Photo-driven composite nanomotor based on oxygen-containing holey cuprous oxide, preparation method and application

Abstract

The application provides a light-driven composite nanomotor based on oxygen-containing hole oxidized cuprous oxide and preparation and application of the light-driven composite nanomotor. 2+1 The rGO / CuO composite nanomotor is prepared by taking CuO material as a matrix and rGO as an outer wall material and by using an electrochemical deposition method as a preparation means. 2+1 The rGO / CuO composite nanomotor can realize high-efficiency movement in a low-concentration biocompatible fuel under visible light irradiation and can realize highly controllable targeted movement in a high-concentration cell isotonic environment under ultraviolet light irradiation. 2+1 The rGO / CuO composite nanomotor can load anticancer drugs in a short time. 2+1 The rGO / CuO composite nanomotor can effectively load drugs, can be applied to targeted drug delivery by using effective light driving, can be applied to environmental remediation, has a large application range, and meanwhile, the preparation method of the composite nanomotor is green, simple and easy to implement, and can realize batch preparation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanomotor, in particular to a light-driven composite nanomotor based on oxygen-containing hole-containing cuprous oxide, a preparation method and application. BACKGROUND

[0002] Targeted drug delivery systems overcome the defects of traditional drug delivery methods, and have the ability of lesion positioning, drug carrying and controllable drug release. In recent years, nanomotors, as a kind of nanoscale power device that can convert external energy (magnetic energy, acoustic energy, light energy and chemical energy, etc.) into its own kinetic energy, have attracted widespread attention from researchers, and have been applied to disease diagnosis, drug delivery, biological detection, environmental pollution and other fields, and are an ideal carrier for targeted drug delivery systems.

[0003] At present, researchers have carried out many studies on drug delivery nanomotors. For example, Joseph Wang et al. developed the first bubble-driven magnesium-based micromotor for gastric drug delivery, and then Joseph Wang and Zhang Liangfang et al. developed enzyme-driven Janus platelet micromotors, which are all based on chemical-driven motors. The advantage of this kind of motor is strong driving force in the body, but it has the problem of uncontrollable movement, and cannot truly realize targeted drug delivery.

[0004] Xie Hui team encapsulates Fe3O4 magnetic particles in pine pollen to prepare a magnetic field-driven micro-nanomotor. Based on fast magnetic response, the motor can achieve efficient active drug delivery in the body, but the movement mode of the motor depends on the complex Helmholtz coil, which limits the application of the magnetic-driven motor.

[0005] Light-driven micro-nanomotors can effectively respond to light, do not depend on complex external field driving sources, have controllable movement mode and convenient movement control, and can solve the problems of complex external field driving sources and uncontrollable movement mode.

[0006] For example, V Sridhard et al. developed the first microswimmer based on C3N4 and two-dimensional polyheptamethyleneimide, which can achieve targeted delivery of anticancer drug doxorubicin (DOX) in a high-sugar high-salt environment by light driving. However, this micrometer-sized drug carrier cannot achieve endocytosis, and the drug can only enter the cell by passive diffusion, which makes only a part of the drug can enter the cell to play a role, limiting the effective utilization rate of the drug. SUMMARY

[0007] The present application aims at the deficiencies of the prior art, and provides a light-driven composite nanomotor based on oxygen-containing hole-containing cuprous oxide and a preparation method. 2+1The light-driven composite nanomotor with the O matrix as the inner layer and the rGO as the outer wall can load drugs in a short time, realize highly controllable targeted movement, directly enter cells, and improve the effective utilization rate of drugs.

[0008] According to a first aspect of the present application, a light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is provided, which comprises an oxygen-containing hole cuprous oxide Cu 2+1 O matrix, and the Cu 2+1 O matrix is a nanotube, and the Cu 2+1 The surface of the O matrix is coated with reduced graphene oxide rGO, thereby forming a double-layer composite structure with the Cu 2+1 O matrix as the inner layer and the rGO as the outer wall.

[0009] Preferably, the diameter of the light-driven composite nanomotor is 350-650 nm, and the length is 800-2000 nm.

[0010] Preferably, the average thickness of the rGO is 10-20 nm, and the average thickness of the Cu 2+1 O matrix is 170-250 nm.

[0011] According to a second aspect of the present application, the light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is applied in a drug delivery system.

[0012] Preferably, the light-driven composite nanomotor is used as a carrier, and drugs are loaded on the carrier.

[0013] Preferably, the light-driven composite nanomotor is controlled to move to cells and enter cells through endocytosis by regulating a light source.

[0014] According to a third aspect of the present application, a preparation method of the light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is provided, which comprises the following steps:

[0015] Reduced graphene oxide rGO is deposited:

[0016] Commercially available graphene oxide is subjected to a large sheet removal treatment to obtain treated graphene oxide GO, and the treated graphene oxide GO is dispersed in a mixed solution of sodium sulfate and sulfuric acid to obtain a suspension A;

[0017] The gold-sprayed polycarbonate PC film is used as a working electrode, the suspension A is used as an electrolyte solution, and the reduced graphene oxide is deposited on the gold-sprayed polycarbonate film. After the deposition is completed, the suspension A is removed, and the PC film with the deposited reduced graphene oxide is cleaned;

[0018] Cu 2+1O base body:

[0019] Slowly add lactic acid into the anhydrous copper sulfate solution, and adjust the pH to alkaline after stirring evenly to obtain solution B;

[0020] Depositing Cu on the PC film deposited with reduced graphene oxide by taking the PC film deposited with reduced graphene oxide as the working electrode and solution B as the electrolyte solution 2+1 O base body, removing the gold layer on the PC film after deposition, and then dissolving and removing the PC film to obtain rGO / Cu 2+1 O composite nanomotor.

[0021] Preferably, rGO is deposited by using a voltammetric cycle method, and the specific process is as follows:

[0022] In a three-electrode system taking the PC film after gold spraying as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum wire as the counter electrode, rGO is deposited on the PC film by taking suspension A as the electrolyte solution, a deposition voltage of-1.5V-0.2V, and a deposition amount of 4-12 cycles.

[0023] Preferably, in the suspension A, the concentration of graphene oxide is 0.08-0.12mg / mL, the concentration of Na2SO4 is 0.4-0.5mol / L, and the concentration of H2SO4 is 0.08-0.12mol / L.

[0024] Preferably, Cu is deposited by using a constant voltage method 2+1 O base body, and the specific process is as follows:

[0025] In a three-electrode system taking the PC film deposited with reduced graphene oxide as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum wire as the counter electrode, Cu is deposited on the PC film deposited with reduced graphene oxide by taking solution B as the electrolyte solution, heating the electrolyte solution to 45-70℃, a deposition voltage of-0.3--0.5V, and a deposition amount of 0.8-1.4C. 2+ 1O base body.

[0026] Preferably, in the solution B, the concentration of CuSO4 is 0.3-0.5mol / L, the concentration of lactic acid is 2.5-3.5mol / L, and the pH value is adjusted to 9-11 by using a NaOH solution.

[0027] Preferably, the method for removing large sheets of graphene oxide is as follows:

[0028] After ball milling a mixture of graphene oxide and sodium chloride at a mass ratio of 1:2, deionized water was added to dissolve the NaCl, resulting in a mixed solution. The graphene oxide was dispersed in the mixed solution in solid form. The solution was filtered twice, first through 15μm and then through 1μm mesh sieves, and finally once through a 450nm aqueous filter membrane to remove large layers of graphene oxide. The filtrate was centrifuged to remove the supernatant containing NaCl. After repeated centrifugation and washing three times with deionized water, the solution was freeze-dried.

[0029] Preferably, the PC membrane has a pore size of 400 nm and a pore length of 1000 nm.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] 1. The light-driven composite nanomotor of the present invention has Cu 2+1 The O matrix forms the inner layer, and rGO forms the outer wall, creating a bilayer composite nanotube structure. rGO and Cu... 2+1 O forms a heterostructure, which, under photoexcitation, induces efficient separation of holes and electrons. The photogenerated charges that jump to the motor surface react with water to generate free radicals, thus creating an uneven concentration gradient and achieving rGO / Cu 2+1 The O nanomotor exhibits negative phototactic autonomous motion under light irradiation. Therefore, this light-driven composite nanomotor can achieve highly controllable targeted motion in a high-concentration cellular isotonic environment under ultraviolet light irradiation.

[0032] After the nanomotor targets the cell, its small size and nanostructure allow it to enter the cell via endocytosis, thereby improving the effective utilization rate of the drug.

[0033] 2. The light-driven composite nanomotor of the present invention can rapidly load doxorubicin through π-π bonding, with a maximum loading rate of 11.7% ± 1.2% (wt%). It has good loading performance. While efficiently loading the drug, it can efficiently target cells through controllable movement, and finally enter the cell through endocytosis to complete the drug delivery. It is an ideal targeted drug delivery carrier with broad application prospects.

[0034] 3. The light-driven composite nanomotor of the present invention has a wide range of applications because it can perform highly controllable targeted movement in a high-concentration cellular isotonic environment when irradiated with ultraviolet light, and therefore can be used for targeted drug delivery. At the same time, the motor can also move efficiently in a low-concentration biocompatible fuel when irradiated with visible light, and therefore can also be used for environmental remediation.

[0035] 4. This invention uses economical Cu 2+1O material is a base, rGO is an outer wall material, and a simple electrochemical deposition method is used as a preparation method, which is low in cost, easy to operate and control, and conducive to further industrialized production. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a preparation flowchart of the light-driven composite nanomotor based on oxygen-containing hole cuprous oxide of the present application.

[0037] Figure 2 a is rGO / Cu 2+1 O composite nanomotor of the present application.

[0038] Figure 2 b is Cu 2+1 O nanomotor of the present application.

[0039] Figure 2 c is rGO / Cu 2+1 O composite nanomotor of the present application.

[0040] Figure 2 d is Figure 2 an enlarged view of c.

[0041] Figure 3 is an XRD pattern of the Cu 2+1 O nanomotor of the present application.

[0042] Figure 4 is rGO / Cu 2+1 O and Cu 2+1 O two nanomotors of the present application.

[0043] Figure 5 is rGO / Cu 2+1 O composite nanomotor of the present application under blue light and ultraviolet light irradiation, respectively, in 0.05mM tannic acid, 5% glucose and pure water.

[0044] Figure 6 is rGO / Cu 2+1 O composite nanomotor of the present application.

[0045] Figure 7 is rGO / Cu 2+1 O composite nanomotor of the present application under ultraviolet light control.

[0046] Figure 8 is rGO / Cu 2+1The fluorescence diagram of the O composite nanomotor after vortex blending with a DOX solution for 120 min. DETAILED DESCRIPTION

[0047] In order to understand the technical content of the present application, specific embodiments are described below with reference to the accompanying drawings.

[0048] Aspects of the present application are described in the disclosure by reference to the accompanying drawings, which show many illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the present application. It should be understood that the various concepts and embodiments introduced above, and those described in more detail below, can be implemented in any of numerous ways.

[0049] In combination Figure 1 , the present application provides a light-driven reduced graphene oxide (rGO) / oxygen-containing hole cuprous oxide (Cu 2+ 1O) composite nanomotor and preparation and application. The present application takes the economical Cu 2+1 O material as the matrix and rGO as the outer wall material, and uses a simple electrochemical deposition method to synthesize rGO / Cu 2+1 O composite nanomotor with different rGO outer wall thicknesses. The composite nanomotor can realize high-efficiency movement in a low-concentration biocompatible fuel under visible light irradiation, and can realize highly controllable targeted movement in a high-concentration cell isotonic environment under ultraviolet light irradiation. At the same time, the rGO / Cu 2+1 O composite nanomotor can load the anticancer drug doxorubicin (DOX) through π-π bond interaction in a short time.

[0050] The rGO / Cu 2+1 O composite nanomotor of the present application can effectively load drugs in combination with surface chemical modification of rGO, and can be applied to targeted drug delivery using effective light driving, and can also be applied to environmental remediation, and has a large application range. At the same time, the preparation method of the composite nanomotor is green and environmentally friendly, simple and easy to implement, and can realize batch preparation.

[0051] The reduced graphene oxide rGO in the present application refers to that the graphene oxide GO loses some functional groups during the electrochemical deposition process, and the obtained product is reduced graphene oxide rGO.

[0052] In an exemplary embodiment of the present application, a light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is provided, which includes an oxygen-containing hole cuprous oxide Cu 2+1 O matrix, the Cu 2+1 O matrix is a nanotube, and the surface of the Cu 2+1 O matrix is coated with reduced graphene oxide rGO, thereby forming a Cu 2+1The double-layer composite structure has an O matrix as an inner layer and rGO as an outer wall.

[0053] In a preferred embodiment, the diameter of the light-driven composite nanomotor is 350-650 nm, and the length is 800-2000 nm.

[0054] In a preferred embodiment, the average thickness of the rGO is 10-20 nm, and the average thickness of the Cu 2+1 The average thickness of the O matrix is 170-250 nm.

[0055] In another exemplary embodiment of the present application, the aforementioned light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is also provided for use in a drug delivery system, the drug is loaded on the carrier, and the light-driven composite nanomotor loaded with the drug is controlled to move to cells and enter the cells by endocytosis to complete drug delivery by adjusting the light source.

[0056] As Figure 1 shown, in another exemplary embodiment of the present application, a preparation method of the aforementioned light-driven composite nanomotor based on oxygen-containing hole cuprous oxide is also provided, comprising the following steps:

[0057] S1, depositing reduced graphene oxide rGO:

[0058] Commercially available graphene oxide is subjected to a large sheet layer removal treatment to obtain treated graphene oxide GO, and the treated graphene oxide GO is dispersed in a mixed solution of sodium sulfate and sulfuric acid to obtain a suspension A.

[0059] The gold-sprayed polycarbonate PC film is used as a working electrode, the suspension A is used as an electrolyte solution, and the reduced graphene oxide is deposited on the gold-sprayed polycarbonate film, after the deposition is completed, the suspension A is removed, and the PC film on which the reduced graphene oxide is deposited is cleaned.

[0060] S2, depositing Cu 2+1 O matrix:

[0061] Lactic acid is slowly added to the anhydrous copper sulfate solution, and after stirring, the pH is adjusted to alkaline to obtain a solution B.

[0062] The PC film on which the reduced graphene oxide is deposited is used as a working electrode, the solution B is used as an electrolyte solution, and the oxygen-containing hole cuprous oxide Cu 2+1 O matrix is deposited on the PC film on which the reduced graphene oxide is deposited, after the deposition is completed, the gold layer on the PC film is removed, and then the PC film is dissolved and removed to obtain the rGO / Cu 2+1 O composite nanomotor.

[0063] In one preferred embodiment, rGO is deposited by using voltammetric method, and the specific process is as follows:

[0064] In a three-electrode system with the PC film after gold spraying as the working electrode, Ag / AgCl electrode as the reference electrode, and platinum wire as the counter electrode, and with suspension A as the electrolyte solution, the deposition voltage is-1.5V-0.2V, and the deposition amount is 4-12 cycles, rGO is deposited on the PC film.

[0065] Preferably, in the suspension A, the concentration of graphene oxide is 0.08-0.12mg / mL, the concentration of Na2SO4 is 0.4-0.5mol / L, and the concentration of H2SO4 is 0.08-0.12mol / L.

[0066] In one preferred embodiment, CuO is deposited by using constant voltage method, and the specific process is as follows: 2+1 O matrix, and the specific process is as follows:

[0067] In a three-electrode system with the PC film on which reduced graphene oxide is deposited as the working electrode, Ag / AgCl electrode as the reference electrode, and platinum wire as the counter electrode, and with solution B as the electrolyte solution, and the electrolyte solution is heated to 45-70℃, the deposition voltage is-0.3--0.5V, and the deposition amount is 0.8-1.4C, CuO is deposited on the PC film on which reduced graphene oxide is deposited. 2+ 1O matrix.

[0068] Preferably, in the solution B, the concentration of CuSO4 is 0.3-0.5mol / L, the concentration of lactic acid is 2.5-3.5mol / L, and the pH value is adjusted to 9-11 by using NaOH solution.

[0069] In other preferred embodiments, the method for removing large sheet graphene oxide is as follows:

[0070] After graphene oxide and sodium chloride are mixed by ball milling at a mass ratio of 1:2, deionized water is added to dissolve NaCl, a mixed solution is obtained, graphene oxide is dispersed in the mixed solution in solid form, and then the mixed solution is filtered twice with 15μm and 1μm mesh screens in sequence, and then filtered once with a water-based filter membrane with a pore size of 450nm to remove large sheet graphene oxide, the filtrate is centrifuged, the supernatant containing NaCl is removed, deionized water is added for repeated centrifugal washing three times, and then freeze-drying is performed.

[0071] In another preferred embodiment, the pore size of the PC film is 400nm, and the pore length is 1000nm.

[0072] In another exemplary embodiment, drug loading is completed by using vortex blending, and the specific process is as follows:

[0073] The aforementioned rGO / Cu2+1 The O composite nanomotor is uniformly dispersed in deionized water to obtain a motor dispersion liquid. The motor dispersion liquid is dropped into the doxorubicin solution, and vortex is performed in a dark room. The rGO / Cu 2+1 The O composite nanomotor is uniformly dispersed in deionized water to obtain a motor dispersion liquid. The motor dispersion liquid is dropped into the doxorubicin solution, and vortex is performed in a dark room. The rGO / Cu

[0074] Vortex refers to the use of a vortex instrument to mix the motor dispersion liquid and the doxorubicin solution by shaking.

[0075] The amount of the motor, and the amount of the doxorubicin solution are not further limited here, and can be adjusted according to actual conditions.

[0076] It should be understood that the drug includes but is not limited to doxorubicin, which can be selected according to actual conditions, and drugs that can form π-π interactions with rGO.

[0077] The above preparation process and the prepared light-driven composite nanomotor are tested and tested in combination with specific examples.

[0078] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels unless otherwise specified.

[0079] The pore size of the PC film used below is 400 nm, and the pore length is 1000 nm.

[0080] Example 1

[0081] Preparation of Cu 2+1 O nanomotor

[0082] A 0.4 mol / L CuSO4 solution of 20 mL is prepared, and then 4.47 mL of lactic acid is slowly added to the CuSO4 solution. After mixing and stirring for 30 min, 4 mol / L NaOH is slowly added to adjust the pH of the solution to the range of 9-11. The mixed solution is heated to 60°C in a water bath as an electrolyte solution.

[0083] In a three-electrode system with the gold-coated PC film as the working electrode, a 3 mol / L Ag / AgCl electrode as the reference electrode, and a platinum wire as the counter electrode, 1.0 C of charge is deposited at a voltage of -0.45 V by constant voltage method.

[0084] After deposition, the gold layer is removed by manual polishing with an alumina polishing liquid. After the gold layer is removed, the PC film is dissolved using dichloromethane, and then sequentially washed with dichloromethane, ethanol, and deionized water by centrifugation to remove the PC film. After centrifugation at a speed of 8000 rpm for 5 min, the supernatant is removed to obtain the Cu 2+1 The precipitate is obtained by centrifugation.2+1 O Placed in a vacuum drying oven for 4 hours, Cu 2+1 O Nanomotor.

[0085] Example 2

[0086] Preparation of rGO / Cu 2+1 O composite nanomotor

[0087] Deposition of rGO

[0088] The purchased graphene oxide was mixed with NaCl at a mass ratio of 1:2 and ball milled for 12 hours. Then, deionized water was added to dissolve the NaCl, obtaining a mixed solution. The graphene oxide was dispersed in the mixed solution in solid form. The solution was filtered twice with 15 μm and 1 μm mesh screens, respectively, and then filtered once with a water-based filter membrane with a pore size of 450 nm to remove large pieces of graphene oxide. The filtrate was centrifuged at 12000 rpm to remove the supernatant. Deionized water was added and repeatedly washed three times. Then, the graphene oxide was freeze-dried to obtain small pieces of graphene oxide.

[0089] The small pieces of graphene oxide were weighed to prepare 20 mL of graphene oxide dispersion solution as the electrolyte solution. In the dispersion solution, the concentration of the small pieces of graphene oxide was 0.1 mg / mL, the concentration of Na2SO4 was 0.5 mol / L, and the concentration of H2SO4 was 0.1 mol / L.

[0090] The PC film after gold spraying was used as the working electrode, a 3 mol / L Ag / AgCl electrode was used as the reference electrode, and a platinum wire was used as the counter electrode in a three-electrode system to deposit and reduce the outer wall of graphene oxide by cyclic voltammetry at a deposition voltage of 0.2 V to -1.5 V for 10 voltammetry cycles. Then, the graphene oxide dispersion solution was removed, and the PC film after deposition and reduction of graphene oxide was washed with deionized water.

[0091] Deposition of Cu 2+1 O

[0092] A 0.4 mol / L CuSO4 solution was prepared at 20 mL. Then, 4.47 mL of lactic acid was slowly added to the CuSO4 solution. After mixing and stirring for 30 min, 4 mol / L NaOH was slowly added to adjust the pH of the solution to the range of 9-11. The mixed solution was heated to 60°C in a water bath as the electrolyte solution.

[0093] The PC film after deposition and reduction of graphene oxide was used as the working electrode, a 3 mol / L Ag / AgCl electrode was used as the reference electrode, and a platinum wire was used as the counter electrode in a three-electrode system to deposit 1.0 C charge at a voltage of -0.45 V by constant voltage method.

[0094] After the deposition is completed, the gold layer is removed by manual polishing with an alumina polishing liquid. After the gold layer is removed, the PC film is dissolved with dichloromethane, and then sequentially washed with dichloromethane, ethanol, and deionized water by centrifugation. After the PC film is removed, the supernatant is removed by centrifugation at a speed of 8000 rpm for 5 min to obtain rGO / Cu 2+1 O is precipitated. After being sequentially washed three times by centrifugation with alcohol and deionized water, the rGO / Cu 2+1 O is placed in a vacuum drying oven for vacuum drying for 4 hours to obtain rGO / Cu 2+1 O composite nanomotor.

[0095] Example 3

[0096] Loading of doxorubicin

[0097] The rGO / Cu 2+1 O composite nanomotor obtained in Example 2 is uniformly dispersed in 1 mL of deionized water to obtain a motor dispersion liquid. The motor dispersion liquid is divided into five groups, each of which is 200 μL (the motor content is 0.51 g). Each group is dripped with 1.9 mL of doxorubicin solution, and the concentration of doxorubicin after dripping is 55.65 mg / L. The five groups of samples are vortexed in a dark room for 15 min, 30 min, 60 min, 120 min, and 180 min, respectively. After the vortexing is completed, the five groups of samples are centrifuged at a speed of 12000 rpm for 5 min to obtain the precipitates. The precipitates are centrifuged again with deionized water at a speed of 12000 rpm for three times to obtain a loaded sample 1 (15 min), a loaded sample 2 (30 min), a loaded sample 3 (60 min), a loaded sample 4 (120 min), and a loaded sample 5 (180 min).

[0098] The following materials used in the tests are from the Cu 2+1 O nanomotor obtained in Example 2. 2+1 O composite nanomotor, and the loaded sample 1, the loaded sample 2, the loaded sample 3, the loaded sample 4, and the loaded sample 5 of Example 3.

[0099] SEM, TEM

[0100] The Cu 2+1 O nanomotor, the rGO / Cu 2+1 O composite nanomotor are subjected to SEM and TEM tests, and the results are shown in Figure 2 .

[0101] As can be seen from Figure 2 a, the rGO / Cu 2+1 O composite nanomotor has a relatively regular nanotube shape, and the Cu2+1 O nanomotor (2b), rGO / Cu 2+1 O composite nanomotor, the surface morphology of the nanomotor changes obviously, which is due to the existence of the outer wall of rGO, making the nanomotor present a rough surface.

[0102] In combination Figure 2 c and 2d, it can be seen that the rGO / Cu 2+1 O composite nanomotor has obvious inner layer and outer wall structure, and the thickness of the outer wall is about 15±4nm, and the inner layer Cu 2+1 O has an average thickness of 190±15nm, and the rGO / Cu 2+1 O composite nanomotor has a tube diameter of about 565±84nm and a tube length of about 1572±252nm.

[0103] The rGO / Cu 2+1 O composite nanomotor of the application has a nanoscale tube diameter, which is far smaller than the size of a cell, and thus can be endocytosed into a cell.

[0104] XRD

[0105] The Cu 2+1 O nanomotor is subjected to XRD test, and the result is shown in Figure 3 .

[0106] As can be seen from the figure, the corresponding PDF card (05-0667) shows that the matrix material of the nanomotor is oxygen hole-containing cuprous oxide, namely Cu 2+1 O.

[0107] FT-IR

[0108] The Cu 2+1 O nanomotor and the rGO / Cu 2+1 O composite nanomotor are subjected to FT-IR test, and the result is shown in Figure 4 .

[0109] As can be seen from the figure, compared with the Cu 2+1 O nanomotor, the rGO / Cu -1 O composite nanomotor has a characteristic peak at 1760cm -1 , which is a characteristic peak of carboxyl, proving the existence of rGO.

[0110] Meanwhile, a characteristic peak of Cu-O bond appears at 628cm 2+1 , in combination with the result of XRD, further proving that the matrix material of the nanomotor is Cu 2+1 O.

[0111] Therefore, in combination with the SEM, TEM, XRD and FT-IR tests, it can be proved that the rGO / Cu2+1 O-composite nanomotor.

[0112] Speed of movement in different biological media and cell-targeted movement tests

[0113] Using blue light with a wavelength of 460 nm and ultraviolet light with a wavelength of 310 nm as driving light sources, rGO / Cu was subjected to oxidation in 0.05 mM tannic acid solution, 5% glucose solution, and pure aqueous solution, respectively. 2+1 The speed of O was tested, and the results are as follows: Figure 5 As shown.

[0114] As can be seen from the figure, under blue light and ultraviolet light irradiation, rGO / Cu 2+1 O-composite nanomotors exhibit high speeds in various biocompatible environments, such as Figure 6 As shown, this is because rGO and Cu 2+1 O forms a heterostructure, which, under photoexcitation, induces efficient separation of holes and electrons. The photogenerated charges that jump to the motor surface react with water to generate free radicals, thus creating an uneven concentration gradient and achieving rGO / Cu 2+1 O nanomotors exhibit negative phototactic autonomous motion under light irradiation.

[0115] In a high-concentration cellular isotonic environment (5% glucose), rGO / Cu 2+1 O-composite nanomotors can be highly targeted to cells under ultraviolet light modulation, and the motor's movement trajectory is as follows: Figure 7 As shown, the red line represents the motor's trajectory. The results indicate that at 1.8 W / cm²... 2 Under 310nm ultraviolet light control, rGO / Cu 2+1 O-composite nanomotors exhibit active targeting motion toward the vicinity of cells.

[0116] The figure also shows that rGO / Cu 2+1 The O-composite nanomotor can not only use low concentrations of biocompatible materials as fuel, but also operate effectively in pure water. This illustrates the rGO / Cu of the present invention. 2+1 O-composite nanomotors can be used in a variety of scenarios and have a wide range of applications.

[0117] The rGO / Cu of the present invention 2+1 The O-composite nanomotor exhibits rapid response to blue and ultraviolet light due to its narrow bandgap, and the rGO / Cu composite can be easily controlled by adjusting the light source. 2+1 O-composite nanomotors can be used for targeted drug delivery by moving into cells.

[0118] Drug loading tests

[0119] (1) Standard DOX solutions with concentrations of 7.6, 15.2, 22.8, 30.4, and 38 mg / L were prepared respectively, and a linear equation (1) between concentration and absorbance was established by measuring their corresponding absorbance:

[0120] Abs = 0.03012 + 0.01893c (1)

[0121] Where Abs is the UV absorbance of the DOX solution, and c is the concentration of the DOX solution.

[0122] In the drug loading experiment, the absorbance of the supernatants of loaded sample 1, loaded sample 2, loaded sample 3, loaded sample 4 and loaded sample 5 were measured to be 0.728179, 0.593498, 0.582271, 0.506415 and 0.546365, respectively, and the absorbance of 55.65 mg / L DOX solution was 1.07201.

[0123] According to formula (1), the corresponding supernatant concentrations are 37.96, 30.63, 30.02, 25.90 and 28.07 mg / L, and the initial concentration is 55.65 mg / L.

[0124] By testing the decrease in absorbance at different mixing times, the rGO / Cu ratio was quantitatively calculated. 2+1 The drug loading efficiency of the O nanomotor is calculated according to formula (2):

[0125]

[0126] The drug loading rates of loaded samples 1, 2, 3, 4, and 5 were 7.28%, 10.30%, 10.55%, 12.25%, and 11.35%, respectively.

[0127] As can be seen from the above, rGO / Cu 2+1 The rGO in the O nanomotor can bind to doxorubicin through π-π bonding, and doxorubicin can be efficiently loaded in 15 min. The highest drug loading rate of 11.7% ± 1.2% (wt%) is achieved after vortexing the motor with DOX solution for 120 min.

[0128] (2) The fluorescence of sample 4 was observed using a laser confocal microscope. The drug loading was qualitatively assessed by observing the fluorescence. The results are as follows: Figure 8 As shown.

[0129] from Figure 8 As can be seen, the fluorescence exhibits a clear motor outline, proving that rGO / Cu 2+1 O-nano motors can efficiently load doxorubicin.

[0130] From the above, the light-driven composite nanomotor of the present application can efficiently load anticancer drugs, and under ultraviolet light irradiation, can carry out highly controllable targeted movement, and through intracellular endocytosis into the cell to complete drug delivery.

[0131] Meanwhile, the light-driven composite nanomotor of the present application can also be fueled by a low concentration of biocompatible substances, and can be effectively driven in pure water, and can be used in various scenarios.

[0132] Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application. Those skilled in the art without departing from the spirit and scope of the present application can make various modifications and improvements. Therefore, the protection scope of the present application shall be subject to the definition of the claims.

Claims

1. A light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide, characterized in that, This light-driven composite nanomotor includes oxygen-hole-containing cuprous oxide (Cu). 2+1 O matrix, the Cu 2+1 The O matrix is ​​nanotube-shaped, Cu 2+1 The surface of the O-based substrate is coated with reduced graphene oxide (rGO), thereby forming a Cu-based matrix. 2+1 A two-layer composite structure with O matrix as the inner layer and rGO as the outer wall; The light-driven composite nanomotor is prepared by electrochemical deposition and has a diameter of 350~650nm and a length of 800~2000nm. The method for preparing the optically driven composite nanomotor includes the following steps: Deposition of reduced graphene oxide (rGO): Commercially available graphene oxide was treated to remove large layers to obtain treated graphene oxide GO. The treated graphene oxide GO was then dispersed in a mixed solution of sodium sulfate and sulfuric acid to obtain suspension A. Using a gold-sprayed polycarbonate (PC) film as the working electrode and suspension A as the electrolyte solution, reduced graphene oxide (rGO) was deposited on the gold-sprayed polycarbonate film. After deposition, suspension A was removed, and the PC film with deposited reduced graphene oxide (rGO) was cleaned. Cu deposition 2+1 O matrix: Slowly add lactic acid dropwise to anhydrous copper sulfate solution, stir well, and adjust the pH to 9-11 to obtain solution B; Using a PC film with deposited reduced graphene oxide as the working electrode, solution B as the electrolyte solution, and heating the electrolyte solution to 45–70 °C, a deposition voltage of -0.3–-0.5 V, and a deposition amount of 0.8–1.4 coulombs were used to deposit Cu on the PC film with deposited reduced graphene oxide. 2+1 After deposition on the O substrate, the gold layer on the PC film is removed, and then the PC film is dissolved and removed to obtain rGO / Cu. 2+1 O-composite nanomotor; In the aforementioned light-driven composite nanomotor, graphene rGO and Cu 2+1 O forms a heterostructure, which, under photoexcitation, induces efficient separation of holes and electrons. The photogenerated charges that jump to the motor surface react with water to generate free radicals, thus creating an uneven concentration gradient and achieving rGO / Cu 2+1 O nanomotors exhibit negative phototactic autonomous motion under light irradiation, efficiently targeting cells through controllable movement, and finally entering the cell via endocytosis.

2. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1, characterized in that, rGO was deposited using the voltammetric cycle method, and the specific process is as follows: Using a gold-sprayed PC film as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum wire as the counter electrode. In a three-electrode system, suspension A was used as the electrolyte solution, deposition voltage was -1.5V to 0.2V, and deposition time was 4 to 12 cycles to deposit rGO on a PC film.

3. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1 or 2, characterized in that, In the suspension A, the concentration of graphene oxide is 0.08~0.12 mg / mL, the concentration of Na2SO4 is 0.4~0.5 mol / L, and the concentration of H2SO4 is 0.08~0.12 mol / L.

4. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1, characterized in that, Cu deposition using constant voltage method 2+1 O-matrix, the specific process is as follows: In a three-electrode system using a PC film with deposited reduced graphene oxide as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum wire as the counter electrode, solution B was used as the electrolyte solution, which was heated to 45–70 °C. The deposition voltage was -0.3–-0.5 V, and the deposition amount was 0.8–1.4 coulombs. Cu was deposited on the PC film with deposited reduced graphene oxide. 2+1 O matrix.

5. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1, characterized in that, In solution B, the concentration of CuSO4 is 0.3~0.5 mol / L, and the concentration of lactic acid is 2.5~3.5 mol / L.

6. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1, characterized in that, The method for removing large sheets of graphene oxide is as follows: After ball milling a mixture of graphene oxide and sodium chloride at a mass ratio of 1:2, deionized water was added to dissolve the NaCl, resulting in a mixed solution. The graphene oxide was dispersed in the mixed solution in solid form. The solution was filtered twice through 15 μm and 1 μm mesh sieves, and then once through a 450 nm pore size aqueous filter membrane to remove large layers of graphene oxide. The filtrate was centrifuged to remove the supernatant containing NaCl. After repeated centrifugation and washing three times with deionized water, the solution was freeze-dried.

7. The light-driven composite nanomotor based on oxygen-hole-containing cuprous oxide according to claim 1, characterized in that, The PC membrane has a pore size of 400 nm and a pore length of 1000 nm.

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