken for 10 min.

(2) Mixing a traditional solid phase extraction adsorbent with a proper amount of pure organic solvent, and performing ultrasonic treatment until the mixture is uniformly dispersed; continuously filling the pretreated material into the solid-phase extraction column in the step (1), and plugging the end part by using a sieve plate to be used as a sample introduction end;

the dosage ratio of the traditional solid phase extraction adsorbent to the pure organic solvent is 100-600 mg: 5-20 mL, and the ultrasonic treatment is carried out for 5-30 min after the traditional solid phase extraction adsorbent is shaken for 10 min.

(3) Cleaning the quinolone drug pass-through solid phase extraction column by using a pure organic solvent, removing residual organic solvent by purging with inert gas, and drying in vacuum at the temperature of 30-90 ℃ for 1-24 hours to obtain a quinolone drug pass-through solid phase extraction column;

the spiral COFs composite material is prepared by the following steps:

(1.1) taking 1,3, 5-tri (p-formylphenyl) benzene, tetraethylenepentamine, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the proportion of 0.4 mmol: 1.2 mmol: 8 mL: 6mL, adding into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min;

(1.2) transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: 0 → 6h, 40 → 80 ℃; 6 → 8h, 80 → 90 ℃, and keeping for 16 h; 24h → 30h, 90 → 60 ℃; 30h → 36h, 60 → 100 ℃, and keeping for 12 h; 48h → 54h, 100 → 60 ℃; 54h → 60h, 60 → 120 ℃ and keeping for 12 h; heating reaction is carried out according to the temperature-rising program;

the expression herein refers to a specific method of programming temperature, not representing different temperatures or time intervals, but to specific parameters of the temperature programming settings. For example, 0 → 6h, 40 → 80 ℃ means that the reaction temperature is increased from 40 ℃ to 80 ℃ within 6 hours from the start of the reaction; 6 → 8h, 80 → 90 ℃ and keeping for 16h means that the reaction temperature is increased from 80 ℃ to 90 ℃ within two hours from the 6 th hour to 8 th hour of the reaction, and the reaction is continued for 16 hours while keeping the temperature.

(1.3) after the reaction is finished, naturally cooling to room temperature; and (3) carrying out vacuum filtration, collecting filter residues, washing with a pure organic solvent, and carrying out vacuum drying at 60 ℃ for 12h to obtain the spiral COFs composite material growing in an unlimited order.

Tests show that the inner diameter of a spiral ring of the spiral COFs composite material is about 400nm, the outer diameter of the spiral ring is about 1500nm, the appearance is regular, and the spiral ring spacing is uniform. The special configuration of the material can realize high-efficiency interception and adsorption of complex matrixes in food samples and reduce the matrix effect.

The pure organic solvent is any one of dimethyl sulfoxide, methanol, ethanol, acetonitrile, acetone and dichloromethane. The traditional solid phase extraction adsorbent is C₁₈One of ion exchange resin, modified silica, alumina or PSA. The mass ratio of the spiral COFs composite material to the traditional solid phase extraction adsorbent is 1: 2-1: 10.

2. The spiral COFs composite material used by the invention is prepared by the following steps:

(1.1) taking 1,3, 5-tri (p-formylphenyl) benzene, tetraethylenepentamine, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the proportion of 0.4 mmol: 1.2 mmol: 8 mL: 6mL, adding into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min;

(1.2) transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: 0 → 6h, 40 → 80 ℃; 6 → 8h, 80 → 90 ℃, and keeping for 16 h; 24h → 30h, 90 → 60 ℃; 30h → 36h, 60 → 100 ℃, and keeping for 12 h; 48h → 54h, 100 → 60 ℃; 54h → 60h, 60 → 120 ℃ and keeping for 12 h; heating reaction is carried out according to the temperature-rising program;

(1.3) after the reaction is finished, naturally cooling to room temperature; and (3) carrying out vacuum filtration, collecting filter residues, washing with a pure organic solvent, and carrying out vacuum drying at 60 ℃ for 12h to obtain the spiral COFs composite material growing in an unlimited order.

3. The application method of the quinolone drug pass-through solid phase extraction column comprises the following steps:

(1) the solid phase extraction column is kept vertical and fixed on a frame, and a container for receiving and separating samples is arranged below the outlet end at the bottom of the solid phase extraction column;

(2) injecting a mixed liquid of water and acetonitrile into a sample introduction end of a solid phase extraction column, and sequentially flowing through a traditional solid phase extraction adsorbent and a spiral COFs composite material to realize activation of the solid phase extraction column;

(3) injecting the sample extracting solution into the sample introduction end of the solid phase extraction column, and enabling the sample extracting solution to sequentially flow through the traditional solid phase extraction adsorbent and the spiral COFs composite material to realize adsorption and interception of a sample matrix.

4. The performance evaluation method of the quinolone drug passing solid phase extraction column is as follows:

(1) activating a quinolone drug passing solid phase extraction column by using 5mL of water and acetonitrile in sequence, then sampling 5mL of tomato sample extracting solution extracted by acidifying acetonitrile at the flow rate of 1.0mL/min, passing the effluent through a 0.22 mu m polytetrafluoroethylene microporous filter membrane, and analyzing by adopting an ultra-fast liquid chromatography-tandem mass spectrometer.

(2) Activating a quinolone drug passing solid phase extraction column by using 5mL of water and acetonitrile in sequence, then loading 5mL of pork sample extracting solution extracted by acidifying acetonitrile at the flow rate of 1.0mL/min, and analyzing the effluent by using an ultra-fast liquid chromatography-tandem mass spectrometer after passing through a 0.22-micron polytetrafluoroethylene microporous filter membrane.

5. Example data:

the raw material substances, raw material formulas and preparation conditions of examples 1 to 8 were all completed as described above, and table 1 shows specific applications of some of the variable parameters or options.

Table 1: in the embodiments 1-8 of the invention, the raw material components and part of the parameters for preparation

6. Application example:

the following application example is to separate and purify 17 quinolone drugs from pork and 17 quinolone drugs from tomatoes by using the pass-through solid-phase extraction column prepared in example 2.

(1) Accurately weighing a certain amount of enrofloxacin, ciprofloxacin, ofloxacin, pefloxacin, norfloxacin, lomefloxacin, flumequine, oxolinic acid, marbofloxacin, sarafloxacin, danofloxacin, difloxacin, fleroxacin, cinoxacin, enoxacin, nalidixic acid and orbifloxacin standard substances into a 5.0mL volumetric flask, dissolving the standard substances with acetonitrile and fixing the volume to a scale to obtain a mixed standard application liquid, wherein the concentration of enrofloxacin, ofloxacin, lomefloxacin, flumequine, oxolinic acid, marbofloxacin, danofloxacin, difloxacin, fleroxacin, cinoxacin, nalidixic acid and orbifloxacin is 1.0 mg/L; the concentration of ciprofloxacin, pefloxacin, norfloxacin and sarafloxacin was 5.0 mg/L.

(2) Weighing 2.0g of a group of homogenized blank matrix samples, respectively adding 17 kinds of quinolone mixed standard application solutions, and preparing matrix standard-adding series working solutions with different concentrations, wherein: the concentration of enrofloxacin, ofloxacin, lomefloxacin, flumequine, oxolinic acid, marbofloxacin, danofloxacin, difloxacin, fleroxacin, cinoxacin, enoxacin, nalidixic acid and orbifloxacin is 0.2-20 mug/kg; the concentration of ciprofloxacin, pefloxacin, norfloxacin and sarafloxacin is 1.0-100 mug/kg.

(3) The sample was extracted with acidified acetonitrile (0.1%, V/V), 5mL of the extract was transferred to the sample at a flow rate of 1.0mL/min, and the effluent was passed through a 0.22 μm teflon microporous membrane and analyzed by ultrafast liquid chromatography-tandem mass spectrometer, the results being shown in fig. 1. The results show that: the carbostyril drug passing solid phase extraction column prepared by the invention has stronger separation and purification capacity to the carbostyril drugs, and the standard recovery rates of 17 carbostyril drugs in pork and 17 carbostyril drugs in tomato are 82.3-112% and 90.1-116% respectively; compared with the traditional PSA solid phase extraction column, the standard recovery rate of the PSA solid phase extraction column on 17 quinolone drugs in tomatoes is better (76.3-90.2%), while the standard recovery rate on 17 quinolone drugs in pork is 50.2-71.6%. The comparison result shows that the quinolone drug pass-through solid phase extraction column prepared by the invention is a potential solid phase extraction column for effectively separating and purifying quinolone drug residues in food.

(4) Chromatographic conditions are as follows:

a chromatographic column: shim-pack XR-ODS II (150 mm. times.2.0 mm i.d.,2.2 μm); mobile phase: phase A: aqueous phase (0.1% formic acid in water); phase B: and (3) acetonitrile. Gradient elution procedure: 0 → 2.00min, 10 → 60.0% B; 2.00 → 5.00min, 60 → 90.0% B; 5.00 → 7.50min, 90.0% B; 7.50 → 8.00min, 90.0 → 10% B; 8.00 → 10.00min, 10% B; flow rate: 0.3 mL/mim; the sample size was 2.0. mu.L.

(5) Mass spectrum conditions:

an ion source: an electrospray ion source; the scanning mode is as follows: scanning positive ions; quantitative detection mode: multiple reaction monitoring mode (MRM); electrospray voltage (IS): 5500V (positive ion mode); atomization gas pressure (GS 1): 50.0 psi; auxiliary airflow rate (GS 2): 50.0 psi; air curtain pressure (CUR): 40.0 psi; collision gas (CAD): 7.0 psi; ion source Temperature (TEM): 500 ℃; scanning time: 30 ms; collision cell exit voltage (CXP): 11.0V; collision cell entrance voltage (EP): 10.0V; the qualitative ion pair, quantitative ion pair, collisional gas energy (CE) and declustering voltage (DP) are shown in Table 2.

TABLE 2 qualitative and quantitative ion pairs and Cone hole Voltage, Collision energy, ion Scan modes for targets

Note: quantification of ions.

The quinolone drug pass-type solid phase extraction column has simple preparation process and low cost. Experiments prove that: the carbostyril drug obtained by the invention is uniformly distributed through the solid-phase extraction column and has stable property; has good purification effect on trace quinolone drugs left in vegetables and meat products. The performance of the quinolone drug passing type solid phase extraction column is evaluated by detecting actual samples. Methanol-water solutions with different proportions are adopted to clean the quinolone drug residue through a solid phase extraction column. The results show that: the carbostyril drug passing solid phase extraction column prepared by the invention can effectively reduce the influence of matrix inhibition effect on the qualitative and quantitative target analytes, the carbostyril drug residue passing solid phase extraction column still has good interception capability on complex matrixes in samples after being used for 10 times, the recovery rate of the carbostyril drugs is more than 90.2%, and the recovery rate of the traditional SPE small column on the carbostyril drugs is only 70% or even lower.