Preparation method and application of magnetic microspheres for drug adsorption

Abstract

The invention discloses a preparation method and application of magnetic microspheres for drug adsorption. Ferric salt is dissolved in water and heated, an alkaline agent is slowly dropwise added and stirred, cleaning is conducted after the reaction is finished, and Fe3O4 nanoparticles are prepared; the preparation method comprises the following steps: dispersing Fe3O4 nanoparticles in water, heating, adding a double-bond compound, and cleaning after the reaction is finished, so as to prepare Fe3O4 nanoparticles with-C = C-double bonds on the surface; fe3O4 nanoparticles with-C = C-double bonds on the surfaces are dispersed in water, an emulsifier and an active group compound are added, the active group compound is sodium p-styrenesulfonate, vinylpyrrolidone or triethyl (4-vinylbenzyl) ammonium chloride, continuous heating is performed, cleaning is performed after the reaction is finished, and the magnetic microspheres for drug adsorption are prepared. The magnetic microspheres can be fully mixed with sewage through the directional movement of the magnetic microspheres, adsorption, purification and concentration of drugs are completed through anion groups or cation groups, the operation steps of testing are greatly simplified, and the working efficiency is improved.

Description

Technical Field

[0001] This invention relates to the field of magnetic microsphere technology, and in particular to a method for preparing magnetic microspheres for drug adsorption and their application. Background Technology

[0002] Detecting methamphetamine, ketamine, heroin, and other drugs in wastewater has always been a challenge. This is because drugs are highly lipophilic and easily adsorbed by some substrates in water, so the concentration of drugs in wastewater is usually extremely low.

[0003] Currently, the commonly used extraction methods for drugs in wastewater are liquid-liquid extraction and solid-phase extraction. Liquid-liquid extraction suffers from significant losses and low sensitivity, while solid-phase extraction requires filtering the wastewater beforehand, followed by sample loading, rinsing, and elution, making the process complex, time-consuming, and severely impacting work efficiency. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing magnetic microspheres for drug adsorption and their application. The magnetic microspheres can be fully mixed with wastewater by means of directional movement, and the adsorption, purification and concentration of drugs can be completed through anionic or cationic groups, which greatly simplifies the test operation steps and improves work efficiency.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing magnetic microspheres for drug adsorption, comprising the following steps:

[0006] S1) Preparation of Fe3O4 nanoparticles: Iron salts were dissolved in water and heated, alkali was slowly added dropwise and stirred. After the reaction was completed, the mixture was washed to obtain Fe3O4 nanoparticles.

[0007] S2) Surface modification with double bonds: Fe3O4 nanoparticles were dispersed in water and heated. Double bond compounds were added to the dispersion. After the reaction was completed, the mixture was washed to obtain Fe3O4 nanoparticles with -C=C- double bonds on the surface.

[0008] S3) Introducing active groups: Fe3O4 nanoparticles with -C=C- double bonds on the surface are dispersed in water, an emulsifier is added to the dispersion, the mixture is stirred evenly and heated, and an active group compound is added. The active group compound includes one or more of sodium p-styrene sulfonate, vinylpyrrolidone, and triethyl(4-vinylbenzyl)ammonium chloride. The mixture is heated continuously, and after the reaction is completed, it is washed to obtain magnetic microspheres for drug adsorption.

[0009] As a further optimization, the iron salt comprises FeCl3·6H2O and FeCl2·4H2O, with a mass ratio of 1:(1.5-5).

[0010] As a further optimization, the alkali is ammonia water, and the ratio of the iron salt to the alkali is 1:(10-15)g / mL.

[0011] As a further optimization, the heating temperature in S1 is 50-70℃, preferably 60℃, and the heating time is 1-5h.

[0012] As a further optimization, the double bond compound includes one or more of oleic acid, undecenoic acid, and acrylic acid.

[0013] As a further optimization, the mass ratio of Fe3O4 nanoparticles to double bond compounds in S2 is 1:(2-5).

[0014] As a further optimization, the heating temperature in S2 is 80-100℃, preferably 80℃, and the heating time is 2-5h.

[0015] As a further optimization, the surfactant includes one or more of sodium dodecyl sulfonate, tetrabutylammonium bromide, Tween 20, and Span 80.

[0016] This invention also provides an application of magnetic microspheres for drug adsorption, comprising the following steps:

[0017] S41) Take 0.5-1L of sewage sample, add 1-2g of magnetic microspheres for drug adsorption prepared by any one of claims 1 to 8, mix well, place the sample in a magnetic field, and discard the sewage after all the magnetic microspheres for drug adsorption are attracted by the magnetic field.

[0018] S42) Transfer the magnetic microspheres for drug adsorption to a small centrifuge tube, wash away contaminants with 5%-30% methanol-water solution, and elute the drugs with solvent. Dry the eluent with nitrogen gas.

[0019] S43) Resolute the sample with phosphate buffer or organic solvent and perform colloidal gold test paper detection or mass spectrometry detection.

[0020] As a further optimization, the solvent described in S42 includes one or more of methanol, ethyl acetate, or cyclohexane.

[0021] Compared with existing technologies, the present invention has the following beneficial effects: magnetic microspheres with surfaces modified by cationic or anionic groups undergo directional movement under the action of an external magnetic field. Utilizing this characteristic of magnetic microspheres, they are introduced into a large volume of wastewater sample and thoroughly mixed. Since sodium styrene sulfonate, vinylpyrrolidone, and triethyl(4-vinylbenzyl)ammonium chloride have a strong affinity for drugs, the adsorption of drugs can be greatly enhanced. This allows for the adsorption, purification, and concentration of drugs, greatly simplifying the testing procedures and improving work efficiency. Detailed Implementation

[0022] The following are specific embodiments of the present invention, which further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0023] Example 1:

[0024] A method for preparing magnetic microspheres for drug adsorption includes the following steps:

[0025] S1) Preparation of Fe3O4 nanoparticles: Dissolve 6g of iron salt (including 2.4g FeCl3·6H2O and 3.6g FeCl2·4H2O) in 100mL of water, stir evenly, and heat to 60-70℃. Then slowly add 65mL of ammonia water dropwise while stirring rapidly. After the ammonia water is added, continue heating for 1-2 hours. After the reaction is completed, repeatedly wash the Fe3O4 nanoparticles, disperse them in pure water by ultrasonication, and set aside for later use.

[0026] S2) Surface modification of double bonds: Take 1.5g of the Fe3O4 nanoparticles prepared above, sonicate them to disperse evenly in 60mL of water, heat to 80℃, keep at a constant temperature for 1-2h, slowly add 6g of oleic acid, after all the oleic acid is added, continue stirring for 1-2h, after the reaction is completed, wash the Fe3O4 nanoparticles with -C=C- double bonds on the surface repeatedly with pure water, sonicate them to disperse in water, and set aside for use;

[0027] S3) Introducing active groups: Take the Fe3O4 nanoparticles with -C=C- double bonds on the surface prepared above, add 30mL of water, disperse by ultrasonication, and add 0.5g of Span 80. Stir the solution evenly, heat to 60-70℃, then add 8mL of sodium p-styrene sulfonate and an initiator such as potassium persulfate. Continue heating for 24-36h. After the reaction is completed, wash the magnetic microspheres repeatedly with ethanol to obtain magnetic microspheres for drug adsorption.

[0028] Example 2:

[0029] A method for preparing magnetic microspheres for drug adsorption includes the following steps:

[0030] S1) Preparation of Fe3O4 nanoparticles: Dissolve 6.3g of iron salt (including 2.5g FeCl3·6H2O and 3.8g FeCl2·4H2O) in 100mL of water, stir evenly, and heat to 60-70℃. Then slowly add 70mL of ammonia water dropwise while stirring rapidly. After the ammonia water is added, continue heating for 1-2 hours. After the reaction is completed, repeatedly wash the Fe3O4 nanoparticles, disperse them in pure water by ultrasonication, and set aside for later use.

[0031] S2) Surface modification of double bonds: Take 1.7g of the above Fe3O4 nanoparticles, sonicate them to disperse evenly in 60mL of water, heat to 80℃, keep at a constant temperature for 1-2h, slowly add 5.5g of acrylic acid, after all the acrylic acid has been added, continue stirring for 1-2h, after the reaction is complete, wash the Fe3O4 nanoparticles with -C=C- double bonds on the surface repeatedly with pure water, sonicate them to disperse in water, and set aside for use;

[0032] S3) Introducing active groups: Take the Fe3O4 nanoparticles with -C=C- double bonds on the surface prepared above, add 30mL of water, disperse by ultrasonication, and add 0.5g of sodium dodecyl sulfonate. Stir the solution evenly, heat to 60-70℃, then add 5mL of sodium p-styrene sulfonate and add an initiator such as potassium persulfate. Continue heating for 24-36h. After the reaction is completed, wash the magnetic microspheres repeatedly with ethanol to obtain magnetic microspheres for drug adsorption.

[0033] Example 3:

[0034] A method for preparing magnetic microspheres for drug adsorption includes the following steps:

[0035] S1) Preparation of Fe3O4 nanoparticles: Dissolve 5.3g of iron salt (including 2.1g FeCl3·6H2O and 3.2g FeCl2·4H2O) in 100mL of water, stir evenly, and heat to 60-70℃. Then slowly add 60mL of ammonia water dropwise while stirring rapidly. After the ammonia water is added, continue heating for 1-2 hours. After the reaction is completed, repeatedly wash the Fe3O4 nanoparticles, disperse them in pure water by ultrasonication, and set aside for later use.

[0036] S2) Surface modification of double bonds: Take 1.6g of the above Fe3O4 nanoparticles, sonicate them to disperse evenly in 60mL of water, heat to 80℃, keep the temperature constant for 1-2h, slowly add 5g of acrylic acid, after all the acrylic acid is added, continue stirring for 1-2h, after the reaction is completed, wash the Fe3O4 nanoparticles with -C=C- double bonds on the surface repeatedly with pure water, sonicate them to disperse in water, and set aside for use;

[0037] S3) Introducing active groups: Take the Fe3O4 nanoparticles with -C=C- double bonds on the surface prepared above, add 30mL of water, disperse by ultrasonication, and add 0.6g of sodium dodecyl sulfonate. Stir the solution evenly, heat to 60-70℃, then add 6mL of sodium p-styrene sulfonate and add an initiator such as potassium persulfate. Continue heating for 24-36h. After the reaction is completed, wash the magnetic microspheres repeatedly with ethanol to obtain magnetic microspheres for drug adsorption.

[0038] Example 4:

[0039] A method for preparing magnetic microspheres for drug adsorption includes the following steps:

[0040] S1) Preparation of Fe3O4 nanoparticles: Dissolve 4.5g of iron salt (including 1.5g FeCl3·6H2O and 3g FeCl2·4H2O) in 100mL of water, stir evenly, and heat to 60-70℃. Then slowly add 60mL of ammonia water dropwise while stirring rapidly. After the ammonia water is added, continue heating for 1-2 hours. After the reaction is completed, repeatedly wash the Fe3O4 nanoparticles, disperse them in pure water by ultrasonication, and set aside for later use.

[0041] S2) Surface modification of double bonds: Take 1.5g of the above Fe3O4 nanoparticles, sonicate them to disperse evenly in 60mL of water, heat to 80℃, keep the temperature constant for 1-2h, slowly add 4g of undecenoic acid, after all the addition is complete, continue stirring for 1-2h, after the reaction is complete, wash the Fe3O4 nanoparticles with -C=C- double bonds on the surface repeatedly with pure water, sonicate them to disperse in water, and set aside for use;

[0042] S3) Introducing active groups: Take the Fe3O4 nanoparticles with -C=C- double bonds on the surface prepared above, add 30mL of water, disperse by ultrasonication, and add 0.5g of Tween 20. Stir the solution evenly, heat to 60-70℃, then add 5mL of sodium p-styrene sulfonate and an initiator such as potassium persulfate. Continue heating for 24-36h. After the reaction is completed, wash the magnetic microspheres repeatedly with ethanol to obtain magnetic microspheres for drug adsorption.

[0043] Example 5:

[0044] A method for preparing magnetic microspheres for drug adsorption includes the following steps:

[0045] S1) Preparation of Fe3O4 nanoparticles: Dissolve 5.6g of iron salt (including 1.8g FeCl3·6H2O and 3.8g FeCl2·4H2O) in 100mL of water, stir evenly, and heat to 60-70℃. Then slowly add 70mL of ammonia water dropwise while stirring rapidly. After the ammonia water is added, continue heating for 1-2 hours. After the reaction is completed, repeatedly wash the Fe3O4 nanoparticles, disperse them in pure water by ultrasonication, and set aside for later use.

[0046] S2) Surface modification of double bonds: Take 1.8g of the above Fe3O4 nanoparticles, sonicate them to disperse evenly in 60mL of water, heat to 80℃, keep the temperature constant for 1-2h, and slowly add 3.7g of acrylic acid. After all the acrylic acid is added, stir continuously for 1-2h. After the reaction is completed, wash the Fe3O4 nanoparticles with -C=C- double bonds on the surface repeatedly with pure water, sonicate them to disperse in water, and set aside for later use.

[0047] S3) Introducing active groups: Take the Fe3O4 nanoparticles with -C=C- double bonds on the surface prepared above, add 30mL of water, disperse by ultrasonication, and add 0.8g of tetrabutylammonium bromide. Stir the solution evenly, heat to 60-70℃, then add 7mL of sodium p-styrene sulfonate and add an initiator such as potassium persulfate. Continue heating for 24-36h. After the reaction is completed, wash the magnetic microspheres repeatedly with ethanol to obtain magnetic microspheres for drug adsorption.

[0048] Application Examples:

[0049] Take 1L of wastewater sample, add 1g of the magnetic microspheres for drug adsorption prepared in Examples 1 to 5, mix well, and place the sample in a magnetic field. After all the magnetic microspheres for drug adsorption are attracted by the magnetic field, discard the wastewater. Transfer the magnetic microspheres for drug adsorption to a small centrifuge tube, wash away contaminants with 5%-30% methanol-water solution, and elute the drugs with methanol. Dry the eluent with nitrogen gas. Resolute the sample with phosphate buffer or organic solvent, and perform colloidal gold test paper detection or mass spectrometry detection.

[0050] Comparative example:

[0051] The wastewater samples were tested using solid-phase extraction, including the following steps:

[0052] (1) Activation: Remove impurities from the column and create a certain solvent environment;

[0053] (2) Sample loading: Dissolve the sample in a certain solvent, transfer it into the column and retain the components on the column;

[0054] (3) Rinsing: to remove interfering substances to the greatest extent possible;

[0055] (4) Elution: Use a small volume of solvent to elute the analyte and collect it.

[0056] The drug concentration test results are shown in the table below:

[0057]

[0058] The test results above show that the magnetic microspheres prepared using the method for preparing magnetic microspheres for drug adsorption in this application, and the application of the magnetic microspheres (drug content testing), yield similar results to those obtained using conventional detection methods for drug content testing. The magnetic microspheres for drug adsorption in this application can complete the adsorption, purification, and concentration of drugs, greatly simplifying the testing procedures and improving work efficiency.

[0059] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A method for preparing magnetic microspheres for drug adsorption, characterized in that, Includes the following steps: S1) Preparation of Fe3O4 nanoparticles: Iron salts were dissolved in water and heated, alkali was slowly added dropwise and stirred. After the reaction was completed, the mixture was washed to obtain Fe3O4 nanoparticles. S2) Surface modification with double bonds: Fe3O4 nanoparticles were dispersed in water and heated. Double bond compounds were added to the dispersion. After the reaction was completed, the mixture was washed to obtain Fe3O4 nanoparticles with -C=C- double bonds on the surface. S3) Introducing active groups: Fe3O4 nanoparticles with -C=C- double bonds on the surface are dispersed in water, an emulsifier is added to the dispersion, the mixture is stirred evenly and heated, and an active group compound is added. The active group compound includes one or more of sodium p-styrene sulfonate, vinylpyrrolidone, and triethyl(4-vinylbenzyl)ammonium chloride. The mixture is heated continuously, and after the reaction is completed, it is washed to obtain magnetic microspheres for drug adsorption.

2. The method for preparing magnetic microspheres for drug adsorption according to claim 1, characterized in that, The iron salts include FeCl3·6H2O and FeCl2·4H2O, with a mass ratio of 1:(1.5-5).

3. The method for preparing magnetic microspheres for drug adsorption according to claim 1 or 2, characterized in that, The alkali is ammonia water, and the ratio of the iron salt to the alkali is 1:(10-15)g / mL.

4. The method for preparing magnetic microspheres for drug adsorption according to claim 1, characterized in that, The heating temperature in S1 is 50-70℃, and the heating time is 1-5h.

5. The method for preparing magnetic microspheres for drug adsorption according to claim 1, characterized in that, The double bond compound includes one or more of oleic acid, undecenoic acid, and acrylic acid.

6. The method for preparing magnetic microspheres for drug adsorption according to claim 1 or 5, characterized in that, The mass ratio of Fe3O4 nanoparticles to double-bonded compounds in S2 is 1:(2-5).

7. The method for preparing magnetic microspheres for drug adsorption according to claim 1, characterized in that, The heating temperature in S2 is 80-100℃, and the heating time is 2-5 hours.

8. The method for preparing magnetic microspheres for drug adsorption according to claim 1, characterized in that, The surfactant includes one or more of sodium dodecyl sulfonate, tetrabutylammonium bromide, Tween 20, and Span 80.

9. An application of magnetic microspheres for drug adsorption, characterized in that, Includes the following steps: S41) Take 0.5-1L of sewage sample, add 1-2g of magnetic microspheres for drug adsorption prepared by any one of claims 1 to 8, mix well, place the sample in a magnetic field, and discard the sewage after all the magnetic microspheres for drug adsorption are attracted by the magnetic field. S42) Transfer the magnetic microspheres for drug adsorption to a small centrifuge tube, wash away contaminants with 5%-30% methanol-water solution, and elute the drugs with solvent. Dry the eluent with nitrogen gas. S43) Resolute the sample with phosphate buffer or organic solvent and perform colloidal gold test paper detection or mass spectrometry detection.

10. The application of the magnetic microspheres for drug adsorption according to claim 9, characterized in that, The solvent described in S42 includes one or more of methanol, ethyl acetate, or cyclohexane.

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