Self-energized enzyme power material as well as preparation method and application thereof

Abstract

The invention provides a self-energized enzyme power material as well as a preparation method and application thereof, and relates to the technical field of intelligent micro / nano materials. The self-energized enzyme power material is formed by compounding a carrier material and a loading material, the carrier material comprises one or more of MOFs, ZIFs, silicon dioxide, polyphenol and polydopamine; the loading material comprises an enzyme and an active component, and the enzyme comprises one or more of urease, catalase and esterase; the active component comprises one or more of urea, hydrogen peroxide and ethyl acetate. The self-energized enzyme power material provided by the invention can effectively load and regulate urease and carry fuel, so that the self-energized enzyme power material has a continuous propulsion capability and an adaptive pH regulation function. The self-energized enzyme power material disclosed by the invention has an environment sensing function and motion durability.

Description

Technical Field

[0001] The present invention relates to the technical field of intelligent micro / nano materials, and in particular to a self-powered enzyme power material and a preparation method and application thereof. Background Art

[0002] Smart nanomaterials can adapt and respond by communicating with the environment, thereby performing different tasks in complex environments within the body. In recent years, the design and development of various micro / nano materials have made significant progress in biomedical applications. Improving the continuous and sustained propulsion capability of micro / nanomotors remains one of the main challenges facing nanomedicine and other related fields. Therefore, how to provide a self-powered enzyme-powered material with sustained motor propulsion capability is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0003] The purpose of the present invention is to provide a self-powered enzyme power material and its preparation method and application in view of the deficiencies in the prior art, so as to solve the technical problem existing in the prior art of how to improve the continuous and sustained propulsion ability of micro / nano material motors.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a self-powered enzyme power material, which is composited by a carrier material and a load material;

[0006] The carrier material comprises one or more of MOFs, ZIFs, silicon dioxide, polyphenols and polydopamine;

[0007] The load material comprises an enzyme and an active component, wherein the enzyme comprises one or more of urease, catalase and esterase; and the active component comprises one or more of urea, hydrogen peroxide and ethyl acetate.

[0008] The present invention also provides a method for preparing a self-energy enzyme power material, comprising the following steps:

[0009] (1) mixing a carrier material with an active component solution to obtain a carrier composite material;

[0010] (2) activating and centrifuging the carrier composite material in sequence;

[0011] (3) The treated carrier composite material, enzyme and active component solution are mixed and reacted and centrifuged in sequence to obtain a self-powered enzyme power material.

[0012] Preferably, in step (1), the active component solution is an ethanol solution of the active component with a concentration of 8 to 13 mg / mL;

[0013] The usage ratio of the carrier material to the active component solution is 1 mg: 1-3 mL.

[0014] Preferably, in step (1), the carrier material and the active component solution are mixed for 2 to 3.5 days.

[0015] Preferably, in step (2), the activation is carried out in a cross-linking agent solution, which is one or more of an ethanol solution of glutaraldehyde, an ethanol solution of succinimide and an ethanol solution of polyaldehyde dextran; the concentration of the cross-linking agent solution is 1.5 to 5 wt.%; and the activation time is 20 to 120 min.

[0016] Preferably, the usage ratio of the carrier composite material to the cross-linking agent solution is 1-10 mg: 0.2-0.5 mL.

[0017] Preferably, in step (2) and step (3), the centrifugal speed is independently 7000-10000 rpm; and the centrifugal time is independently 5-30 min.

[0018] Preferably, in step (3), the usage ratio of the carrier composite material, enzyme and active component solution is 10-30 mg: 1-3 mg: 8-15 mL; the active component solution is a PBS solution of the active component with a concentration of 0.01-0.03 mol / L.

[0019] Preferably, in step (3), the reaction temperature is 10 to 40° C. and the reaction time is 5 to 10 h.

[0020] The present invention also provides the use of the self-powered enzyme power material as a fuel to increase the propulsion force of a motor.

[0021] Beneficial effects of the present invention:

[0022] The self-powered enzyme power material provided by the present invention can effectively load and regulate urease and carry fuel and enable it to have continuous propulsion capability and adaptive pH control function;

[0023] The material provided by the invention has environmental sensing function and motion persistence. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A scanning electron microscope image of the Nd-BDC-NH2 material prepared in Example 1;

[0025] Figure 2 This is a nitrogen adsorption curve of the Nd-BDC-NH2 material prepared in Example 1;

[0026] Figure 3Zeta potential diagrams of MOFs, MOFs-GA and MOFs-urease materials;

[0027] Figure 4 Thermogravimetric diagrams of the MOFs material and urea@MOFs material prepared in Example 1;

[0028] Figure 5 The urea content of the urea@MOFs supernatant of Example 1 on the first and fourth days;

[0029] Figure 6 The urea release percentage diagram of urea@MOFs and urea@MOFs-urease materials prepared in Example 1;

[0030] Figure 7 Mean square displacement diagram of urea@MOFs-urease and MOFs-urease prepared in Example 1;

[0031] Figure 8 This is the mean square displacement diagram of ester@MOFs-esterase and ester@MOFs prepared in Example 2. DETAILED DESCRIPTION

[0032] The present invention provides a self-powered enzyme power material, which is composited by a carrier material and a load material;

[0033] The carrier material comprises one or more of MOFs, ZIFs, silicon dioxide, polyphenols and polydopamine;

[0034] The load material comprises an enzyme and an active component, wherein the enzyme comprises one or more of urease, catalase and esterase; and the active component comprises one or more of urea, hydrogen peroxide and ethyl acetate.

[0035] In the present invention, the carrier material is preferably one or more of MOFs, silica and polyphenols, and more preferably MOFs and / or silica.

[0036] In the present invention, the enzyme is preferably urease and / or catalase, and more preferably urease; the active component is preferably urea and / or hydrogen peroxide, and more preferably urea.

[0037] In the present invention, the carrier material is preferably a porous MOFs material with a particle size of 2.5 μm.

[0038] The present invention also provides a method for preparing a self-energy enzyme power material, comprising the following steps:

[0039] (1) mixing a carrier material with an active component solution to obtain a carrier composite material;

[0040] (2) activating and centrifuging the carrier composite material in sequence;

[0041] (3) The treated carrier composite material, enzyme and active component solution are mixed and reacted and centrifuged in sequence to obtain a self-powered enzyme power material.

[0042] In the present invention, in step (1), the active component solution is an ethanol solution of the active component, and the concentration is 8 to 13 mg / mL, preferably 9 to 12 mg / mL, and more preferably 10 to 11 mg / mL;

[0043] The usage ratio of the carrier material to the active component solution is 1 mg: 1-3 mL, preferably 1 mg: 2 mL.

[0044] In the present invention, in step (1), the time for mixing the carrier material and the active component solution is 2 to 3.5 days, preferably 2.2 to 3.2 days, and more preferably 2.5 to 3 days.

[0045] In the present invention, in step (2), the activation is carried out in a cross-linking agent solution, and the cross-linking agent solution is one or more of an ethanol solution of glutaraldehyde, an ethanol solution of succinimide and an ethanol solution of polyaldehyde dextran, preferably an ethanol solution of glutaraldehyde and / or an ethanol solution of polyaldehyde dextran, and more preferably an ethanol solution of glutaraldehyde; the concentration of the cross-linking agent solution is 1.5 to 5 wt.%, preferably 2 to 4.5 wt.%, and more preferably 2.5 to 4 wt.%.

[0046] In the present invention, the activation time is 20 to 120 min, preferably 30 to 100 min, and more preferably 40 to 90 min.

[0047] In the present invention, the usage ratio of the carrier composite material to the cross-linking agent solution is 1-10 mg: 0.2-0.5 mL, preferably 2-8 mg: 0.3-0.4 mL, and more preferably 3-6 mg: 0.4 mL.

[0048] In the present invention, in step (2) and step (3), the centrifugal speed is independently 7000-10000 rpm, preferably 7500-9500 rpm, and more preferably 8000-9000 rpm; the centrifugal time is independently 5-30 min, preferably 12-28 min, and more preferably 15-25 min.

[0049] In the present invention, in step (3), the usage ratio of the carrier composite material, enzyme and active component solution is 10-30 mg: 1-3 mg: 8-15 mL, preferably 12-28 mg: 1.5-2.5 mg: 9-14 mL, and further preferably 13-23 mg: 1-2 mg: 10-13 mL; the active component solution is a PBS solution of the active component, and the concentration is 0.01-0.03 mol / L, preferably 0.01 mol / L.

[0050] In the present invention, in step (3), the reaction temperature is 10 to 40°C, preferably 15 to 35°C, and more preferably 20 to 30°C; the reaction time is 5 to 10 hours, preferably 6 to 9 hours, and more preferably 7 to 8 hours.

[0051] In the present invention, the carrier composite material needs to be cleaned with an ethanol solution.

[0052] In the present invention, the cleaning time is 5 min to 30 min, preferably 10 min to 25 min, and more preferably 15 min to 20 min.

[0053] In the present invention, the number of cleaning is 3 to 5 times, preferably 4 times.

[0054] In the present invention, the MOFs can be prepared by a solvothermal method, specifically, dissolving neodymium chloride hexahydrate and 2-aminoterephthalic acid in N,N-dimethylformamide in sequence, mixing and reacting, filtering, drying, collecting a khaki solid, and obtaining a Nd-BDC-NH2 material.

[0055] In the present invention, the concentration of the neodymium chloride hexahydrate in N,N-dimethylformamide is 0.015-0.030 g / mL, preferably 0.018-0.028 g / mL, and more preferably 0.020-0.025 g / mL; the concentration of the 2-aminoterephthalic acid in N,N-dimethylformamide is 0.008-0.018 g / mL, preferably 0.010-0.015 g / mL, and more preferably 0.011-0.013 g / mL; the usage ratio of the neodymium chloride hexahydrate to the 2-aminoterephthalic acid is 1-3:1-3, preferably 1.5-2.8:1.5-2.8, and more preferably 1.8-2.5:1.8-2.5.

[0056] In the present invention, in the preparation of MOFs, the reaction temperature is 110 to 130° C., preferably 115 to 125° C., and more preferably 120° C.; the reaction time is 3 to 20 h, preferably 5 to 15 h, and more preferably 8 to 10 h.

[0057] In the present invention, the self-energy enzyme power material comprises a urea@MOFs-urease composite material and an ester@MOFs-esterase composite material.

[0058] The concentration of urea in the urea@MOFs-urease composite material reaction is ≥1 g / mL, preferably 1 g / mL, 2 g / mL, or 3 g / mL.

[0059] In the present invention, the diameter of the urea@MOFs-urease composite material is 50 to 100 μm, preferably 60 to 90 μm, and more preferably 70 to 80 μm;

[0060] In the present invention, the volume of the urea@MOFs-urease composite material reaction system is 50 to 120 mL, preferably 60 to 110 mL, and more preferably 100 mL.

[0061] In the present invention, the urea@MOFs-urease composite material has a porous structure and has a good drug-carrying capacity, and can be used as a drug carrier.

[0062] In the present invention, the combination of the carrier material and the enzyme in the self-energy enzyme power material is in the form of one or more of covalent cross-linking, adsorption, and coating.

[0063] The present invention also provides the use of the self-powered enzyme power material as a fuel to increase the propulsion force of a motor.

[0064] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0065] Example 1

[0066] 1 mg MOFs was dissolved in 2 mL of 10 mg / mL urea ethanol solution, stirred at 400 rpm for three days, centrifuged at 7000 rpm for 25 min, washed three times with ethanol solution, and dried in an oven to obtain urea@MOFs material;

[0067] 10mgurea@MOFs material was activated in 0.5mL2.5wt.% glutaraldehyde ethanol solution for 30 minutes, taken out and centrifuged at 8000rpm for 20min, and ultrasonicated with PBS buffer for 15 minutes, washed three times, and the unreacted glutaraldehyde ethanol solution was washed away; 10g urea was weighed and dissolved with 10mL PBS buffer (the solution was a supersaturated solution at this time), and then the centrifuged 10mgurea@MOFs was put into the solution, 1mg urease was added, and the reaction was carried out in a shaker at 25°C for 8h; taken out and centrifuged and washed three times with 0.01mol / L PBS buffer to obtain urea@MOFs-urease material, which was stored in a refrigerator.

[0068] Example 2

[0069] 5 mg MOFs were dissolved in 10 mL of 11 mg / mL ethyl acetate ethanol solution, stirred at 300 rpm for three days, centrifuged at 1000 rpm for 15 min, washed three times with ethanol solution, and dried in an oven to obtain ester@MOFs material.

[0070] After activating 10mgester@MOFs material in 0.5mL3wt.% glutaraldehyde ethanol solution for 30 minutes, take it out and centrifuge it at 900rpm for 20min, and use PBS buffer to ultrasonicate for 15 minutes, wash it four times, and wash away the unreacted glutaraldehyde ethanol solution. Then put the centrifuged 10mgester@MOFs into 10mL ethyl acetate, add 2mg esterase, react in a shaker at 30℃ for 10h, and then take it out. After centrifugation, wash it three times with 0.01mol / L PBS buffer to obtain ester@MOFs-esterase, and store it in a refrigerator.

[0071] The performance test of the self-energy enzyme power material obtained in the above examples 1 to 2 was carried out: Figure 1 As can be seen from the scanning electron microscope image of the MOFs material, it can be clearly seen that the material has holes and is evenly distributed in a spherical shape.

[0072] Figure 2 This is the nitrogen adsorption curve of MOFs material. It can be seen that the MOFs material Nd-BDC-NH2 is a mesoporous material and can be used as a matrix for adsorbing urea.

[0073] Figure 3 is the zeta potential of MOFs, MOFs-GA and MOFs-urease, indicating that urease is successfully cross-linked to the surface of MOFs material through the cross-linker. Figure 4 This is a comparison of the thermogravimetric data of MOFs and urea@MOFs materials. The urea@MOFs material has a significant drop at 120°C, which is due to the decomposition of urea at around 120°C. Figure 5 is the urea concentration of the supernatant of the urea adsorbed solution on different days. The urea concentration of the supernatant on the fourth day is less than that on the first day, indicating that urea is gradually adsorbed into the pores of MOFs. Figure 6 is the urea release percentage of urea@MOFs and urea@MOFs-urease materials, indicating that urea is successfully adsorbed into the pores of MOFs and the urea adsorbed in the pores of MOFs can be released in aqueous solution. Figure 7 It can be seen that in the mean square displacement of the self-powered motor (urea@MOFs-urease) and the ordinary motor (MOFs-urease), the diffusivity of the self-powered motor is better than that of the ordinary motor. Figure 8 The mean square displacement of ester@MOFs-esterase and ester@MOFs was obtained by replacing the enzyme and substrate with esterase and ethyl acetate, which was synthesized using the same method. This proves that the diffusivity of the self-powered motor is better than that of the ordinary motor.

[0074] As can be seen from the above embodiments, the present invention provides a self-powered enzyme power material and its preparation method and application. The self-powered enzyme power material provided by the present invention can effectively load and regulate urease and carry fuel and enable it to have continuous propulsion ability and adaptive pH control function; the material of the present invention has environmental sensing function and motion persistence.

[0075] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A self-powered enzyme power material, It is characterized in that The self-energy enzyme power material is composited by a carrier material and a load material; The carrier material comprises one or more of MOFs, ZIFs, silicon dioxide, polyphenols and polydopamine; The load material comprises an enzyme and an active component, wherein the enzyme comprises one or more of urease, catalase and esterase; and the active component comprises one or more of urea, hydrogen peroxide and ethyl acetate.

2. The method for preparing the self-energy enzyme power material according to claim 1, It is characterized in that The steps include: (1) mixing a carrier material with an active component solution to obtain a carrier composite material; (2) activating and centrifuging the carrier composite material in sequence; (3) The treated carrier composite material, enzyme and active component solution are mixed and reacted and centrifuged in sequence to obtain a self-powered enzyme power material.

3. The preparation method according to claim 2, It is characterized in that In step (1), the active component solution is an ethanol solution of the active component with a concentration of 8 to 13 mg / mL; The usage ratio of the carrier material to the active component solution is 1 mg: 1-3 mL.

4. The preparation method according to claim 3, It is characterized in that In step (1), the carrier material and the active component solution are mixed for 2 to 3.5 days.

5. The preparation method according to claim 2 or 4, It is characterized in that In step (2), the activation is carried out in a cross-linking agent solution, which is one or more of an ethanol solution of glutaraldehyde, an ethanol solution of succinimide and an ethanol solution of polyaldehyde dextran; the concentration of the cross-linking agent solution is 1.5 to 5 wt.%; and the activation time is 20 to 120 minutes.

6. The preparation method according to claim 5, It is characterized in that The usage ratio of the carrier composite material to the cross-linking agent solution is 1-10 mg: 0.2-0.5 mL.

7. The preparation method according to claim 6, It is characterized in that In step (2) and step (3), the centrifugal speed is independently 7000-10000 rpm; the centrifugal time is independently 5-30 min.

8. The preparation method according to claim 2, 3, 4, 6 or 7, It is characterized in that In step (3), the usage ratio of the carrier composite material, enzyme and active component solution is 10-30 mg: 1-3 mg: 8-15 mL; the active component solution is a PBS solution of the active component with a concentration of 0.01-0.03 mol / L.

9. The preparation method according to claim 8, It is characterized in that In step (3), the reaction temperature is 10 to 40° C. and the reaction time is 5 to 10 hours.

10. Use of the self-powered enzyme power material according to claim 1 as a fuel to increase the propulsion force of a motor.

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