CN114573038A - Granular magnetic drive micro motor and magnetic control preparation method thereof - Google Patents

Granular magnetic drive micro motor and magnetic control preparation method thereof Download PDF

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CN114573038A
CN114573038A CN202210304636.XA CN202210304636A CN114573038A CN 114573038 A CN114573038 A CN 114573038A CN 202210304636 A CN202210304636 A CN 202210304636A CN 114573038 A CN114573038 A CN 114573038A
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magnetic
rice
grain
micro motor
shaped
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成昱
李珍光
刘雅丽
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Tongji University
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/08Ferroso-ferric oxide (Fe3O4)
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00Compounds of cobalt
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/02Particle morphology depicted by an image obtained by optical microscopy
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/42Magnetic properties

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Abstract

The invention relates to the technical field of micro motors, in particular to a rice-shaped magnetic drive micro motor and a magnetic control preparation method thereof. The magnetic-field-controlled micro motor takes hydrogel with high biological safety as a main material, magnetic nano materials are encapsulated in hydrogel microspheres, and the assembly and orientation of the magnetic nano materials in the hydrogel microspheres are regulated by applying a static magnetic field, so that the rice-grain-shaped magnetic-drive micro motor with different sizes and length-diameter ratios can be obtained. The rice-grain-shaped micro motor has excellent biocompatibility and excellent magnetic driving motion performance, and the special rice-grain-shaped structure is beneficial to the surface motion of the rice-grain-shaped micro motor in a low Reynolds number environment and a complex structure. The magnetic control preparation method is simple, convenient and quick, can freely adjust the raw material composition and preparation parameters according to the use requirements so as to obtain the rice grain-shaped magnetic drive micro-motors with different performances, and has wide applicability.

Description

Granular magnetic drive micro motor and magnetic control preparation method thereof
Technical Field
The invention relates to the technical field of micro motors, in particular to a rice-shaped magnetic drive micro motor and a magnetic control preparation method thereof.
Background
The micro swimming motor has the advantages of small structure size and precise devices, can enter a narrow space beyond the reach of human beings and macroscopic robots for micro operation, and has very important potential application in the fields of biomedicine, environmental treatment and the like, such as minimally invasive surgery, targeted therapy, cell operation, heavy metal detection, pollutant degradation application and the like. The micro motor moves in the fluid in a low Reynolds number environment, viscous force is dominant, inertial force is negligible, and the micro motor is required to be continuously powered if the micro motor is driven, unlike the traditional macro robot which can move by inertia. However, because of their small size, power sources such as batteries, engines, etc. are difficult to load on the micro-motors, and thus how to drive the micro-motors has been a major concern of researchers. The conventional self-driven micro motor usually changes the surrounding environment by self reaction to provide power and is difficult to last; the micromotor driven by an external field (such as an optical field, a magnetic field and the like) is usually prepared from noble metal and transition metal oxide, has potential safety risk in the field of biomedicine, still has limited driving performance and low movement capability, and is difficult to meet the driving requirements in the environment of body fluid and the like.
Disclosure of Invention
In order to solve the above problems, the present invention provides a rice-shaped magnetic-drive micro motor and a magnetic control manufacturing method thereof. The micro motor takes hydrogel with high biological safety as a main material, magnetic nano materials are encapsulated in hydrogel microspheres, and the assembly and orientation of the magnetic nano materials in the hydrogel microspheres are regulated by applying a static magnetic field; specifically, computational fluid dynamics research shows that the micromotor with the anisotropic structure shows better hydrodynamic interaction in a fluid and is beneficial to propelling the micromotor on the surface of complex terrain, and the magnetic nanoparticles arranged in the micromotor in an oriented mode cause the magnetic nanoparticles to be asymmetric in frictional resistance borne by the micromotor in the fluid and show stronger surface motion performance. The magnetic control preparation method is simple, convenient and quick, can freely adjust the raw material composition and preparation parameters according to the use requirements so as to obtain the rice-grain-shaped magnetic drive micro motor with different performances, and has wide applicability.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a magnetic control preparation method of a rice-shaped magnetic drive micromotor, which comprises the following steps:
(1) uniformly mixing the magnetic nano material with the hydrogel precursor solution to obtain an aqueous phase solution;
(2) adding the aqueous phase solution prepared in the step (1) into the oil phase/emulsifier mixed solution to obtain a water-in-oil type inverse emulsion;
(3) and (3) after the water-in-oil type inverse emulsion prepared in the step (2) is stable, applying a static magnetic field to the emulsion, stirring until the aqueous phase solution is gelatinized, and performing post-treatment to obtain the water-in-oil type inverse emulsion with the length-diameter ratio of 1: 1-2: 1 a rice grain-shaped magnetic-driven micro motor.
In one embodiment of the present invention, in the step (1), the concentration of the magnetic nanomaterial in the aqueous solution is 2 to 10 mg/mL.
In one embodiment of the present invention, the magnetic nanomaterial includes, but is not limited to, iron powder, ferroferric oxide, cobalt ferrite, or nickel ferrite.
In one embodiment of the present invention, in step (1), the hydrogel precursor solution includes, but is not limited to, chitosan/glutaraldehyde system, polyethyleneimine/polyethylene glycol diglycidyl ether system, gelatin/genipin system.
In one embodiment of the invention, the hydrogel precursor solution is a chitosan/glutaraldehyde system.
In one embodiment of the invention, the concentration of chitosan in the aqueous solution is 20-50mg/mL and the concentration of glutaraldehyde in the aqueous solution is 2-10 mg/mL.
In one embodiment of the present invention, in the step (2), in the oil phase/emulsifier mixed solution, the volume ratio of the oil phase to the emulsifier is 10: 1-50: 1.
in one embodiment of the invention, the volume ratio of aqueous phase solution to oil phase is 10: 1-20: 1.
in one embodiment of the present invention, the oil phase is selected from one or more of n-hexane, cyclohexane, mineral oil or liquid paraffin.
In one embodiment of the invention, the emulsifier is selected from Span 80.
In one embodiment of the present invention, in the step (3), the static magnetic field intensity is 50-200 Gs.
In one embodiment of the invention, the post-treatment is washing away the oil phase and the emulsifier by magnetic sorting.
A second object of the present invention is to provide a rice-grain-shaped magnetic drive micromotor prepared by any one of the above methods, wherein the rice-grain-shaped magnetic drive micromotor has an aspect ratio of 1: 1-2: 1.
compared with the prior art, the invention has the following beneficial effects:
(1) the rice-grain-shaped magnetic-drive micromotor is prepared by wrapping magnetic nanoparticles with a hydrogel shell, so that direct contact between metal oxide and organisms is avoided, and the biological safety is high;
(2) the magnetic control preparation method provided by the invention has high customizability, and can select the hydrogel main material and the magnetic nano material for preparing the micro motor according to requirements, so as to regulate and control the biosafety, biodegradability, swellability and magnetic driving capability of the rice-grain-shaped magnetic-driven micro motor; the shape and the size of the rice grain-shaped magnetic drive micro motor can be regulated and controlled by adjusting the strength of the applied static magnetic field. In the preparation process, due to the guidance of a static magnetic field, the magnetic nano material is directionally assembled in the hydrogel microsphere, and the obtained magnetic-drive micromotor with the controllable length-diameter ratio has the advantages of more excellent motion capability and accurate track control, and has wide application prospect in the implementation of biomedical related tasks such as cell transportation, drug delivery and the like.
(3) The magnetic control preparation method provided by the invention is simple, convenient and quick, and has wide applicability.
Drawings
FIG. 1 is an optical micrograph of a rice grain-shaped magnetically driven micromotor prepared in example 1 of the present invention;
FIG. 2 is an optical micrograph of a rice-grain-shaped magnetically-driven micromotor prepared in example 2 of the present invention;
FIG. 3 is an optical micrograph of a rice-grain-shaped magnetically-driven micromotor prepared in example 3 of the present invention;
FIG. 4 is an optical micrograph of a rice grain-shaped magnetically driven micromotor prepared in example 4 of the present invention;
FIG. 5 is an optical micrograph of a rice grain-shaped magnetically driven micromotor prepared in example 5 of the present invention;
FIG. 6 is an optical micrograph of a rice-grain-shaped magnetically-driven micromotor prepared in example 6 of the present invention.
Detailed Description
The invention provides a magnetic control preparation method of a rice-shaped magnetic drive micro motor, which comprises the following steps:
(1) uniformly mixing the magnetic nano material with the hydrogel precursor solution to obtain an aqueous phase solution;
(2) adding the aqueous phase solution prepared in the step (1) into the oil phase/emulsifier mixed solution to obtain a water-in-oil type inverse emulsion;
(3) and (3) after the water-in-oil type inverse emulsion prepared in the step (2) is stable, applying a static magnetic field to the emulsion, stirring until the aqueous phase solution is gelatinized, and performing post-treatment to obtain the water-in-oil type inverse emulsion with the length-diameter ratio of 1: 1-2: 1 a rice grain-shaped magnetic-driven micro motor.
In one embodiment of the present invention, in the step (1), the concentration of the magnetic nanomaterial in the aqueous solution is 2 to 10 mg/mL.
In one embodiment of the present invention, the magnetic nanomaterial includes, but is not limited to, iron powder, ferroferric oxide, cobalt ferrite, or nickel ferrite.
In one embodiment of the present invention, in step (1), the hydrogel precursor solution includes, but is not limited to, chitosan/glutaraldehyde system, polyethyleneimine/polyethylene glycol diglycidyl ether system, gelatin/genipin system.
In one embodiment of the invention, the hydrogel precursor solution is a chitosan/glutaraldehyde system.
In one embodiment of the invention, the concentration of chitosan in the aqueous solution is 20-50mg/mL and the concentration of glutaraldehyde in the aqueous solution is 2-10 mg/mL.
In one embodiment of the present invention, in the step (2), in the oil phase/emulsifier mixed solution, the volume ratio of the oil phase to the emulsifier is 10: 1-50: 1.
in one embodiment of the invention, the volume ratio of aqueous phase solution to oil phase is 10: 1-20: 1.
in one embodiment of the present invention, the oil phase is selected from one or more of n-hexane, cyclohexane, mineral oil or liquid paraffin.
In one embodiment of the invention, the emulsifier is selected from Span 80.
In one embodiment of the present invention, in the step (3), the static magnetic field intensity is 50-200 Gs.
In one embodiment of the invention, the post-treatment is washing away the oil phase and the emulsifier by magnetic sorting.
The invention provides a rice-grain-shaped magnetic drive micromotor prepared by any one of the methods, wherein the length-diameter ratio of the rice-grain-shaped magnetic drive micromotor is 1: 1-2: 1.
the technical solutions of the present invention are described in detail below with reference to the accompanying drawings and specific examples, which are further illustrative of the present invention and do not limit the applicable scope of the present invention.
Example 1
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion, applying a static magnetic field of 50Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1: 1 <500 μm micron-sized magnetic drive motor.
Example 2
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion, applying a static magnetic field of 80Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1: 1 <1000 μm rice-grain-shaped magnetic-driven micromotor.
Example 3
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion, applying a static magnetic field of 100Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1.2 as shown in figure 3: 1 a magnetic drive motor with a millimeter level and a shape of a rice grain and an ellipsoid.
Example 4
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type reverse phase emulsion;
(3) placing a permanent magnet around the emulsion, applying a static magnetic field of 120Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1.3: 1 a magnetic drive motor with a millimeter level and a shape of a rice grain and an ellipsoid.
Example 5
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing permanent magnets around the emulsion, applying a static magnetic field of 150Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing off an oil phase and an emulsifier through magnetic separation to obtain the chitosan with the length-diameter ratio of 1.5 as shown in figure 5: 1 a magnetic drive motor with a millimeter level and a shape of a rice grain and an ellipsoid.
Example 6
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a 20mg/mL chitosan and 2mg/mL glutaraldehyde mixed aqueous solution, then adding 10mg ferroferric oxide nanoparticles, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 10mL of normal hexane and 0.2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion, applying a static magnetic field of 200Gs to the emulsion, continuing to mechanically stir for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 2: 1 a magnetic drive motor with a millimeter level and a shape of a rice grain and an ellipsoid.
Example 7
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a mixed aqueous solution of 30mg/mL of chitosan and 4mg/mL of glutaraldehyde, then adding 2mg of iron powder, and performing ultrasonic dispersion uniformly;
(2) adding the aqueous phase solution into an oil phase/emulsifier mixed solution consisting of 13mL of cyclohexane and 0.4mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion to apply a static magnetic field of 100Gs to the emulsion, continuously mechanically stirring for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1.2: 1, a magnetic drive motor in the shape of a millimeter grain.
Example 8
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of mixed aqueous solution of 35mg/mL of chitosan and 6mg/mL of glutaraldehyde, adding 4mg of nano cobalt ferrite, and performing ultrasonic dispersion uniformly;
(2) adding the aqueous phase solution into an oil phase/emulsifier mixed solution consisting of 15mL of mineral oil and 0.9mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion to apply a static magnetic field of 120Gs to the emulsion, continuously mechanically stirring for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1.3: 1, a magnetic drive motor in the shape of a millimeter grain.
Example 9
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a mixed aqueous solution of 40mg/mL of chitosan and 8mg/mL of glutaraldehyde, adding 6mg of nano nickel ferrite, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 18mL of liquid paraffin and 1.5mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion to apply a static magnetic field of 150Gs to the emulsion, continuously mechanically stirring for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 1.5: 1, a magnetic drive motor in the shape of a millimeter grain.
Example 10
The embodiment provides a rice-shaped magnetic drive micro motor and a preparation method thereof.
(1) Preparing 1mL of a mixed aqueous solution of 50mg/mL of chitosan and 10mg/mL of glutaraldehyde, then adding 8mg of nano ferroferric oxide, and performing ultrasonic dispersion uniformly;
(2) adding the water phase solution into an oil phase/emulsifier mixed solution consisting of 20mL of n-hexane/cyclohexane mixed solvent and 2mL of Span80 under high-speed mechanical stirring to form a stable water-in-oil type inverse emulsion;
(3) placing a permanent magnet around the emulsion to apply a static magnetic field of 200Gs to the emulsion, continuously mechanically stirring for 1h to fully crosslink the chitosan, and washing away an oil phase and an emulsifier by magnetic separation to obtain the chitosan with the length-diameter ratio of 2: 1, a magnetic drive motor in the shape of a millimeter grain.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A magnetic control preparation method of a rice-shaped magnetic drive micro motor is characterized by comprising the following steps:
(1) uniformly mixing the magnetic nano material with the hydrogel precursor solution to obtain an aqueous phase solution;
(2) adding the aqueous phase solution prepared in the step (1) into the oil phase/emulsifier mixed solution to obtain a water-in-oil type inverse emulsion;
(3) and (3) after the water-in-oil type inverse emulsion prepared in the step (2) is stable, applying a static magnetic field to the emulsion, stirring until the aqueous phase solution is gelatinized, and performing post-treatment to obtain the water-in-oil type inverse emulsion with the length-diameter ratio of 1: 1-2: 1 a rice grain-shaped magnetic-driven micro motor.
2. The method of claim 1, wherein in step (1), the concentration of the magnetic nanomaterial in the aqueous solution is 2-10 mg/mL.
3. The method of claim 2, wherein the magnetic nanomaterial includes, but is not limited to, iron powder, ferroferric oxide, cobalt ferrite, or nickel ferrite.
4. The magnetron manufacturing method of a rice-shaped magnetic-drive micromotor as claimed in claim 1, wherein in step (1), the hydrogel precursor solution includes but is not limited to chitosan/glutaraldehyde system, polyethyleneimine/polyethylene glycol diglycidyl ether system, gelatin/genipin system.
5. The magnetron manufacturing method of a rice-grain-shaped magnetically-actuated micromotor according to claim 1, wherein in the step (2), the volume ratio of the oil phase to the emulsifier in the oil phase/emulsifier mixed solution is 10: 1-50: 1.
6. the method of claim 5, wherein the volume ratio of the aqueous phase solution to the oil phase is 10: 1-20: 1.
7. the method of claim 5, wherein the oil phase is selected from one or more of n-hexane, cyclohexane, mineral oil, and liquid paraffin.
8. The method as claimed in claim 5, wherein the emulsifier is selected from Span 80.
9. The method of claim 1, wherein in step (3), the static magnetic field strength is 50-200 Gs.
10. A rice grain-shaped magnetic drive micromotor produced by the method of any one of claims 1 to 9, wherein the rice grain-shaped magnetic drive micromotor has an aspect ratio of 1: 1-2: 1.
CN202210304636.XA 2022-03-21 2022-03-21 Granular magnetic drive micro motor and magnetic control preparation method thereof Pending CN114573038A (en)

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