A customizable construction-based MOF-based magnetic micro-robot and a preparation method and application thereof

Abstract

This invention discloses a customizable MOF-based magnetically controlled microrobot, its fabrication method, and its applications, belonging to the field of microrobot technology. The fabrication method includes the following steps: coupling a micro / nano fabrication template method with a two-phase interface self-assembly method to prepare a magnetic MOF microrobot; modifying the magnetic MOF microrobot with amino groups using a ligand exchange method; and then loading lipase using an ion adsorption method to finally obtain the customizable MOF-based magnetically controlled microrobot. The microrobot prepared by this invention can achieve efficient actuation under a magnetic field and can achieve precise control and perform complex tasks; at the same time, the fabrication method disclosed in this invention is simple and easy to implement, and is a process for mass-producing customizable magnetically controlled MOF microrobots.

Description

Technical Field

[0001] This invention belongs to the field of microrobot technology, and particularly relates to a customizable MOF-based magnetically controlled microrobot, its fabrication method, and its applications. Background Technology

[0002] Microrobots are miniature devices capable of converting external energy into their own kinetic energy, demonstrating enormous application potential in fields such as environmental remediation, biomedical engineering, and microfluidics. The energy sources driving microrobots are diverse, including sound waves, light, electricity, heat, and magnetism. Among these, magnetically controlled microrobots possess unique advantages in the biomedical field.

[0003] First, the excellent penetrating power of magnetic fields enables microrobots to achieve precise manipulation without disturbing biological tissues. This non-invasive approach makes magnetically controlled microrobots particularly effective for in vivo navigation and targeted drug delivery. For example, guided by an external magnetic field, magnetically controlled microrobots can accurately reach tumor areas, achieving efficient local drug release and reducing systemic side effects. Furthermore, magnetically controlled microrobots offer rapid response and high controllability. By adjusting the strength and direction of the magnetic field, the movement path and speed of the microrobot can be controlled in real time, maintaining precise operation even in complex biological environments. Simultaneously, by selecting appropriate materials and surface modifications, magnetically controlled microrobots can gradually degrade in vivo, releasing harmless byproducts and avoiding the potential risks of long-term retention. This characteristic ensures their safety in biomedical applications.

[0004] Metal-organic frameworks (MOFs) have shown great potential in the biomedical field due to their unique structure and properties. MOFs are composed of metal ions or clusters linked to organic ligands via coordination bonds, possessing highly ordered channels and extremely high specific surface areas, enabling efficient loading and release of drug molecules. By adjusting the organic ligands and metal ions, the pore size and shape of MOFs can be precisely controlled, thereby achieving selective loading of different drug molecules. This tunability offers possibilities for personalized therapy and improved drug bioavailability. MOFs also exhibit excellent performance in terms of biocompatibility and degradability. Many MOF materials can gradually degrade under physiological conditions, releasing harmless decomposition products and avoiding the potential risks of long-term retention. Furthermore, through surface modification or functionalization, MOFs can further enhance their biocompatibility and endow them with specific biological functions, such as targeting and stimulus responsiveness. For example, magnetic MOFs can achieve targeted delivery under the guidance of an external magnetic field, while pH-responsive MOFs can rapidly release drugs in the tumor microenvironment, improving therapeutic efficacy.

[0005] Combining magnetically controlled microrobots with MOFs (Metal-Oxide-Facility) will offer unique advantages in the biomedical field. Magnetically controlled microrobots enable precise navigation and manipulation, while MOFs provide efficient drug loading and release capabilities. Their combination allows for intelligent control and precise operation of drug delivery systems. For example, a magnetically controlled microrobot can carry an MOF structure and, guided by an external magnetic field, accurately reach the target region, achieving quantitative drug release through the pore structure of the MOF, thereby improving therapeutic efficacy. Furthermore, the combination of magnetically controlled microrobots and MOFs can achieve multifunctionality. For instance, embedding magnetic nanoparticles into MOF structures can simultaneously achieve magnetic navigation and drug delivery; or functionalizing the MOF surface can enable targeted recognition and binding of specific biomolecules. These multifunctional characteristics make the combination of magnetically controlled microrobots and MOFs a promising candidate for applications in the biomedical field.

[0006] However, despite the immense potential of combining magnetically controlled microrobots with MOFs in the biomedical field, current research still faces several challenges. For example, existing MOF microrobot designs lack flexibility, making it difficult to customize their shape and function to meet specific needs. This design limitation restricts their effectiveness in complex biological environments. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a customizable MOF-based magnetically controlled microrobot, its fabrication method, and its applications. The microrobot fabricated using this invention's method can achieve efficient actuation under magnetic field conditions and can be precisely controlled to perform complex tasks. Furthermore, the fabrication method disclosed in this invention is simple and represents a process for mass-producing customizable magnetically controlled MOF microrobots.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] One of the technical solutions of this invention:

[0010] A method for fabricating customizable MOF-based magnetically controlled microrobots includes the following steps:

[0011] Magnetic MOF microrobots were fabricated by coupling the micro-nano fabrication template method with the two-phase interface self-assembly method.

[0012] The magnetic MOF microrobot was modified with amino groups using ligand exchange, and then loaded with lipase using ion adsorption, ultimately yielding the customizable MOF-based magnetically controlled microrobot.

[0013] Preferably, the specific process of the micro / nano fabrication template method is as follows:

[0014] After spin-coating a sacrificial layer (Omnicot) onto a silicon wafer and drying it, photoresist is spin-coated, dried, and then a patterned mask is applied. The process of exposure, drying, development, and immersion is then performed sequentially to obtain a SU-8 film with the desired pattern.

[0015] Furthermore, the photoresist is SU-8 photoresist;

[0016] The developing solution used in the developing process is PGMEA.

[0017] Furthermore, the thickness of the SU-8 film with the desired pattern is 20 μm.

[0018] Furthermore, the pattern includes any one of the following: spiral, S-shaped, triangular, quadrilateral, circular, multi-petaled plum blossom, serrated, or bowl-shaped.

[0019] Beneficial effects: The different shapes defined in this invention correspond to different functions and applications. For example, spiral-shaped microrobots can be used for targeted drug delivery. Through their spiral design, they can move efficiently in body fluids and accurately reach the lesion area for treatment. Bowl-shaped microrobots can be used for micromanipulation and pickup applications, such as manipulating and transporting objects in a microscopic environment. Serrated microrobots can be used for cell manipulation and tissue engineering, and can perform cutting actions at specific locations to achieve cell disruption and thrombus removal. Multi-lobed plum blossom-shaped microrobots can be used for fluid dynamics research, and can efficiently propel and stir liquids, which helps in mixing and reaction processes.

[0020] Preferably, the specific steps of the two-phase interface self-assembly method are as follows:

[0021] A metal salt solution was first added to the container; then an SU-8 membrane was placed in it; and finally, a n-octanol solution containing Fe3O4 and organic ligands was added to carry out the self-assembly reaction.

[0022] Furthermore, the MOF constructed from the metal salt solution and organic ligand includes any one of ZIF-8, HKUST-1, MOF-177, MOF-5, and MOF-74.

[0023] Furthermore, the concentration of the metal salt solution is 0.17 mol / L; and / or

[0024] The Fe3O4 content in the n-octanol solution is 800 mg / mL, and the concentration of the organic ligand is 0.08 mol / L.

[0025] Furthermore, the metal salt solution is a zinc nitrate solution; and / or

[0026] The organic ligand is 2-methylimidazole.

[0027] Furthermore, the conditions for the self-assembly reaction are: reacting at room temperature for 120 min.

[0028] Preferably, the specific process of the ligand exchange method is as follows:

[0029] The magnetic MOF microrobot was immersed in a 3-amino-1,2,4-triazole solution and reacted at 50°C for 120 minutes.

[0030] Furthermore, the concentration of the 3-amino-1,2,4-triazole solution is 0.08 mol / L.

[0031] Preferably, the specific process of the ion adsorption method is as follows:

[0032] The amino-modified magnetically controlled MOF microrobots were placed in a lipase solution and reacted for 12 hours.

[0033] Furthermore, the lipase solution is obtained by dissolving lipase in PBS, with a lipase concentration of 2 mg / mL and a PBS concentration of 10 mM.

[0034] The second technical solution of the present invention:

[0035] A customizable MOF-based magnetically controlled microrobot is prepared by the above-described method.

[0036] The third technical solution of this invention:

[0037] A method for manipulating a customizable MOF-based magnetically controlled microrobot includes the following steps:

[0038] Under the condition of applying an external magnetic field, the movement mode of the MOF-based magnetically controlled microrobot is controlled by a handle;

[0039] The applied magnetic field conditions include any one of the following: a constant field (1-10 mT, 0.1-35 Hz), an XY plane rotating field (5-10 mT, 8-15 Hz), or an XZ plane rotating field (3-10 mT, 1-6 Hz).

[0040] Preferably, a MOF-based magnetically controlled microrobot with a helical shape can move efficiently and reach a designated target position under an external XZ plane rotational field (3-10mT, 1-6Hz).

[0041] Preferably, a bowl-shaped MOF-based magnetically controlled microrobot, under the combined control of an external XY plane rotation field (5-8mT, 8-15Hz) and a handle, can move to the target position and pick up the target object, thus realizing the picking and transportation of goods.

[0042] Preferably, a serrated MOF-based magnetically controlled microrobot, under the combined control of an external XY plane rotational field (8-10 mT, 8-10 Hz) and a handle, can achieve high-speed rotational motion to cut target cells or tissues.

[0043] Preferably, a multi-petaled plum blossom-shaped MOF-based magnetically controlled microrobot can move and stir efficiently in a liquid under an applied magnetic field (1-10mT, 0.1-35Hz).

[0044] Fourth technical solution of the present invention:

[0045] A customizable MOF-based magnetically controlled microrobot is proposed for applications in degrading triglycerides, delivering targeted drugs, or treating thrombolysis. The MOF-loaded DOX achieves a drug loading rate of up to 68.43% and can target breast cancer. Furthermore, the loaded drug can also be t-PA with thrombolytic properties.

[0046] Preferably, the degradation process of the triglycerides is as follows:

[0047] In an acidic microenvironment, the MOF is decomposed by acid, thereby releasing the lipase for the degradation of triglycerides.

[0048] Compared with the prior art, the present invention has the following advantages and technical effects:

[0049] 1. This invention realizes microrobots with designable structures by coupling a mature interfacial diffusion self-assembly strategy in metal-organic framework (MOF) material synthesis with a micro / nano fabrication template method. This method enables the design of various structures to flexibly meet different application requirements. Furthermore, magnetic nanoparticles and drugs or enzymes can be integrated and loaded, thereby effectively utilizing the porous structure of MOF materials and simplifying the synthesis process. This lays a solid foundation for subsequent magnetic manipulation and drug therapy.

[0050] 2. This invention achieves targeted and precise manipulation by optimizing magnetic field parameters. Combined with different cutting motion patterns, it can further improve degradation efficiency caused by diffusion. Furthermore, the release of responsive drugs or enzymes will further enhance the therapeutic effect. The integration of these unique microrobots with image-guided manipulation technology will greatly expand its applications in the biomedical field, providing an effective strategy for precision medicine. Attached Figure Description

[0051] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0052] Figure 1This invention provides a pathway for the preparation of customizable SU-8 membranes and the synthesis of MOF magnetically controlled microrobots via self-assembly at a two-phase interface.

[0053] Figure 2 An optical microscope image of the customizable magnetically controlled MOF microrobot prepared in Example 2;

[0054] Figure 3 SEM and EDX images of the customizable magnetically controlled MOF microrobot prepared in Example 2;

[0055] Figure 4 Optical microscope images of MOF microrobots of different shapes prepared in Example 4;

[0056] Figure 5 The graph shows the relationship between the thickness of the non-magnetic MOF microrobot prepared in Example 3 and time.

[0057] Figure 6 The graph showing the relationship between the velocity and magnetic field frequency of the customizable magnetically controlled MOF microrobot prepared in Example 6;

[0058] Figure 7 The motion behavior diagram of the customizable magnetically controlled MOF microrobot under the action of a constant magnetic field was prepared in Example 6;

[0059] Figure 8 Example 6 shows the repeating motion trajectory of a customizable magnetically controlled MOF microrobot under the action of a rotating magnetic field in the YZ plane.

[0060] Figure 9 The graph shows the degradation of triglycerides by the customizable magnetically controlled MOF microrobot in Example 8 under different conditions.

[0061] Figure 10 for Figure 9 The image shows the process of MOF decomposing and releasing lipase during the degradation of triglycerides by a customizable magnetically controlled MOF microrobot under experimental conditions in group C. Detailed Implementation

[0062] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0063] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0064] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0065] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0066] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0067] In a first aspect, the present invention discloses a method for fabricating customizable MOF-based magnetically controlled microrobots, comprising the following steps: firstly, a SU-8 film with the desired pattern is prepared, then a magnetic MOF microrobot is synthesized by a two-phase interface self-assembly method, and after amino modification, it is combined with lipase to obtain a functional magnetic MOF microrobot.

[0068] The preparation process of the SU-8 film with the desired pattern includes the following steps:

[0069] A sacrificial layer (Omnicoat) is spin-coated onto a clean silicon wafer, followed by a photolithography step. Finally, the silicon wafer with the desired pattern is immersed in N-methylpyrrolidone to remove the Omnicoat, thus obtaining the SU-8 film.

[0070] In some preferred embodiments, the SU-8 membrane may have any shape.

[0071] In some preferred embodiments, the thickness of the SU-8 film is approximately 20 μm.

[0072] In some preferred embodiments, the method for self-assembly of the two-phase interface is as follows: first, add an aqueous solution of zinc nitrate to a container, then place in an SU-8 membrane containing the desired pattern, and finally add an octanol solution containing Fe3O4 and 2-methylimidazole.

[0073] In some preferred embodiments, the reaction time for self-assembly of the two-phase interface is 120 min.

[0074] In some preferred embodiments, the amino modification process is as follows: the magnetic MOF microrobot is placed in a 3-amino-1,2,4-triazole solution and reacted for 120 min.

[0075] In some preferred embodiments, the process of loading lipase is as follows: amino-modified magnetic MOF microrobots are added to the lipase solution and reacted for 12 hours.

[0076] Secondly, the present invention discloses a process for releasing lipase using a MOF magnetically controlled microrobot loaded with lipase, comprising: in an acidic microenvironment, using acid to decompose MOF (ZIF-8), thereby releasing lipase.

[0077] Thirdly, the present invention provides a customizable functional MOF magnetically controlled microrobot prepared according to the above-described preparation method.

[0078] Fourthly, this invention provides an application of MOF-based magnetically controlled microrobots in the fields of triglyceride degradation, targeted drug delivery, and thrombolytic therapy. Specifically, it utilizes MOF-based magnetically controlled microrobots to achieve precise navigation and manipulation under the influence of a magnetic field.

[0079] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0080] All raw materials used in this invention were purchased from the market.

[0081] The technical solution of the present invention will be further illustrated by the following embodiments.

[0082] Example 1

[0083] The preparation of customizable SU-8 membranes includes the following steps:

[0084] (1) Cleaning silicon wafers: The cleaning solution is prepared by mixing 30% hydrogen peroxide and 98% concentrated sulfuric acid at a volume ratio of 1:7. Then, the silicon wafers are immersed in the cleaning solution and heated to 180°C for cleaning. After cleaning, the silicon wafers are cleaned alternately with water, isopropanol and acetone to ensure that their surfaces are thoroughly cleaned. Then, a sacrificial layer (Omnicot) is spin-coated on them.

[0085] (2) Preparation of SU-8 film with five-petal plum blossom pattern by photolithography: The selected photoresist is SU-8 photoresist, the spin coating condition is 1500r / min, after spinning for 30s, it is dried at 95℃ for 5min, and then a patterned mask with a pattern size of 25×25cm is covered on it, exposed for 120s and then dried at 95℃ for 6min, and developed using PGMEA developer; finally, the sacrificial layer is removed by immersing the patterned silicon wafer in N-methylpyrrolidone, and the SU-8 film with five-petal plum blossom pattern is obtained.

[0086] Example 2

[0087] The following steps are taken to synthesize a magnetically controlled MOF microrobot through self-assembly at a two-phase interface:

[0088] First, add 3 mL of zinc nitrate solution with a concentration of 0.17 mol / L to the container; then place the SU-8 membrane prepared in Example 1 on top of the aqueous solution; then add 1 mL of n-octanol solution containing Fe3O4 and 2-methylimidazole, and react for 120 minutes, wherein the content of Fe3O4 is 800 mg / mL and the concentration of 2-methylimidazole is 0.08 mol / L.

[0089] Example 3

[0090] The steps for self-assembly synthesis of MOF microrobots at two-phase interfaces are as follows:

[0091] First, add 3 mL of zinc nitrate solution with a concentration of 0.17 mol / L to the container; then place the SU-8 membrane prepared in Example 1 on top of the aqueous solution; then add 1 mL of 2-methylimidazole in n-octanol solution and react for 120 minutes. The concentration of 2-methylimidazole is 0.08 mol / L.

[0092] In this embodiment, the thickness of the obtained MOF robot is approximately 5 μm.

[0093] Example 4

[0094] The following steps illustrate the self-assembly of MOF microrobots of different shapes at two-phase interfaces:

[0095] First, add 3 mL of zinc nitrate solution (0.17 mol / L) to the container; then place SU-8 membranes with different patterns on top of the aqueous solution; next, add 1 mL of 2-methylimidazole in n-octanol solution and react for 120 minutes. The concentration of 2-methylimidazole is 0.08 mol / L.

[0096] The preparation process of the SU-8 film with different patterns mentioned in this embodiment is the same as in Embodiment 1, except that the pattern in the photomask is different from that in Embodiment 1. The specific pattern is as follows: Figure 4 As shown.

[0097] Example 5

[0098] The amino modification of magnetically controlled MOF microrobots follows these steps:

[0099] The magnetically controlled MOF microrobot prepared in Example 2 was added to a 3-amino-1,2,4-triazole solution with a concentration of 0.08 mol / L, and the reaction was carried out at 50°C for 120 minutes.

[0100] Example 6

[0101] The steps for loading lipases onto a magnetically controlled MOF microrobot are as follows:

[0102] The amino-modified magnetically controlled MOF microrobot of Example 5 was placed in a lipase solution (lipase dissolved in PBS at a concentration of 2 mg / mL and PBS concentration of 10 mM) and reacted for 12 hours.

[0103] Example 7

[0104] The steps for manipulating a magnetically controlled MOF microrobot are as follows:

[0105] like Figure 7 As shown, the magnetically controlled MOF microrobot prepared in Example 6 can stand upright when a constant field (10mT, 0.1Hz) is applied, that is, perpendicular to the XY plane; when the magnetic field is removed, the magnetically controlled MOF microrobot returns to its original lying state; in addition, when a rotating field (10mT, 8Hz) is applied to the XY plane, clockwise or counterclockwise rotation can be achieved by controlling the direction of rotation with a handle.

[0106] like Figure 8 As shown, when an XZ plane rotational field (7mT, 8Hz) is applied, combined with handle control, the magnetically controlled MOF microrobot can perform repetitive motions along a specified shape.

[0107] Furthermore, helical magnetically controlled microrobots achieve efficient movement and reach designated locations by applying an XZ-plane rotational field (3-10 mT, 1-6 Hz); bowl-shaped magnetically controlled microrobots, by applying an XY-plane rotational field (5-8 mT, 8-15 Hz) combined with handle control, can move to target locations and pick up target objects, realizing cargo pickup and transportation; serrated magnetically controlled microrobots, by applying an XY-plane rotational field (8-10 mT, 8-10 Hz) combined with handle control, can achieve high-speed rotational motion to cut target cells or tissues; multi-lobed plum blossom-shaped magnetically controlled microrobots, by utilizing different magnetic fields and frequencies (1-10 mT, 0.1-35 Hz), demonstrate their motion behavior and surrounding fluid dynamics, enabling efficient movement and stirring in liquids.

[0108] Example 8

[0109] The following steps were taken to degrade triglycerides using a magnetically controlled MOF microrobot:

[0110] Four sets of experiments were set up with glyceryl tributylate as the degradation target:

[0111] Group A: Magnetically Controlled MOF Microrobot (Example 2)

[0112] Group B: Magnetically controlled MOF microrobot (Example 2) + magnetic field

[0113] Group C: Magnetically controlled MOF microrobots loaded with lipase (Example 6)

[0114] Group D: Magnetically controlled MOF microrobot loaded with lipase (Example 6) + magnetic field; compare the efficiency of each group in degrading tributyrate.

[0115] Figure 1 The present invention demonstrates the path diagram for preparing customizable SU-8 membranes and synthesizing magnetically controlled MOF microrobots via two-phase interface self-assembly. The process is as follows: 1) Obtaining SU-8 membranes using micro-nano fabrication methods; 2) Synthesizing magnetically controlled MOF microrobots using interface self-assembly methods; 3) Modifying the magnetically controlled MOF microrobots with amino groups; 4) Loading lipases onto the amino-modified magnetically controlled MOF microrobots using the principle of ion adsorption.

[0116] Figure 2 Optical microscope images of the customizable magnetically controlled MOF microrobot prepared according to Example 2 of this invention are shown. Figure 2 As can be seen, the microrobots are arranged in a regular pattern and are approximately 140 micrometers in size.

[0117] Figure 3 The SEM and EDX elemental distribution maps of the customizable magnetically controlled MOF microrobot prepared in Example 2 of this invention are shown. Figure 3 As can be seen, elements such as Fe, N, and Zn are uniformly distributed on the surface of the magneto-controlled MOF microrobot.

[0118] Figure 4 The invention demonstrates MOF microrobots of different shapes made of non-magnetic materials, prepared according to Example 4 of this invention.

[0119] Figure 5 The graph shows the relationship between the thickness of the non-magnetic MOF microrobot prepared in Example 3 of the present invention and time.

[0120] Testing of magnetically controlled MOF microrobots:

[0121] The microrobot prepared in Example 6 was placed in deionized water and then transferred to a PDMS tank. Its movement could be observed and recorded under the control of a magnetic field.

[0122] The movement speed of the microrobot changes with the frequency of the magnetic field, as follows: Figure 6 As shown, the speed of the microrobot first increases and then decreases under different magnetic field strengths, with the speed reaching 379 μm / s at 10 mT 6 Hz.

[0123] Figure 7 Example 6 shows the motion behavior of a customizable magnetically controlled MOF microrobot under a constant magnetic field. It demonstrates the motion manipulation of the MOF magnetically controlled microrobot under the control of a constant magnetic field (10mT 0.1Hz). The micro-nano robot can exhibit "standing" and "lying down" motion behaviors, thus proving that the motion behavior of micro-nano robots can be controlled by a magnetic field.

[0124] Figure 8 Example 6 shows the motion trajectory of a customizable MOF magnetically controlled microrobot, manipulated by a magnetic field (XZ plane, 7mT, 8Hz), repeating 30 times along a rectangle. Figure 8 It can be seen that precise control of the movement of microrobots can be achieved under the control of an external magnetic field.

[0125] Figure 9 For the degradation of tributyrate in each group of Example 7 of the present invention, after 55 minutes, the degradation rates of groups A to D were 5.53%, 14.39%, 80.94%, and 100%, respectively. Under a magnetic field, MMWRs loaded with lipase (Example 6) were observed to have a higher degradation percentage; this indicates that mechanical interactions enhanced diffusion, thereby enhancing the degradation of tributyrate droplets. Simultaneously, the acid generated during the degradation process caused ZIF-8 to decompose, further releasing lipase and forming a positive feedback mechanism that accelerated the degradation of tributyrate droplets.

[0126] Figure 10 In Example 7, during the degradation of triglycerides under the experimental conditions of Group C, the MOF microrobots decomposed and their area decreased under acidic conditions (i.e., butyric acid produced by lipase during the catalytic degradation of tricresyltriglyceride, making the microenvironment acidic, with a pH of 4.56).

[0127] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for preparing a customizable built MOF-based magnetically controlled micro-robot, characterized in that, The method comprises the following steps: The micro-nano processing template method is coupled with the two-phase interface self-assembly method to prepare a magnetic MOF micro robot; The magnetic MOF micro robot is modified with amino groups by using a ligand exchange method, and then loaded with lipase by using an ion adsorption method, so as to finally obtain the customizable MOF-based magnetic micro robot; The specific process of the micro-nano processing template method is as follows: a sacrificial layer is spin-coated on a silicon wafer, and then photoresist is spin-coated after drying; then, a mask plate with a pattern is covered, and then exposure, drying, development and immersion are sequentially performed to obtain an SU-8 film with a required pattern; The specific steps of the two-phase interface self-assembly method are as follows: a metal salt solution is first added into a container; then, the SU-8 film is added; and then, a n-octanol solution containing Fe3O4 and an organic ligand is added for self-assembly reaction; wherein, the MOF constructed by the metal salt solution and the organic ligand comprises any one of ZIF-8, HKUST-1, MOF-177, MOF-5 or MOF-74; The specific process of the ligand exchange method is as follows: the magnetic MOF micro robot is immersed in a 3-amino-1, 2, 4-triazole solution, and reacts at 50 DEG C for 120 minutes.

2. The method for fabricating a customizable MOF-based magnetically controlled microrobot according to claim 1, characterized in that, The pattern comprises any one of a spiral shape, an S shape, a triangular shape, a quadrilateral shape, a circular shape, a multi-petal plum blossom shape, a zigzag shape or a bowl shape.

3. The method for fabricating a customizable MOF-based magnetically controlled microrobot according to claim 1, characterized in that, The specific process of the ion adsorption method is as follows: The amino-modified magnetic MOF micro robot is placed in a lipase solution and reacts for 12 hours.

4. A customizable built MOF-based magnetic microrobot, characterized in that, Prepared by the preparation method of any one of claims 1-3.

5. A method for manipulating a customizable built MOF-based magnetic microrobot, characterized in that, The method comprises the following steps: Under the condition of applying an external magnetic field, the motion mode of the MOF-based magnetic micro robot of claim 4 is controlled by a handle; The external magnetic field condition is as follows: a constant field with a magnetic field of 1-10 mT and a frequency of 0.1-35 Hz; and / or an XY plane rotating field with a magnetic field of 5-10 mT and a frequency of 8-15 Hz; and / or an XZ plane rotating field with a magnetic field of 3-10 mT and a frequency of 1-6 Hz.

6. The application of the customizable MOF-based magnetic micro robot of claim 4 in the preparation of a drug for degrading triglyceride, or in the preparation of a carrier for delivering a targeted drug.

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