阅读说明：本技术 一种新型功能化磁性离子液体及其制备方法和应用 (Novel functionalized magnetic ionic liquid and preparation method and application thereof ) 是由 许旭 高佳欣 李响 刘桂彬 张蕾 于 2021-08-11 设计创作，主要内容包括：本发明涉及一种新型功能化磁性离子液体的制备方法和应用。所述的新型功能化离子液体中,阳离子具有长链烷基、苄基结构或羰基结构或甲氧基结构。阴离子为硫氰酸钴离子。本发明提供的新型功能化离子液体作为微萃取相,显示出良好的疏水性,对水体中的氟喹诺酮类药物有较高的提取能力,并具有明显的蓝色颜色标记,易于通过磁铁从水溶液中视觉分离。本发明涉及的合成方法简单,反应条件温和。(The invention relates to a preparation method and application of a novel functionalized magnetic ionic liquid. In the novel functionalized ionic liquid, cations have long-chain alkyl, benzyl structures or carbonyl structures or methoxy structures. The anion is cobalt thiocyanate ion. The novel functionalized ionic liquid provided by the invention is used as a micro-extraction phase, shows good hydrophobicity, has higher extraction capacity on fluoroquinolone medicines in a water body, has an obvious blue color mark, and is easy to visually separate from an aqueous solution through a magnet. The synthesis method provided by the invention is simple and mild in reaction conditions.)

1. A novel functionalized magnetic ionic liquid is characterized in that the structural formulas are shown as formulas (I) to (III):

2. the preparation method of the novel functionalized magnetic ionic liquid as claimed in claim 1, characterized by comprising the following steps:

1) mixing n-octylamine and benzyl compounds with different functional groups in an organic solvent, reacting under the reflux condition, removing the organic solvent through rotary evaporation, washing crude substances for a plurality of times by using n-hexane under ultrasonic treatment, and then carrying out vacuum drying to obtain an intermediate;

2) mixing the intermediate, cobalt chloride hexahydrate and potassium thiocyanate in an organic solvent, reacting under the reflux condition, centrifuging to remove unreacted substances, performing rotary evaporation on supernate to remove the organic solvent, washing a product with excessive deionized water, and performing vacuum drying to obtain the novel functionalized ionic liquid.

3. The method for preparing a novel functionalized magnetic ionic liquid according to claim 2, wherein the molar ratio of the benzyl compound: n-octylamine: cobalt chloride hexahydrate: potassium thiocyanate is 1: 1: 1: 4.

4. the method for preparing the novel functionalized magnetic ionic liquid according to claim 3, wherein in the step 1), the benzyl compound is one of benzyl bromide, 1, 4- (bromomethyl) phenyl) ethanone and 3-methoxybenzyl bromide.

5. The method for preparing the novel functionalized magnetic ionic liquid according to claim 4, wherein in the step 1), the organic solvent is chloroform.

6. The method for preparing the novel functionalized magnetic ionic liquid according to claim 5, wherein in the step 1), the reaction temperature is 70-90 ℃ and the reaction time is 72 hours.

7. The method for preparing the novel functionalized magnetic ionic liquid according to claim 6, wherein in the step 2), the organic solvent is acetone.

8. The method for preparing a novel functionalized magnetic ionic liquid according to claim 7, wherein in the step 2), the reaction temperature is 50-60 ℃ and the reaction time is 5 hours.

9. The use of a novel functionalized magnetic ionic liquid according to claim 1 for the extraction of fluoroquinolones.

10. The use according to claim 9, characterized in that it consists in adding a new functionalized magnetic ionic liquid according to claim 1 to an aqueous solution containing fluoroquinolone antibiotics, extracting it with a vortexer and then separating it with a magnet.

Technical Field

The invention relates to the technical field of ionic liquid, in particular to a preparation method and application of novel functionalized magnetic ionic liquid, and especially relates to ionic liquid with benzyl or carbonyl or methoxy and application thereof in liquid-liquid extraction of fluoroquinolone medicines in water.

Background

Fluoroquinolone antibiotics are widely used as broad-spectrum active drugs against various pathogenic bacterial infections. With the increasing use of fluoroquinolone antibiotics in human and veterinary clinical treatments, fluoroquinolone antibiotics have been discharged into the aqueous environment in their original form or as potentially active metabolites, which may lead to the development of bacterial resistance or have adverse effects on humans and the environment. Therefore, selective extraction of trace fluoroquinolone antibiotics in water is critical to human health and environmental protection.

Ionic liquids have low vapor pressure, good solubility and high chemical stability, and are promising extraction solvents in liquid-liquid extraction. In recent years, new magnetic ionic liquids have been developed which combine the above-mentioned excellent properties of ionic liquids with magnetic properties. These properties bring more advantages and potential application prospects than traditional solvents in the separation process. Hydrophobic magnetic ionic liquids are more suitable as extraction solvents to obtain phase separation of aqueous samples. By using a magnet to easily recover dispersed magnetic ionic liquid droplets, the centrifugation step is eliminated, greatly reducing analysis time.

With the continuous and deep research and application of the ionic liquid, the conventional ionic liquid cannot meet the requirement. Therefore, it is necessary to design an ionic liquid having a specific functional group according to the structure or properties of the target.

Disclosure of Invention

The novel functionalized ionic liquid provided by the invention is used as a micro-extraction phase, shows good hydrophobicity, has higher extraction capacity on fluoroquinolone medicines in a water body, has obvious color marks (blue), and is easy to visually separate from an aqueous solution through a magnet. The synthesis method provided by the invention is simple and mild in reaction conditions.

An ionic liquid with benzyl or carbonyl or methoxy, wherein the ionic liquid with benzyl or carbonyl or methoxy consists of an anion and a cation;

the anion is:

the cation with benzyl is as follows:

the cation with carbonyl is as follows:

the cation with the methoxyl is as follows:

a novel functionalized magnetic ionic liquid has structural formulas shown in formulas (I) to (III):

the preparation method of the novel functionalized magnetic ionic liquid comprises the following steps:

1) mixing n-octylamine and benzyl compounds with different functional groups in an organic solvent, reacting under the reflux condition, removing the organic solvent through rotary evaporation, washing crude substances for a plurality of times by using n-hexane under ultrasonic treatment, and then carrying out vacuum drying to obtain an intermediate;

2) mixing the intermediate, cobalt chloride hexahydrate and potassium thiocyanate in an organic solvent, reacting under the reflux condition, centrifuging to remove unreacted substances, performing rotary evaporation on supernate to remove the organic solvent, washing a product with excessive deionized water, and performing vacuum drying to obtain the novel functionalized ionic liquid.

The preparation method of the novel functionalized magnetic ionic liquid comprises the following steps of (1) according to molar ratio, benzyl compound: n-octylamine: cobalt chloride hexahydrate: potassium thiocyanate is 1: 1: 1: 4.

in the preparation method of the novel functionalized magnetic ionic liquid, in the step 1), the benzyl compound is one of benzyl bromide, 1, 4- (bromomethyl) phenyl) ethanone and 3-methoxybenzyl bromide.

In the preparation method of the novel functionalized magnetic ionic liquid, in the step 1), the organic solvent is chloroform.

In the preparation method of the novel functionalized magnetic ionic liquid, in the step 1), the reaction temperature is 70-90 ℃, and the reaction time is 72 hours.

In the preparation method of the novel functionalized magnetic ionic liquid, in the step 2), the organic solvent is acetone.

In the step 2), the reaction temperature is 50-60 ℃ and the reaction time is 5 hours.

The novel functionalized magnetic ionic liquid is applied to extraction of fluoroquinolone medicines.

The application method comprises the following steps of adding the novel functionalized magnetic ionic liquid into the fluoroquinolone antibiotic-containing aqueous solution, extracting by using a vortex instrument, and then separating by using a magnet.

The invention has the beneficial effects that: taking hydrophobic magnetic ionic liquid with long-chain alkyl, benzyl structure or carbonyl structure or methoxyl structure as micro-extraction phase, and performing liquid-liquid extraction on trace fluoroquinolone drugs in water. Compared with the traditional ionic liquid, the novel functionalized magnetic ionic liquid has higher extraction capacity, is easy to be visually separated from the aqueous solution through a magnet, and avoids a centrifugation step. The synthesis method provided by the invention is simple and mild in reaction conditions.

Drawings

Fig. 1 is a raman spectrum of the carbonyl-functionalized ionic liquid obtained in example 2.

Fig. 2 is a raman spectrum of the methoxy-functionalized ionic liquid obtained in example 3.

FIG. 3 is a graphical representation of the extraction capacities obtained in examples 4, 5 and 6.

Detailed Description

Example 1 preparation of benzyl-functionalized magnetic Ionic liquids

4mmol of n-octylamine and 4mmol of benzyl bromide are mixed, dissolved in 100mL of chloroform, and the reaction is carried out under reflux at 70 ℃ for 72 hours. The solvent chloroform was removed by rotary evaporation, the crude material was washed four times with 200mL of n-hexane under sonication and dried under vacuum at 60 ℃ for 24h to give an intermediate. 2mmol of cobalt chloride hexahydrate and 8mmol of potassium thiocyanate are mixed, dissolved in acetone together with an intermediate, and condensed and refluxed for 5 hours at 50 ℃. Centrifuging to remove unreacted substances, performing rotary evaporation on the supernatant to remove the organic solvent, washing the product with excessive deionized water, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid with benzyl groups, wherein the structural formula is as follows:

example 2 preparation of carbonyl functionalized magnetic Ionic liquids

4mmol of n-octylamine and 4mmol of 1, 4- (bromomethyl) phenyl) ethanone are mixed, dissolved in 100mL of chloroform, and condensed and refluxed at 70 ℃ for 72 hours. The solvent chloroform was removed by rotary evaporation, the crude material was washed four times with 200mL of n-hexane under sonication and dried under vacuum at 60 ℃ for 24h to give an intermediate. 2mmol of cobalt chloride hexahydrate and 8mmol of potassium thiocyanate are mixed, dissolved in acetone together with an intermediate, and condensed and refluxed for 5 hours at 50 ℃. Centrifuging to remove unreacted substances, performing rotary evaporation on the supernatant to remove the organic solvent, washing the product with excessive deionized water, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid with carbonyl groups, wherein the structural formula is as follows:

FIG. 1 shows Raman spectra of ionic liquid at 139cm^-1、571cm^-1、803cm^-1Characteristic peaks show that the intermediate, cobalt chloride hexahydrate and potassium thiocyanate successfully carry out a complex reaction, and the carbonyl functionalized ionic liquid is successfully prepared.

Example 3 preparation of methoxy functionalized magnetic Ionic liquid

4mmol of n-octylamine and 4mmol of 3-methoxybenzyl bromide are mixed, dissolved in 100mL of chloroform, and the reaction is carried out for 72 hours under reflux at 70 ℃. The solvent chloroform was removed by rotary evaporation, the crude material was washed four times with 200mL of n-hexane under sonication and dried under vacuum at 60 ℃ for 24h to give an intermediate. 2mmol of cobalt chloride hexahydrate and 8mmol of potassium thiocyanate are mixed, dissolved in acetone together with an intermediate, and condensed and refluxed for 5 hours at 50 ℃. Centrifuging to remove unreacted substances, performing rotary evaporation on the supernatant to remove the organic solvent, washing the product with excessive deionized water, and performing vacuum drying at 60 ℃ for 24 hours to obtain the ionic liquid with the methoxyl, wherein the structural formula is as follows:

FIG. 2 shows the Raman spectrum of an ionic liquid at 305cm^-1、578cm^-1、834cm^-1Characteristic peaks show that the intermediate, cobalt chloride hexahydrate and potassium thiocyanate successfully carry out a complex reaction, and the methoxy functional ionic liquid is successfully prepared.

Example 4 application of benzyl functionalized magnetic ionic liquid in extraction of fluoroquinolone antibiotics

Adding 1-5 microliter of benzyl functionalized magnetic ionic liquid into 5-10ppm fluoroquinolone antibiotic aqueous solution, extracting for 5-10min by using a vortex apparatus at 2500rpm, and then separating the ionic liquid from the aqueous solution by using a magnet. The supernatant is measured by a high performance liquid chromatography-ultraviolet detector, the result shows that the extraction efficiency of the fluoroquinolone antibiotics is 64.95%, and compared with the extraction efficiency of other two functionalized ionic liquids (see figure 3), the extraction efficiency is the lowest because pi-pi conjugation only exists between the fluoroquinolone antibiotics and benzyl functionalized ionic liquid. After the ionic liquid is eluted by methanol, the fluoroquinolone antibiotics can still be effectively extracted by recycling for 3 times.

Example 5 application of carbonyl functionalized magnetic ionic liquid in extraction of fluoroquinolone antibiotics

Adding 1-5 microliter of carbonyl functionalized magnetic ionic liquid into 5-10ppm fluoroquinolone antibiotic aqueous solution, extracting for 5-10min by using a vortex apparatus at 2500rpm, and then separating the ionic liquid from the aqueous solution by using a magnet. The supernatant is measured by a high performance liquid chromatography-ultraviolet detector, and the result shows that the extraction efficiency of the fluoroquinolone antibiotics is 96.97 percent, compared with the extraction efficiency of other two functionalized ionic liquids (see figure 3), except that pi-pi conjugation exists between the fluoroquinolone antibiotics and the carbonyl functionalized ionic liquid, the carbonyl in the ionic liquid and the hydroxyl in the fluoroquinolone antibiotics also form hydrogen bonds, so the extraction efficiency is highest. After the ionic liquid is eluted by methanol, the fluoroquinolone antibiotics can still be effectively extracted by recycling for 3 times.

Example 6 application of methoxy functionalized magnetic ionic liquid in extraction of fluoroquinolone antibiotics

Adding 1-5 microliter of methoxy functionalized magnetic ionic liquid into 5-10ppm fluoroquinolone antibiotic aqueous solution, extracting for 5-10min by using a vortex apparatus at 2500rpm, and then separating the ionic liquid from the aqueous solution by using a magnet. The supernatant is measured by a high performance liquid chromatography-ultraviolet detector, and the result shows that the extraction efficiency of the fluoroquinolone antibiotics is 72 percent, compared with the extraction efficiency of other two kinds of functionalized ionic liquids (see figure 3), pi-pi conjugation effect and hydrogen bond effect also exist between the fluoroquinolone antibiotics and the methoxyl functionalized ionic liquid, so the extraction efficiency is higher than that of benzyl functionalized ionic liquid. However, this effect is weaker than that of the carbonyl-functionalized ionic liquid, and the extraction efficiency is lower than that of the carbonyl-functionalized ionic liquid. After the ionic liquid is eluted by methanol, the fluoroquinolone antibiotics can still be effectively extracted by recycling for 3 times.