CN117226806A - Cluster magnetic control micro-nano robot and preparation method thereof - Google Patents
Cluster magnetic control micro-nano robot and preparation method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 86
- 239000002105 nanoparticle Substances 0.000 claims abstract description 74
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 67
- 238000012545 processing Methods 0.000 claims abstract description 45
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 36
- 229940079593 drug Drugs 0.000 claims abstract description 29
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 18
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
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Abstract
The application discloses a cluster magnetic control micro-nano robot and a preparation method thereof, comprising the following steps: A. adding anhydrous ferric trichloride into deionized water; B. coating ferric trichloride solution on the surface of a carbon-based film, and heating to obtain the carbon-based film with ferric trichloride hexahydrate attached on the surface; C. carrying out laser processing on the carbon-based film with the ferric trichloride hexahydrate attached to the surface to obtain a carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface; D. stripping the graphene-ferroferric oxide conjugate on the surface of the carbon-based film, and performing ultrasonic vibration to obtain graphene-ferroferric oxide nano particles; E. and (3) putting the graphene-ferroferric oxide nano particles into deionized water, and applying a rotating magnetic field to obtain the clustered magnetic control micro-nano robot. The preparation method of the clustered magnetic control micro-nano robot provided by the application has the advantages of simplicity, high processing speed, strong drug carrying capacity and accurate positioning of the obtained clustered magnetic control micro-nano robot, and can be used for treating sewage.
Description
Technical Field
The application relates to the field of micro-nano robots, in particular to a clustered magnetic control micro-nano robot and a preparation method thereof.
Background
The magnetic control micro-nano robot is a robot with the size in the micro-nano level, can intelligently control the motion of the robot under the action of an external magnetic field, has great development and application prospects in the fields of medical engineering, nano engineering and the like by virtue of the advantages of strong controllability, excellent modifiable property and the like.
Compared with a single micro-nano robot with limited loading capacity, the clustered micro-nano robot assembled by a large number of magnetic nano particles under the action of a magnetic field has the characteristics of higher loading capacity and higher task completion efficiency. And because the clustered micro-nano robot has self-assembly and deformation capability, the application possibility is more than that of a single micro-nano robot. Based on this, the research of the cluster micro-nano robot is conducted well.
The ferroferric oxide has the characteristics of paramagnetism, stable chemical property and remote driving through a magnetic field; in addition, the ferroferric oxide has good biocompatibility, does not cause harm in organisms, and can be discharged outwards along with biological excreta, so that the ferroferric oxide is widely used as a raw material in clustered micro-nano robots. However, since the ferroferric oxide does not have the capability of binding with a substance, the clustered micro-nano robot prepared by only using the ferroferric oxide does not have the loading capability. In order to improve the defects, the prior art combines ferroferric oxide with other materials into a micro-nano robot, thereby endowing the clustered micro-nano robot with loading capability.
The application patent No. CN113966988A discloses a magnetically-driven micro-robot, which combines ferroferric oxide, degradable components and structural components by a photo-curing method to obtain a magnetically-driven clustered micro-nano robot, but the combination method of the three components is complex, and the preparation difficulty of the clustered micro-nano robot is easy to increase.
The application patent No. CN115671302A discloses a catalase-nano ferroferric oxide conjugate and a preparation method thereof, wherein the catalase-nano ferroferric oxide conjugate is used for catalyzing hydrogen peroxide to generate oxygen to drive particles to advance through the cooperation of enzyme and ferrous ions so as to obtain the drug carrying capacity, but the drug carrying capacity is greatly limited due to the limited oxygen generated by the method; in addition, although the method adopts enzyme and magnetic dual drive to improve the problem of inaccurate positioning caused by enzyme drive, the improvement degree is limited, and the problem of inaccurate positioning caused by enzyme drive still exists.
In conclusion, the existing method for preparing the clustered micro-nano robot generally has the problems of complex preparation method, weak medicine carrying capacity, inaccurate positioning and the like.
Disclosure of Invention
The first aim of the application is to provide a preparation method of the clustered magnetic control micro-nano robot, which is simple and has high processing speed, and the obtained clustered magnetic control micro-nano robot has strong medicine carrying capacity and accurate positioning, and can be used for treating sewage at the same time so as to overcome the defects in the prior art.
The second object of the application is to provide the clustered magnetic micro-nano robot prepared by the preparation method of the clustered magnetic micro-nano robot, which has the characteristics of oval shape, diameter of 2-4 mm, drug loading rate of 70-75%, strong drug loading capability and accurate positioning, and can be used for treating sewage, thereby greatly meeting the actual application demands.
To achieve the purpose, the application adopts the following technical scheme:
a preparation method of a cluster magnetic control micro-nano robot comprises the following steps:
A. adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a carbon-based film, and heating to obtain the carbon-based film with ferric trichloride hexahydrate attached on the surface;
C. performing laser processing on the carbon-based film with the ferric trichloride hexahydrate attached to the surface in the step B to obtain a carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the carbon-based film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate to obtain graphene-ferroferric oxide nano particles;
E. d, putting the graphene-ferroferric oxide nano particles obtained in the step D into deionized water for dispersion, and applying a rotating magnetic field to magnetize the graphene-ferroferric oxide nano particles to obtain a clustered magnetic control micro-nano robot;
in the step A, the mixing ratio of the anhydrous ferric trichloride to the deionized water is 1: (2-4);
in the step E, the weight of the graphene-ferroferric oxide nano particles is 0.1-0.3 mg.
Further, in the step a, the mixing ratio of the anhydrous ferric trichloride and the deionized water is 1:2.
further, in the step B, the heating temperature of the heating step is 60-80 ℃.
Further, in the step B, the thickness of the carbon-based film is 80-150 mu m;
the carbon-based film includes any one of a polyimide film and a polyamideimide film.
In the step C, the laser wavelength of the laser processing step is 350-360 nm, and the laser power is 10-15W.
Further, in the step D, the ultrasonic vibration time of the ultrasonic vibration step is 30-60 s, and the ultrasonic vibration frequency is 30-40 kHz.
Further, in the step E, the strength of the rotating magnetic field is 6 to 10mT.
Further, the step C further comprises the steps of immersing the carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface in deionized water, and then drying.
Further, in the step C, the drying temperature of the drying step is 75-85 ℃.
The cluster magnetic control micro-nano robot is prepared by the preparation method of the cluster magnetic control micro-nano robot, and the cluster magnetic control micro-nano robot is elliptical in shape, 2-4 mm in diameter and 70-75% in medicine carrying rate.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
1. according to the technical scheme, superparamagnetism of the ferroferric oxide is fully utilized, so that graphene-ferroferric oxide nano particles are assembled into the oval cluster magnetic control micro-nano robot under the action of a rotating magnetic field, and the cluster magnetic control micro-nano robot can be accurately positioned under the action of the rotating magnetic field to accurately transfer a target drug to a target position; meanwhile, as the graphene has the characteristics of being porous and high in specific surface area, compared with a clustered micro-nano robot prepared by utilizing a catalase-nano ferroferric oxide conjugate, the clustered magnetic control micro-nano robot of the technical scheme has stronger drug carrying capacity, and is more beneficial to improving the transmission efficiency of targeted drugs; in addition, the graphene has the adsorption capacity on pollutants, so that the clustered magnetic control micro-nano robot can also perform directional sewage treatment under the control of a magnetic field. Furthermore, the raw materials of the technical scheme are simpler, the product of the technical scheme can be obtained only by processing the two raw materials, the preparation method is simple, the cost is low, the controllable operability is strong, and the method is suitable for further development and industrialization application; and the laser can be utilized to realize rapid machining, so that the machining speed is greatly improved, and the production efficiency of products is improved.
2. Before laser processing, firstly preparing ferric trichloride solution, uniformly smearing the ferric trichloride solution on the surface of a carbon-based film, forming ferric trichloride hexahydrate when ferric trichloride is separated from the ferric trichloride solution by heating, and heating to obtain the carbon-based film with the surface attached with the ferric trichloride hexahydrate, so that laser can directly process the ferric trichloride hexahydrate, and the laser processing effect is ensured. Meanwhile, the carbon-based film is used for providing a carbon source, and the ferric trichloride solution is smeared on the surface of the carbon-based film, so that in the subsequent laser processing, the processed product of ferric trichloride hexahydrate is directly combined with the laser processed product of the carbon-based film, a target product is obtained, and the preparation method is further simplified.
3. And C, carrying out laser processing on the carbon-based film with the ferric trichloride hexahydrate adhered on the surface in the step B. The laser enables ferric trichloride hexahydrate to undergo oxidation-reduction reaction to generate ferric oxide nano particles, meanwhile, laser beams can penetrate through the ferric trichloride hexahydrate to process a carbon-based film, elements contained in the carbon-based film are mainly carbon, nitrogen and oxygen, the laser processing temperature is high, in the laser processing process, bonding between atoms or molecules of the carbon-based film is broken, carbon dioxide, carbon monoxide, nitrogen dioxide and nitric oxide and graphene are converted, wherein the carbon dioxide, the carbon monoxide, the nitrogen dioxide and the nitric oxide enter the air in a gas mode, and finally a processed product only remains the graphene. And in the process, the graphene and the ferroferric oxide nano particles are tightly combined together to form a graphene-ferroferric oxide combination. In the process of laser processing, laser does not completely break down the carbon-based film, only part of the carbon-based film is converted into graphene under the action of the laser, and the other part of the carbon-based film still exists in the form of the carbon-based film, so that the carbon-based film can be used as a carrier and a raw material, the preparation process is greatly simplified, the raw material is saved, and the cost is reduced.
Drawings
Fig. 1 is an EDS diagram of graphene-ferroferric oxide nanoparticles in example 1 in a preparation method of a clustered magnetic micro-nano robot of the present application.
Fig. 2 is a schematic diagram of a process of assembling graphene-ferroferric oxide nanoparticles of example 1 into an elliptical clustered micro-nano robot in the preparation method of the clustered magnetic micro-nano robot.
Fig. 3 is a physical diagram of the clustered magnetic micro-nano robot obtained in example 1 in the preparation method of the clustered magnetic micro-nano robot.
Detailed Description
Embodiments of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the application.
The technical scheme provides a preparation method of a clustered magnetic control micro-nano robot, which comprises the following steps:
A. adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a carbon-based film, and heating to obtain the carbon-based film with ferric trichloride hexahydrate attached on the surface;
C. performing laser processing on the carbon-based film with the ferric trichloride hexahydrate attached to the surface in the step B to obtain a carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the carbon-based film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate to obtain graphene-ferroferric oxide nano particles;
E. d, putting the graphene-ferroferric oxide nano particles obtained in the step D into deionized water for dispersion, and applying a rotating magnetic field to magnetize the graphene-ferroferric oxide nano particles to obtain a clustered magnetic control micro-nano robot;
in the step A, the mixing ratio of the anhydrous ferric trichloride to the deionized water is 1: (2-4);
in the step E, the weight of the graphene-ferroferric oxide nano particles is 0.1-0.3 mg.
In order to solve the problems of complex preparation method, weak drug carrying capability and inaccurate positioning in the prior art, the technical scheme provides a preparation method of a clustered magnetic control micro-nano robot, which comprises five steps of A (preparation of ferric trichloride solution), B (smearing of the ferric trichloride solution), C (laser processing), D (stripping) and E (dispersing and magnetizing), and the clustered magnetic control micro-nano robot with strong drug carrying capability and accurate positioning is obtained by controlling the mixing proportion of anhydrous ferric trichloride and deionized water and the weight of graphene-ferroferric oxide nano particles.
Specifically, in the prior art, a method for combining ferroferric oxide, a degradable component and a structural component is complex, and the preparation difficulty of the clustered micro-nano robot is easily increased; in addition, in the prior art, a catalase-nano ferroferric oxide conjugate is also used for preparing a clustered micro-nano robot, and the hydrogen peroxide is catalyzed by enzyme and ferrous ions cooperatively to generate oxygen so as to drive particles to advance, so that the drug carrying capacity is obtained, but the method has the problems that the drug carrying capacity is greatly limited due to the limited amount of oxygen generated by the method, and the positioning is inaccurate.
According to the technical scheme, superparamagnetism of the ferroferric oxide is fully utilized, so that graphene-ferroferric oxide nano particles are assembled into the oval cluster magnetic control micro-nano robot under the action of a rotating magnetic field, and the cluster magnetic control micro-nano robot can be accurately positioned under the action of the rotating magnetic field to accurately transfer a target drug to a target position; meanwhile, as the graphene has the characteristics of being porous and high in specific surface area, compared with a clustered micro-nano robot prepared by utilizing a catalase-nano ferroferric oxide conjugate, the clustered magnetic control micro-nano robot of the technical scheme has stronger drug carrying capacity, and is more beneficial to improving the transmission efficiency of targeted drugs; in addition, the graphene has the adsorption capacity on pollutants, so that the clustered magnetic control micro-nano robot can also perform directional sewage treatment under the control of a magnetic field. Furthermore, the raw materials of the technical scheme are simpler, the product of the technical scheme can be obtained only by processing the two raw materials, the preparation method is simple, the cost is low, the controllable operability is strong, and the method is suitable for further development and industrialization application; and the laser can be utilized to realize rapid machining, so that the machining speed is greatly improved, and the production efficiency of products is improved.
More specifically, when adopting laser to directly process ferric trichloride solution, because the ferric trichloride solution contains a large amount of moisture, laser needs to permeate moisture and can process ferric trichloride, leads to the processing effect relatively poor, therefore this technical scheme prepares the ferric trichloride solution at first before laser processing to evenly scribble the surface at the carbon-based film with the ferric trichloride solution, form ferric trichloride hexahydrate when making ferric trichloride separate from the ferric trichloride solution through heating, heat and obtain the carbon-based film of surface adhesion ferric trichloride hexahydrate, make laser can directly process ferric trichloride hexahydrate, ensure laser processing effect. Meanwhile, the carbon-based film is used for providing a carbon source, and the ferric trichloride solution is smeared on the surface of the carbon-based film, so that in the subsequent laser processing, the processed product of ferric trichloride hexahydrate is directly combined with the laser processed product of the carbon-based film, a target product is obtained, and the preparation method is further simplified.
And secondly, carrying out laser processing on the carbon-based film with the ferric trichloride hexahydrate adhered on the surface in the step B. The laser enables ferric trichloride hexahydrate to undergo oxidation-reduction reaction to generate ferric oxide nano particles, meanwhile, laser beams can penetrate through the ferric trichloride hexahydrate to process a carbon-based film, elements contained in the carbon-based film are mainly carbon, nitrogen and oxygen, the laser processing temperature is high, in the laser processing process, bonding between atoms or molecules of the carbon-based film is broken, carbon dioxide, carbon monoxide, nitrogen dioxide and nitric oxide and graphene are converted, wherein the carbon dioxide, the carbon monoxide, the nitrogen dioxide and the nitric oxide enter the air in a gas mode, and finally a processed product only remains the graphene. And in the process, the graphene and the ferroferric oxide nano particles are tightly combined together to form a graphene-ferroferric oxide combination. In the process of laser processing, laser does not completely break down the carbon-based film, only part of the carbon-based film is converted into graphene under the action of the laser, and the other part of the carbon-based film still exists in the form of the carbon-based film, so that the carbon-based film can be used as a carrier and a raw material, the preparation process is greatly simplified, the raw material is saved, and the cost is reduced.
And (C) stripping the graphene-ferroferric oxide conjugate on the surface of the carbon-based film in the step (C) to obtain a graphene-ferroferric oxide conjugate, and performing ultrasonic vibration on the graphene-ferroferric oxide conjugate to obtain graphene-ferroferric oxide nano particles, wherein the stripping method is simple. In the step D, the specific step of peeling is to scrape the graphene-ferroferric oxide conjugate on the surface of the carbon-based film with a blade.
And thirdly, putting the graphene-ferroferric oxide nano particles into deionized water for dispersion, and applying a rotating magnetic field, wherein the ferroferric oxide nano particles are magnetized to form magnetic dipoles under the action of the magnetic field, the magnetic dipoles are attracted by magnetic force to gather, and rotate around the central point of the rotating magnetic field continuously to generate vortex, and finally the graphene-ferroferric oxide nano particles are assembled into an ellipse shape to obtain the clustered magnetic control micro-nano robot.
Finally, as the mixing proportion of anhydrous ferric trichloride and deionized water is related to the amount of the graphene-ferroferric oxide micro-nano robot obtained after laser processing, if the content of ferric trichloride in a ferric trichloride solution is too low, the amount of graphene-ferroferric oxide nano particles obtained after laser processing is smaller, and the volume of the cluster magnetic control micro-nano robot assembled under the action of a rotating magnetic field is smaller, so that the use requirement of high drug carrying capacity cannot be met; if the content of ferric trichloride in the ferric trichloride solution is too high, the ferric trichloride hexahydrate crystallized on the surface of the carbon-based film is too thick, so that laser beams cannot penetrate through the ferric trichloride hexahydrate to convert the carbon-based film into graphene, and graphene-ferric oxide nanoparticles cannot be obtained. Therefore, in the technical scheme, the mixing ratio of anhydrous ferric trichloride to deionized water is defined as 1: (2-4) ensuring that the carbon-based film can be converted into graphene, and simultaneously ensuring the performance of the clustered magnetic control micro-nano robot.
Furthermore, since the stability and the size of the clustered magnetic micro-nano robot are closely related to the number of graphene-ferroferric oxide nanoparticles, if the weight of the graphene-ferroferric oxide nanoparticles is less than 0.1mg, the number of the graphene-ferroferric oxide nanoparticles contained in the clustered magnetic micro-nano robot is smaller, and the clustered magnetic micro-nano robot formed under the action of a rotating magnetic field has smaller volume and cannot meet the use requirement of high drug carrying capacity; if the weight of the graphene-ferroferric oxide nano particles is higher than 0.3mg, the number of the graphene-ferroferric oxide nano particles contained in the graphene-ferroferric oxide nano particles is excessive, the clustered magnetic control micro-nano robot obtained under the action of a rotating magnetic field is easy to disperse, the stability is extremely poor, and the complete oval clustered magnetic control micro-nano robot is difficult to assemble; meanwhile, the production cost is also increased. Therefore, the mass of the graphene-ferroferric oxide nano particles in the step E is 0.1-0.3 mg, so that the obtained clustered magnetic control micro-nano robot is moderate in size and high in stability.
Further described, in the step a, the mixing ratio of the anhydrous ferric trichloride and the deionized water is 1:2.
in a preferred embodiment of the present disclosure, the mixing ratio of the anhydrous ferric trichloride and the deionized water is further defined, so that the amount of the graphene-ferroferric oxide nanoparticles prepared in the mixing ratio is most suitable, and the laser beam can penetrate through the ferric trichloride hexahydrate, so that the carbon-based film can be converted into graphene, and the carbon-based film is not broken down, thereby improving the yield and quality of the graphene-ferroferric oxide nanoparticles, and improving the performance and yield of the clustered magnetic micro-nano robot.
Further, in the step B, the heating temperature in the heating step is 60 to 80 ℃.
Since ferric trichloride is a covalent ferric salt compound, it is readily soluble in water and has a strong water absorption, ferric trichloride hexahydrate is formed as it precipitates from solution. When the heating temperature is lower than 60 ℃, the crystallization speed of the ferric trichloride solution on the carbon-based film is too slow, so that the processing efficiency is affected; when the heating temperature is higher than 80 ℃, the ferric trichloride solution is hydrolyzed to generate hydrogen chloride and ferric hydroxide precipitates, which affect the processing environment and the subsequent laser processing, so that the heating temperature of the ferric trichloride solution is limited to 60-80 ℃ in a preferred embodiment of the technical scheme, and the processing speed and the processing performance are ensured.
Further, in the step B, the thickness of the carbon-based thin film is 80 to 150 μm;
the carbon-based film includes any one of a polyimide film and a polyamideimide film.
If the thickness of the carbon-based film is less than 80 mu m, the carbon-based film is easy to break down by laser in the processing process, and the processing performance of the carbon-based film is affected; if the thickness of the carbon-based film is more than 150. Mu.m, the cost is high due to the excessive thickness, and the cost performance of the product is deteriorated. Therefore, in a preferred embodiment of the present technical solution, the thickness of the carbon-based thin film is 80 to 150 μm, ensuring the processability and the cost performance of the carbon-based thin film.
Further, the carbon-based film comprises any one of a polyimide film and a polyamide-imide film, and graphene processed by the polyimide film or the polyamide-imide film under the action of laser is porous and has more excellent characteristic of high specific surface area, so that the drug carrying capacity and the sewage treatment capacity of the finally obtained clustered magnetic control micro-nano robot are further improved.
Further, in the step C, the laser wavelength of the laser processing step is 350-360 nm, and the laser power is 10-15W.
In a preferred embodiment of the present disclosure, the laser wavelength and the laser power are limited to ensure that the laser energy is sufficient to break the bonding between the atoms or molecules in the ferric trichloride and the carbon-based film, so as to convert the ferric trichloride into the ferric oxide, convert the carbon-based film into the graphene, and further ensure that the target product can be obtained. Meanwhile, the laser with the wavelength of 350-360 nm and the power of 10-15W is used for processing, and the method has the characteristics of high processing speed, high processing precision and stable power, and avoids the occurrence of larger damage to the carbon-based film during processing.
Preferably, in the step C, the laser wavelength of the laser processing step is 355nm, and the laser power is 15W.
Further, in the step D, the ultrasonic vibration time of the ultrasonic vibration step is 30-60 s, and the ultrasonic vibration frequency is 30-40 kHz.
In a preferred embodiment of the technical scheme, the ultrasonic oscillation time and frequency are controlled, so that the graphene-ferroferric oxide conjugate is dispersed under the action of ultrasonic oscillation to form graphene-ferroferric oxide nano particles with the particle size of 800 nm-10 mu m, on one hand, the situation that the particle size of the graphene-ferroferric oxide nano particles is too large, the requirement on the strength of a driving magnetic field is high, and the stability of the obtained clustered magnetic control micro-nano robot is weakened is avoided; on the other hand, the size of the obtained cluster magnetic control micro-nano robot is convenient to control, and the use requirement of the size miniaturization of the existing cluster magnetic control micro-nano robot is met.
Further, in the step E, the strength of the rotating magnetic field is 6 to 10mT.
If the strength of the rotating magnetic field is lower than 6mT, the difficulty of assembling the nano particles into the clustered micro-nano robot by magnetic field driving is increased; if the magnetic field intensity is higher than 10mT, the nano particles rotate rapidly under the action of the rotating magnetic field, and the assembled cluster micro-nano robot is unstable and easy to disperse. Therefore, in a preferred embodiment of the present solution, the strength of the rotating magnetic field is limited to 6-10 mT (millitesla), ensuring that a stable clustered micro-nano robot can be obtained.
More preferably, in step E, the rotating magnetic field has a strength of 8mT.
Further, the step C further comprises immersing the carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface in deionized water, and then drying.
In one embodiment of the technical scheme, the carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface is placed into deionized water for soaking, residual ferric trichloride hexahydrate on the surface of the carbon-based film is removed, and then the deionized water is removed by drying, so that the graphene-ferroferric oxide conjugate is peeled off from the carbon-based film more easily, and the production efficiency is improved.
Preferably, in the step C, the soaking step specifically includes: adding 50-100 ml of deionized water into a glassware, putting the carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface into the deionized water, soaking for 30-45 s, and taking out to ensure that the residual ferric trichloride hexahydrate is completely removed, and avoiding the residual iron trichloride from affecting the performance of a final product.
Further, in the step C, the drying temperature of the drying step is 75-85 ℃.
In a preferred embodiment of the present technical solution, in step C, the drying temperature is 75 ℃ to 85 ℃, so as to ensure that the deionized water on the surface of the carbon-based film is sufficiently removed, so that the graphene-ferroferric oxide conjugate can be peeled off more conveniently and easily.
The cluster magnetic control micro-nano robot is prepared by the preparation method of the cluster magnetic control micro-nano robot, and the cluster magnetic control micro-nano robot is elliptical in shape, 2-4 mm in diameter and 70-75% in medicine carrying rate.
The technical scheme also provides the clustered magnetic micro-nano robot prepared by the preparation method of the clustered magnetic micro-nano robot, the diameter of the clustered magnetic micro-nano robot is 2-4 mm, the medicine carrying rate is 70-75%, and the clustered magnetic micro-nano robot has the characteristics of strong medicine carrying capability and accurate positioning, and can be used for treating sewage and meeting the actual application demands.
The technical scheme of the application is further described by the following specific embodiments.
Example 1
A. Adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution; according to the mass percentage, the mixing proportion ratio of the anhydrous ferric trichloride to the deionized water is 1:2;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a polyimide film with the thickness of 80 mu m, and heating at 60 ℃ to obtain the polyimide film with ferric trichloride hexahydrate attached on the surface;
C. b, carrying out laser processing on the polyimide film with the ferric trichloride hexahydrate attached on the surface in the step B by utilizing laser with the wavelength of 350nm and the laser power of 10W to obtain a polyimide film with the graphene-ferroferric oxide conjugate attached on the surface;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the polyimide film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate in an ultrasonic oscillator with the vibration frequency of 30kHz for 30s to obtain graphene-ferroferric oxide nano particles; the EDS diagram of the graphene-ferroferric oxide nano particles is shown in figure 1;
E. c, putting 0.1mg of graphene-ferroferric oxide nano particles in the step D into 30ml of deionized water for dispersion, and applying a rotating magnetic field with the intensity of 6mT to magnetize to obtain the clustered magnetic control micro-nano robot; wherein, the physical picture of the clustered magnetic control micro-nano robot is shown in figure 2; a schematic diagram of a process of forming the clustered magnetic micro-nano robot by the graphene-ferroferric oxide nano particles is shown in fig. 3.
And D, measuring the diameter of the clustered magnetic micro-nano robot in the embodiment 1 and the graphene-ferroferric oxide nano particles obtained in the step D by using a scanning electron microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 1 in a doxorubicin solution with the concentration of 50-60 mug/ml, standing for 2 hours, and taking out to obtain the clustered magnetic micro-nano robot loaded with doxorubicin; the cluster magnetic control micro-nano robot is driven to target the affected part for recruitment in a rotating magnetic field with the intensity of 6 mT. And measuring the concentration of the doxorubicin solution after the cluster magnetic control micro-nano robot is immersed by using a fluorescence spectrophotometer, so as to calculate the drug loading rate of the cluster micro-nano robot, and observing the motion trail of the cluster magnetic control micro-nano robot under a microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 1 in domestic sewage, standing for 2 hours, taking out, and detecting the components in the sewage by using a fluorescence spectrophotometer.
The result shows that the particle size of the graphene-ferroferric oxide nano particles obtained in the embodiment 1 is 10 mu m, the diameter of the clustered micro-nano robot is 2mm, the drug loading rate is 70%, and the graphene-ferroferric oxide nano particles can be targeted to an affected part under the action of a rotating magnetic field, so that doxorubicin can be accurately and directionally delivered to a target position; meanwhile, the content of organic components in the sewage is reduced.
Example 2
A. Adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution; according to the mass percentage, the mixing proportion ratio of the anhydrous ferric trichloride to the deionized water is 1:3, a step of;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a polyimide film with the thickness of 100 mu m, and heating at 70 ℃ to obtain the polyimide film with ferric trichloride hexahydrate attached on the surface;
C. b, carrying out laser processing on the polyimide film with the ferric trichloride hexahydrate attached on the surface in the step B by utilizing laser with the wavelength of 355nm and the laser power of 15W to obtain a polyimide film with the graphene-ferroferric oxide conjugate attached on the surface; placing the polyimide film with the graphene-ferroferric oxide conjugate attached to the surface into a glassware filled with 80ml of deionized water, soaking for 30 seconds, and drying at 80 ℃;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the polyimide film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate in an ultrasonic oscillator with the vibration frequency of 35kHz for 45s to obtain graphene-ferroferric oxide nano particles;
E. and D, putting 0.2mg of graphene-ferroferric oxide nano particles in the step D into 30ml of deionized water for dispersion, and applying a rotating magnetic field with the strength of 8mT to magnetize to obtain the clustered magnetic control micro-nano robot.
And D, measuring the diameter of the clustered magnetic micro-nano robot in the embodiment 2 and the graphene-ferroferric oxide nano particles obtained in the step D by using a scanning electron microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 2 in a doxorubicin solution with the concentration of 50-60 mug/ml, standing for 2 hours, and taking out to obtain the clustered magnetic micro-nano robot loaded with doxorubicin; the cluster magnetic control micro-nano robot is driven to target the affected part for recruitment in a rotating magnetic field with the intensity of 8mT. And measuring the concentration of the doxorubicin solution after the cluster magnetic control micro-nano robot is immersed by using a fluorescence spectrophotometer, so as to calculate the drug loading rate of the cluster micro-nano robot, and observing the motion trail of the cluster magnetic control micro-nano robot under a microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 2 in domestic sewage, standing for 2 hours, taking out, and detecting the components in the sewage by using a fluorescence spectrophotometer.
The result shows that the particle size of the graphene-ferroferric oxide nano particles obtained in the embodiment 2 is 5 mu m, the diameter of the clustered micro-nano robot is 3mm, the drug loading rate is 72%, and the graphene-ferroferric oxide nano particles can be targeted to an affected part under the action of a rotating magnetic field, so that doxorubicin can be accurately and directionally delivered to a target position; meanwhile, the content of organic components in the sewage is reduced.
Example 3
A. Adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution; according to the mass percentage, the mixing proportion ratio of the anhydrous ferric trichloride to the deionized water is 1:4, a step of;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a polyamide imide film with the thickness of 150 mu m, and heating at 80 ℃ to obtain the polyamide imide film with ferric trichloride hexahydrate attached on the surface;
C. performing laser processing on the polyamide imide film with the ferric trichloride hexahydrate surface in the step B by utilizing laser with the wavelength of 360nm and the laser power of 15W to obtain a polyamide imide film with the graphene-ferroferric oxide conjugate surface; placing the polyamide imide film with the graphene-ferroferric oxide conjugate attached to the surface into a glassware filled with 100ml of deionized water, soaking for 40s, and drying at 80 ℃;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the polyamide imide film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate in an ultrasonic oscillator with the vibration frequency of 40kHz for 60 seconds to obtain graphene-ferroferric oxide nano particles;
E. and E, putting 0.3mg of graphene-ferroferric oxide nano particles in the step E into 30g of deionized water for dispersion, and applying a rotating magnetic field with the intensity of 10mT to magnetize to obtain the clustered magnetic control micro-nano robot.
And D, measuring the diameter of the clustered magnetic micro-nano robot in the embodiment 3 and the graphene-ferroferric oxide nano particles obtained in the step D by using a scanning electron microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 3 in a doxorubicin solution with the concentration of 50-60 mug/ml, standing for 2 hours, and taking out to obtain the clustered magnetic micro-nano robot loaded with doxorubicin; the cluster magnetic control micro-nano robot is driven to target the affected part for recruitment in a rotating magnetic field with the intensity of 10mT. And measuring the concentration of the doxorubicin solution after the cluster magnetic control micro-nano robot is immersed by using a fluorescence spectrophotometer, so as to calculate the drug loading rate of the cluster micro-nano robot, and observing the motion trail of the cluster magnetic control micro-nano robot under a microscope.
Immersing the clustered magnetic micro-nano robot obtained in the embodiment 3 in domestic sewage, standing for 2 hours, taking out, and detecting the components in the sewage by using a fluorescence spectrophotometer.
The result shows that the particle size of the graphene-ferroferric oxide nano particles obtained in the embodiment 3 is 800nm, the diameter of the clustered micro-nano robot is 4mm, the drug loading rate is 75%, and the graphene-ferroferric oxide nano particles can be targeted to an affected part under the action of a rotating magnetic field, so that doxorubicin can be accurately and directionally delivered to a target position; meanwhile, the content of organic components in the sewage is reduced.
Comparative example 1
The procedure of example 1 was repeated except that the mixing ratio of anhydrous ferric trichloride to deionized water in the step C was different from that of example 1. In the comparative example 1, in the step C, the mixing ratio of anhydrous ferric trichloride to deionized water is 1:5.
and D, measuring the diameter of the cluster magnetic micro-nano robot in comparative example 1 and the graphene-ferroferric oxide nano particles obtained in the step D by using a scanning electron microscope.
Immersing the clustered magnetic micro-nano robot obtained in the comparative example 1 in a doxorubicin solution with the concentration of 50-60 mug/ml, standing for 2 hours, and taking out to obtain the clustered magnetic micro-nano robot loaded with doxorubicin; the cluster magnetic control micro-nano robot is driven to target the affected part for recruitment in a rotating magnetic field with the intensity of 6 mT. And measuring the concentration of the doxorubicin solution after the cluster magnetic control micro-nano robot is immersed by using a fluorescence spectrophotometer, so as to calculate the drug loading rate of the cluster micro-nano robot, and observing the motion trail of the cluster magnetic control micro-nano robot under a microscope.
Immersing the clustered magnetic micro-nano robot obtained in the comparative example 1 in domestic sewage, standing for 2 hours, taking out, and detecting the components in the sewage by using a fluorescence spectrophotometer.
The result shows that the particle size of the graphene-ferroferric oxide nano particles obtained in the comparative example 1 is 10 mu m, and the clustered micro-nano robot can reduce the content of organic components in sewage; meanwhile, the doxorubicin can be targeted to an affected part under the action of a rotating magnetic field, and is accurately and directionally delivered to a target position, but the diameter of the doxorubicin is only 1.5mm, the medicine carrying rate is only 57%, and the medicine carrying requirement cannot be met. The method is characterized in that the content of ferric trichloride in the ferric trichloride solution is too low, so that the amount of graphene-ferroferric oxide nano particles obtained after laser processing is small, the volume of the clustered magnetic control micro-nano robot assembled under the action of a rotating magnetic field is small, and the use requirement of high drug carrying capacity cannot be met.
Comparative example 2
The procedure of example 1 was repeated except that the mixing ratio of anhydrous ferric trichloride to deionized water in the step C was different from that of example 1. In the comparative example 1, in the step C, the mixing ratio of anhydrous ferric trichloride to deionized water is 1:1.
the result of observing the product in the step E in the comparative example 2 by using a scanning electron microscope shows that the comparative example 2 is not assembled into the clustered micro-nano robot, and the graphene-ferroferric oxide nano particles cannot be obtained because too high ferric trichloride content in the ferric trichloride solution can cause too thick ferric trichloride hexahydrate crystallized on the surface of the carbon-based film, so that the laser beam cannot penetrate through the ferric trichloride hexahydrate to convert the carbon-based film into graphene.
Comparative example 3
The procedure was as in example 1, except that in step E, the weight of the graphene-ferroferric oxide nanoparticles was different from that of example 1. Wherein, in comparative example 3, the weight of the graphene-ferroferric oxide nanoparticle was 0.08mg.
And D, measuring the diameter of the cluster magnetic micro-nano robot in the comparative example 3 and the graphene-ferroferric oxide nano particles obtained in the step D by using a scanning electron microscope.
Immersing the clustered magnetic micro-nano robot obtained in the comparative example 3 in a doxorubicin solution with the concentration of 50-60 mug/ml, standing for 2 hours, and taking out to obtain the clustered magnetic micro-nano robot loaded with doxorubicin; the cluster magnetic control micro-nano robot is driven to target the affected part for recruitment in a rotating magnetic field with the intensity of 6 mT. And measuring the concentration of the doxorubicin solution after the cluster magnetic control micro-nano robot is immersed by using a fluorescence spectrophotometer, so as to calculate the drug loading rate of the cluster micro-nano robot, and observing the motion trail of the cluster magnetic control micro-nano robot under a microscope.
Immersing the clustered magnetic micro-nano robot obtained in the comparative example 3 in domestic sewage, standing for 2 hours, taking out, and detecting the components in the sewage by using a fluorescence spectrophotometer.
The result shows that the particle size of the graphene-ferroferric oxide nano particles obtained in the comparative example 1 is 9.9 mu m, and the clustered micro-nano robot can reduce the content of organic components in sewage; meanwhile, the doxorubicin can be targeted to an affected part under the action of a rotating magnetic field, and is accurately and directionally delivered to a target position, but the diameter of the doxorubicin is only 1.6mm, the medicine carrying rate is only 60%, and the medicine carrying requirement cannot be met. The size of the clustered magnetic control micro-nano robot is closely related to the number of graphene-ferroferric oxide nano particles, and if the mass of the graphene-ferroferric oxide nano particles is smaller than 0.1mg, the number of the graphene-ferroferric oxide nano particles contained in the clustered magnetic control micro-nano robot is smaller, and the clustered magnetic control micro-nano robot formed under the action of a rotating magnetic field has smaller volume and cannot meet the use requirement of high drug carrying capacity.
Comparative example 4
The procedure was as in example 1, except that in step E, the weight of the graphene-ferroferric oxide nanoparticles was different from that of example 1. Wherein, in comparative example 3, the weight of the graphene-ferroferric oxide nanoparticle was 0.4mg.
The result of observing the product obtained in the comparative example 4 by using a scanning electron microscope shows that the comparative example 1 is not assembled into the clustered micro-nano robot, because the weight of the graphene-ferroferric oxide nanoparticles is too high, the number of the graphene-ferroferric oxide nanoparticles contained in the clustered micro-nano robot is too large, the clustered micro-nano robot obtained under the action of a rotating magnetic field is easy to disperse, the stability is extremely poor, and the clustered micro-nano robot is difficult to assemble into a complete elliptic clustered micro-nano robot.
The technical principle of the present application is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the application and should not be taken in any way as limiting the scope of the application. Other embodiments of the application will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (10)
1. The preparation method of the clustered magnetic control micro-nano robot is characterized by comprising the following steps of:
A. adding anhydrous ferric trichloride into deionized water, and uniformly stirring to obtain a ferric trichloride solution;
B. uniformly coating the ferric trichloride solution in the step A on the surface of a carbon-based film, and heating to obtain the carbon-based film with ferric trichloride hexahydrate attached on the surface;
C. performing laser processing on the carbon-based film with the ferric trichloride hexahydrate attached to the surface in the step B to obtain a carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface;
D. stripping the graphene-ferroferric oxide conjugate on the surface of the carbon-based film in the step C to obtain the graphene-ferroferric oxide conjugate; carrying out ultrasonic vibration on the graphene-ferroferric oxide conjugate to obtain graphene-ferroferric oxide nano particles;
E. d, putting the graphene-ferroferric oxide nano particles obtained in the step D into deionized water for dispersion, and applying a rotating magnetic field to magnetize the graphene-ferroferric oxide nano particles to obtain a clustered magnetic control micro-nano robot;
in the step A, the mixing ratio of the anhydrous ferric trichloride to the deionized water is 1: (2-4);
in the step E, the weight of the graphene-ferroferric oxide nano particles is 0.1-0.3 mg.
2. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step A, the mixing ratio of the anhydrous ferric trichloride to the deionized water is 1:2.
3. the method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step B, the heating temperature of the heating step is 60-80 ℃.
4. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step B, the thickness of the carbon-based film is 80-150 mu m;
the carbon-based film includes any one of a polyimide film and a polyamideimide film.
5. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step C, the laser wavelength of the laser processing step is 350-360 nm, and the laser power is 10-15W.
6. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step D, the ultrasonic oscillation time of the ultrasonic oscillation step is 30-60 s, and the ultrasonic oscillation frequency is 30-40 kHz.
7. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: in the step E, the strength of the rotating magnetic field is 6-10 mT.
8. The method for preparing the clustered magnetic micro-nano robot according to claim 1, which is characterized in that: and C, soaking the carbon-based film with the graphene-ferroferric oxide conjugate attached to the surface in deionized water, and then drying.
9. The method for preparing the clustered magnetic micro-nano robot as set forth in claim 8, wherein: in the step C, the drying temperature in the drying step is 75-85 ℃.
10. The utility model provides a cluster magnetic control micro-nano robot which characterized in that: the clustered magnetic micro-nano robot is prepared by the preparation method of any one of claims 1-9, the clustered magnetic micro-nano robot is elliptical in shape, the diameter is 2-4 mm, and the drug loading rate is 70-75%.
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