Bullet-shaped nano motor with hole at tail part and preparation method of bullet-shaped nano motor
By designing a bullet-shaped nanomotor with a tail hole, using gold nanobicone and Ag nanorods, combined with asymmetric etching technology, the problems of degradation of kinetic performance and meaningless kinetic energy in the nanomotor are solved, and the problem of Efficient directional movement and versatility.
Patent Information
- Application Number
- CN202411207003.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-30
- Publication Date
- 2025-01-03
AI Technical Summary
The spherical structure of existing nanomotors is susceptible to solvent thermal fluctuations, the kinetic performance is degraded, and the kinetic energy is difficult to accurately control, resulting in meaningless kinetic energy loss in spin motion.
The bullet-shaped nanomotor design is designed with a tail opening, and consists of gold nanobicone AuNBPs and Ag nanorods. The tail opening of the Ag nanorod is loaded with a metal oxide power source, combined with asymmetric etching technology to form a unique morphology and improve directionality and kinetic performance.
The directional movement ability and propulsion force in the solution are achieved, the versatility and scope of application of the nanomotor is improved, the resistance is reduced, and the dynamic performance and guidance are enhanced.
Smart Images
Figure CN119237723A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of nanomaterials, and in particular relates to a bullet-shaped nanomotor with a hole at the tail and a preparation method thereof. Background Art
[0002] Artificial nanomotors are valuable tools that can enhance diffusion-enhanced therapy and expand the application range of active materials. Inspired by organisms, nanomotors can convert various energy sources into mechanical work, thereby generating translational or rotational motion. However, the inertial force in solutions is small, and viscosity has a significant impact on the motion of nanomotors. In addition, Brownian motion and rotational diffusion caused by thermal fluctuations make precise control of nanomotor motion extremely challenging.
[0003] Recently, nanomotors have been widely studied by researchers in various fields due to their excellent kinetic properties. Their mobility and diffusion properties enable them to travel and treat lesions rather than being confined to one location, thereby achieving enhanced therapeutic effects. However, current research on nanomotors has largely focused on spherical structures, primarily using ligands or surface capping agents to partially graft onto the surface of spherical nanoparticles, thereby exposing another portion of the active surface and allowing the in situ growth of functional units that act as power sources. However, because spherical nanoparticles are too symmetrical, the grafted surface capping agents are difficult to control and exhibit a non-uniform distribution, making them extremely susceptible to solvothermal fluctuations, resulting in reduced kinetic performance and uncontrollable direction. Most of the kinetic energy is used in meaningless spin motion in situ, leading to kinetic energy loss. Summary of the Invention
[0004] To address the shortcomings of the existing technology, the present invention aims to provide a bullet-shaped nanomotor with a tail opening and a method for its preparation. This bullet-shaped nanomotor breaks through the limitations of traditional spherical structures. Its tip is a pointed cone, and the tail opening is loaded with a metal oxide as a power source, resulting in excellent dynamic performance and good guidance.
[0005] To achieve the above object, the present invention is implemented through the following technical solutions:
[0006] The present invention provides a bullet-shaped nanomotor with a hole at the tail. The bullet-shaped nanomotor includes a bullet-shaped AuNBPs@Ag nanomaterial and a power source. The bullet-shaped AuNBPs@Ag nanomaterial is composed of gold nanobipyramids AuNBPs and Ag nanorods. One end of the gold nanobipyramids AuNBPs is exposed to form a tip structure, and the other end is wrapped by the Ag nanorod to form a rod-shaped structure. The Ag nanorod has an opening at the tail, and the power source is loaded on the opening.
[0007] As a further optimized solution of the present invention, the power source includes metal oxide.
[0008] As a further optimized solution of the present invention, the metal oxide includes any one of manganese dioxide, titanium dioxide, cerium dioxide and cuprous oxide.
[0009] The present invention also provides a method for preparing a bullet-shaped nanomotor with a hole at the tail, the method comprising:
[0010] preparing Au seeds;
[0011] Utilizing the Au seeds to induce growth and form gold nanobipyramids AuNBPs;
[0012] A layer of silver nanomaterial is wrapped and grown on the surface of the gold nanobipyramids AuNBPs to form AuNBPs@Ag nanorods;
[0013] Asymmetrically etching the AuNBPs@Ag nanorod to hollow one end thereof, and then opening a hole at the other end thereof to obtain a bullet-shaped AuNBPs@Ag nanomaterial with an opening at the tail;
[0014] A hole is opened at the tail of the bullet-shaped AuNBPs@Ag nanomaterial to load a power source, and finally a bullet-shaped nanomotor is obtained.
[0015] As a further optimization solution of the present invention, the preparation of the gold nanobipyramids AuNBPs includes:
[0016] Au seeds were added to a solution containing hexadecyltrimethylammonium bromide, chloroauric acid, silver nitrate, hydrochloric acid and ascorbic acid to form gold nanobipyramids (AuNBPs) through a self-assembly and growth process.
[0017] As a further optimization solution of the present invention, the preparation of the AuNBPs@Ag nanorods includes:
[0018] Gold nanobipyramids AuNBPs were mixed with hexadecyltrimethylammonium chloride, silver nitrate and ascorbic acid, and a silver nanolayer was grown on the surface of the gold nanobipyramids AuNBPs through the reduction reaction of silver ions.
[0019] As a further optimization solution of the present invention, the asymmetric etching step includes:
[0020] A mixed solution comprising chloroauric acid, ascorbic acid, sodium hydroxide, and cetyltrimethylammonium bromide is prepared and stirred uniformly at room temperature; the AuNBPs@Ag nanorods are added to the mixed solution and reacted in a water bath at 25-35°C for 5-8 hours to hollow one end thereof, and purified after the reaction is completed;
[0021] The purified AuNBPs@Ag nanorods were redispersed in a solution containing hexadecyltrimethylammonium bromide, and sodium bicarbonate, hydrogen peroxide, potassium thiocyanate, and cobalt nitrate were added in sequence. The reaction was carried out in a water bath at 70-90°C for 20-30 minutes to open a hole at the other end. After the reaction was completed, the rods were purified to obtain a bullet-shaped AuNBPs@Ag nanomaterial with a hole at the tail.
[0022] As a further optimization solution of the present invention, the step of opening a hole at the tail of the bullet-shaped AuNBPs@Ag nanomaterial to load a power source includes:
[0023] The bullet-shaped AuNBPs@Ag nanomaterial with an opening at the tail is dispersed in a solution containing a ligand, and then a solution containing a power source precursor is added and mixed and stirred. Then, sodium hydroxide solution and hydroxylamine hydrochloride solution are added, and the mixture is reacted at 50-80°C for 90-150 minutes to obtain a bullet-shaped nanomotor with a power source loaded on the tail opening.
[0024] As a further optimized solution of the present invention, the ligand includes any one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and polyvinylpyrrolidone.
[0025] Compared with the prior art, the present invention has the following beneficial effects:
[0026] (1) The present invention adopts asymmetric etching technology to achieve precise control of the morphology of nanomaterials, obtaining a unique bullet-shaped morphology that gives it good directionality. Among them: the bullet-shaped structure can reduce the resistance of the nanomotor in the fluid and improve its directional movement ability in the solution; at the same time, the special design of the tail opening + loaded metal oxide helps to generate propulsion force, allowing the bullet-shaped nanomotor to move more effectively to the target area.
[0027] (2) The tail of the bullet-shaped nanomotor can be loaded with different specific target materials as needed. By opening a hole in the tail of the bullet-shaped nanomotor and loading Cu2O or other materials (such as MnO2, CeO2, TiO2, etc.), the performance of the bullet-shaped nanomotor can be adjusted according to specific application requirements. This design allows researchers to choose different fuel sources or functional materials according to the experimental purpose, enhancing the versatility and applicability of the bullet-shaped nanomotor. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 This is a transmission electron microscope image of the gold nanobipyramids AuNBPs prepared in Example 1.
[0029] Figure 2 This is a transmission electron microscopy image of the AuNBPs@Ag nanorods prepared in Example 1.
[0030] Figure 3 This is a transmission electron microscopy image of the AuNBPs@Ag nanorods with one end hollowed out by preliminary etching in Example 1.
[0031] Figure 4 This is a transmission electron microscope image of the solid bullet-shaped AuNBPs@Ag nanorods obtained by further etching in Example 1.
[0032] Figure 5 This is a transmission electron micrograph of the bullet-shaped AuNBPs@Ag nanomaterial obtained by opening the tail of the solid bullet-shaped AuNBPs@Ag nanorod in Example 1.
[0033] Figure 6 This is a transmission electron microscope image of the bullet-shaped nanomotor obtained by loading Cu2O on the tail opening of the bullet-shaped AuNBPs@Ag nanomaterial in Example 1.
[0034] Figure 7 This is the motion trajectory of the bullet-shaped nanomotor prepared in Example 1 in 5mM H2O2.
[0035] Figure 8 The cumulative movement distance of the bullet-shaped nanomotor prepared in Example 1 within 60 seconds in different concentrations of H2O2. DETAILED DESCRIPTION
[0036] In order to enable those skilled in the art to better understand the technical solutions of the present invention, preferred embodiments of the present invention are described below in conjunction with specific examples. However, these examples are not to be construed as limiting the present invention and are merely examples.
[0037] On the one hand, the present invention provides a bullet-shaped nanomotor with an opening at the tail, wherein the bullet-shaped nanomotor includes a bullet-shaped AuNBPs@Ag nanomaterial and a power source, wherein the bullet-shaped AuNBPs@Ag nanomaterial is composed of gold nanobipyramids AuNBPs and Ag nanorods; one end of the gold nanobipyramids AuNBPs is exposed to form a tip structure, and the other end is wrapped by the Ag nanorod to form a rod-shaped structure; the Ag nanorod has an opening at the tail, and the power source is loaded on the opening.
[0038] In some embodiments, the power source comprises a metal oxide, and the metal oxide comprises any one of manganese dioxide, titanium dioxide, cerium dioxide, and cuprous oxide.
[0039] On the other hand, the present invention also provides a method for preparing a bullet-shaped nanomotor with a hole at the tail, the preparation method comprising:
[0040] Synthesis of Au seeds:
[0041] Weigh 150-180 mg of cetyltrimethylammonium chloride (CTAC) and dissolve it in 10 ml of ultrapure water. Once completely dissolved, add 50 ml of a 50-80 mM HAuCl4 solution, followed by 9-12 mg of citric acid. Stir for 3-5 minutes. Quickly add 250 ml of a 30-60 mM NaBH4 solution and stir for 3-5 minutes. Stir in an oil bath at 80-90°C for 90-120 minutes.
[0042] Synthesis of AuNBPs:
[0043] To a round-bottom flask, add 200 ml of 80-150 mM cetyltrimethylammonium bromide (CTAB), 3 ml of 20-50 mM HAuCl₄ solution, 2 ml of 10-20 mM AgNO₃ solution, 4 ml of 1-3 M HCl solution, and 2 ml of 80-120 mM ascorbic acid (AA) solution. Mix and stir at room temperature for 3-5 minutes. Then, add 3-5 ml of the Au seeds prepared above. Incubate in a water bath at 25-35°C for 3-5 hours.
[0044] Synthesis of AuNBPs@Ag nanorods:
[0045] The AuNBPs prepared above were purified by centrifugation at 9500 rpm for 8-12 minutes and centrifuged twice. The purified AuNBPs were then redispersed in ultrapure water until the absorbance was 0.5-1. 10-30 ml of the redispersed AuNBPs were added to 30 ml of 30-50 mM CTAC solution. Stir and disperse for 3-5 minutes, then add 300-400 ml of AgNO3 solution, stir and disperse for 3-5 minutes, and then add 0.1-0.5 M ascorbic acid, which is half the volume of the AgNO3 solution. Incubate in a water bath at 50-70°C for 3-6 hours. After the reaction is complete, centrifuge and purify at 9500 rpm for 8-12 minutes and redisperse in 10-20 ml of ultrapure water.
[0046] Asymmetric etching of AuNBPs@Ag nanorods:
[0047] To a round-bottom flask, add 750 ml of a 0.01-0.03 M HAuCl₄ solution, 500 ml of a 0.1-0.3 M AA solution, 500 ml of a 0.05-0.15 M NaOH solution, and 50 ml of a 0.1-0.3 M CTAB solution. After complete addition, stir at room temperature for 3-5 minutes. Then, add 10-15 ml of the previously redispersed AuNBPs@Ag nanorods. Incubate in a water bath at 25-35°C for 5-8 hours to hollow one end. After the reaction is complete, purify by centrifugation at 9500 rpm.
[0048] The AuNBPs@Ag nanorods purified by centrifugation were redispersed in 200 ml of a 1-5 mM CTAB solution. Subsequently, 2 ml of a 0.1-0.5 M NaHCO solution, 2 ml of a 0.1-0.5 M H2O2 solution, 1 ml of a 0.05-0.15 M KSCN solution, and 2 ml of a 10-30 mM Co(NO3)2 solution were gradually added. The mixture was incubated in a water bath at 70-90°C for 20-30 minutes. The other end of the nanorods was then pore-opened and purified by centrifugation at 9500 rpm until ready for use.
[0049] Mechanism analysis of asymmetric etching: During the asymmetric etching process, HAuCl4 is used to break the balance and perform asymmetric etching. - The standard electrode potential of Au / Au is 1.002, and the standard electrode potential of Ag / AgCl is -0.222. - The standard electrode potentials of Au / Au and Ag / AgCl indicate that the redox reaction between the two can proceed spontaneously. Therefore, during the etching process, HAuCl4 can replace the Ag in the AuNBPs@Ag rod with free Ag. + , thus achieving the purpose of etching. However, due to the high symmetry between the two ends of the AuNBPs@Ag rod, the HAuCl4 etching process initially proceeds simultaneously from both ends. However, as the etching reaction occurs, the etching reaction at one end will preferentially break the equilibrium. Under the influence of reaction kinetics, the subsequent HAuCl4 etching process will be concentrated on the end that breaks the equilibrium, thus leading to the occurrence of asymmetric etching.
[0050] After the HAuCl4 solution completes the asymmetric etching, under the combined action of KSCN and H2O2, the surface Ag of the hollowed AuNBPs@Ag rod at one end reacts with KSCN to generate free Ag(SCN)2 - ions and dispersed in the solution, thereby achieving the purpose of etching. By controlling the reaction time, the etching part of the AuNBPs@Ag rod can be controlled. When the etching time is 20 minutes, only the hollow end will be etched; when the etching time is 25 minutes, after the hollow end is etched, the solid end will continue to be etched, and the effect of opening a hole at the tail will be achieved.
[0051] In situ synthesis of metal oxides on the AuNBPs@Ag tail openings:
[0052] The purified AuNBPs@Ag was redispersed in 2ml of 0.1-0.3M cetyltrimethylammonium bromide (CTAB) solution (cetyltrimethylammonium chloride (CTAC) or polyvinylpyrrolidone (PVP)) and stirred for 3-5 minutes. After mixing, 50ml of a 20-60mM metal oxide precursor solution was slowly added dropwise to the AuNBPs@Ag solution and stirred for 5-10 minutes. Subsequently, 0.25ml of a 0.1-1M NaOH solution and 0.5ml of a 0.3-0.6M NH2OH·HCl solution were added dropwise. The mixture was then oven-dried at 50-80°C for 90-150 minutes to obtain bullet-shaped nanomotors loaded with metal oxides. The metal oxides can be selected from Cu2O, MnO2, CeO2, TiO2, and others.
[0053] Unless otherwise specified, the experimental methods or test methods described in the following examples are all conventional methods; the reagents and materials described are all obtained from conventional commercial channels or prepared by conventional methods unless otherwise specified.
[0054] Example 1
[0055] Weigh 150 mg of cetyltrimethylammonium chloride (CTAC) and dissolve it in 10 ml of ultrapure water. Once completely dissolved, add 50 ml of a 50 mM HAuCl4 solution, followed by 9 mg of citric acid. Stir for 3 minutes, then quickly add 250 ml of 30 mM NaBH4. Stir for 3 minutes, and then stir in an 80°C oil bath for 90 minutes.
[0056] To a round-bottom flask, add 200 ml of 80 mM cetyltrimethylammonium bromide (CTAB), 3 ml of 20 mM HAuCl₄ solution, 2 ml of 10 mM AgNO₃ solution, 4 ml of 1 M HCl solution, and 2 ml of 80 mM ascorbic acid (AA) solution. Mix and stir at room temperature for 3 minutes. Then, add 3 ml of the Au seeds prepared above. Incubate in a water bath at 25°C for 3 hours.
[0057] The AuNBPs prepared above were purified by centrifugation at 9500 rpm for 8 minutes and centrifuged twice. The purified AuNBPs were then redispersed in ultrapure water until the absorbance was 0.5. 10 ml of the redispersed AuNBPs were added to 30 ml of 30 mM CTAC solution. Stir and disperse for 3 minutes, then add 300 ml of AgNO3 solution, stir and disperse for 3 minutes, and then add 0.1 M ascorbic acid, half the volume of the AgNO3 solution. Incubate in a water bath at 50°C for 3 hours. After the reaction is complete, centrifuge and purify at 9500 rpm for 8 minutes and redisperse in 10 ml of ultrapure water.
[0058] To a round-bottom flask, add 750 ml of 0.01 M HAuCl₄ solution, 500 ml of 0.1 M AA solution, 500 ml of 0.05 M NaOH solution, and 50 ml of 0.1 M CTAB solution. After complete addition, stir at room temperature for 3 minutes. Then, add 10 ml of the previously redispersed AuNBPs@Ag nanorods. Incubate in a water bath at 25°C for 5 hours. After the reaction is complete, purify by centrifugation at 9500 rpm.
[0059] The AuNBPs@Ag nanorods purified by centrifugation were redispersed in 200 mL of 1 mM CTAB solution. Subsequently, 2 mL of 0.1 M NaHCO₃ solution, 2 mL of 0.1 M H₂O₂ solution, 1 mL of 0.05 M KSCN solution, and 2 mL of 10 mM Co(NO₃)₂ solution were gradually added. The mixture was incubated in a 70°C water bath for 20 minutes. The mixture was then centrifuged at 9500 rpm for purification.
[0060] The purified AuNBPs@Ag was redispersed in 2ml of 0.1M cetyltrimethylammonium bromide (CTAB) solution (cetyltrimethylammonium chloride (CTAC) or polyvinylpyrrolidone (PVP)) and stirred for 3 minutes. After mixing, 50ml of 20mM CuCl2 solution was slowly added dropwise to the AuNBPs@Ag solution and stirred for 5 minutes. Subsequently, 0.25ml of 0.1M NaOH solution and 0.5ml of 0.3M NH2OH·HCl solution were added dropwise. The mixture was then oven-dried at 50°C for 90 minutes to obtain the Cu2O-loaded bullet-shaped nanomotors.
[0061] Example 2
[0062] Weigh 160 mg of cetyltrimethylammonium chloride (CTAC) and dissolve it in 10 ml of ultrapure water. Once completely dissolved, add 50 ml of a 60 mM HAuCl4 solution, followed by 10 mg of citric acid. Stir for 5 minutes, then quickly add 250 ml of 50 mM NaBH4. Stir for 5 minutes, and then stir in a 90°C oil bath for 120 minutes.
[0063] To a round-bottom flask, add 200 ml of 100 mM cetyltrimethylammonium bromide (CTAB), 3 ml of 30 mM HAuCl₄ solution, 2 ml of 15 mM AgNO₃ solution, 4 ml of 2 M HCl solution, and 2 ml of 100 mM ascorbic acid (AA) solution. Mix and stir at room temperature for 5 minutes. Then, add 4 ml of the Au seeds prepared above. Incubate in a water bath at 30°C for 5 hours.
[0064] The AuNBPs prepared above were purified by centrifugation at 9500 rpm for 12 minutes, and then centrifuged twice. The purified AuNBPs were then redispersed in ultrapure water until the absorbance was 0.7. 20 ml of the redispersed AuNBPs were added to 30 ml of 40 mM CTAC solution. Stir and disperse for 5 minutes, then add 350 ml of AgNO3 solution, stir and disperse for 5 minutes, and then add 0.3 M ascorbic acid, half the volume of the AgNO3 solution. Incubate in a water bath at 60°C for 5 hours. After the reaction is complete, centrifuge at 9500 rpm for 10 minutes and redisperse in 15 ml of ultrapure water.
[0065] To a round-bottom flask, add 750 ml of 0.02 M HAuCl₄ solution, 500 ml of 0.2 M AA solution, 500 ml of 0.10 M NaOH solution, and 50 ml of 0.2 M CTAB solution. After complete addition, stir at room temperature for 5 minutes. Then, add 12 ml of the previously redispersed AuNBPs@Ag nanorods and incubate in a 30°C water bath for 6 hours. After the reaction is complete, purify by centrifugation at 9500 rpm.
[0066] The AuNBPs@Ag nanorods purified by centrifugation were redispersed in 200 mL of 3 mM CTAB solution. Subsequently, 2 mL of 0.3 M NaHCO₃ solution, 2 mL of 0.3 M H₂O₂ solution, 1 mL of 0.10 M KSCN solution, and 2 mL of 20 mM Co(NO₃)₂ solution were gradually added. The mixture was incubated in an 80°C water bath for 30 minutes. The mixture was then centrifuged at 9500 rpm for purification.
[0067] The purified AuNBPs@Ag was redispersed in 2ml of 0.2M cetyltrimethylammonium bromide (CTAB) solution (cetyltrimethylammonium chloride (CTAC) or polyvinylpyrrolidone (PVP)) and stirred for 5 minutes. After mixing, 50ml of 40mM CuCl2 solution was slowly added dropwise to the AuNBPs@Ag solution and stirred for 10 minutes. Subsequently, 0.25ml of 0.5M NaOH solution and 0.5ml of 0.4M NH2OH·HCl solution were added dropwise. The mixture was then oven-dried at 70°C for 90 minutes to obtain the Cu2O-loaded bullet-shaped nanomotors.
[0068] Example 3
[0069] Weigh 180 mg of cetyltrimethylammonium chloride (CTAC) and dissolve it in 10 ml of ultrapure water. Once completely dissolved, add 50 ml of 80 mM HAuCl₄ solution, followed by 12 mg of citric acid. Stir for 5 minutes, then quickly add 250 ml of 60 mM NaBH₄. Stir for 5 minutes, and then stir in a 90°C oil bath for 120 minutes.
[0070] To a round-bottom flask, add 200 ml of 150 mM cetyltrimethylammonium bromide (CTAB), 3 ml of 50 mM HAuCl₄ solution, 2 ml of 20 mM AgNO₃ solution, 4 ml of 3 M HCl solution, and 2 ml of 120 mM ascorbic acid (AA) solution. Mix and stir at room temperature for 5 minutes. Then, add 5 ml of the Au seeds prepared above. Incubate in a 35°C water bath for 5 hours.
[0071] The AuNBPs prepared above were purified by centrifugation at 9500 rpm for 12 minutes, and then centrifuged twice. The purified AuNBPs were then redispersed in ultrapure water until the absorbance was 1. 30 ml of the redispersed AuNBPs were added to 30 ml of 50 mM CTAC solution. Stir and disperse for 5 minutes, then add 400 ml of AgNO3 solution, stir and disperse for 5 minutes, and then add 0.5 M ascorbic acid, half the volume of the AgNO3 solution. Incubate in a water bath at 70°C for 6 hours. After the reaction is complete, centrifuge at 9500 rpm for 12 minutes and redisperse in 20 ml of ultrapure water.
[0072] To a round-bottom flask, add 750 ml of 0.03 M HAuCl₄ solution, 500 ml of 0.3 M AA solution, 500 ml of 0.15 M NaOH solution, and 50 ml of 0.3 M CTAB solution. After complete addition, stir at room temperature for 5 minutes. Then, add 15 ml of the previously redispersed AuNBPs@Ag nanorods. Incubate in a water bath at 35°C for 8 hours. After the reaction is complete, purify by centrifugation at 9500 rpm.
[0073] The AuNBPs@Ag nanorods purified by centrifugation were redispersed in 200 ml of 5 mM CTAB solution. Subsequently, 2 ml of 0.5 M NaHCO solution, 2 ml of 0.5 M H2O2 solution, 1 ml of 0.15 M KSCN solution, and 2 ml of 30 mM Co(NO3)2 solution were gradually added. The mixture was incubated in a 90°C water bath for 30 minutes. The mixture was then centrifuged at 9500 rpm for purification.
[0074] The purified AuNBPs@Ag was redispersed in 2ml of 0.3M cetyltrimethylammonium bromide (CTAB) solution (cetyltrimethylammonium chloride (CTAC) or polyvinylpyrrolidone (PVP)) and stirred for 5 minutes. After mixing, 50ml of 60mM CuCl2 solution was slowly added dropwise to the AuNBPs@Ag solution and stirred for 10 minutes. Subsequently, 0.25ml of 1M NaOH solution and 0.5ml of 0.6M NH2OH·HCl solution were added dropwise. The mixture was then oven-dried at 80°C for 150 minutes to obtain the Cu2O-loaded bullet-shaped nanomotors.
[0075] Figure 1 This is a transmission electron microscope image of the gold nanobipyramid AuNBPs prepared in Example 1. Figure 1 It can be seen that the longitudinal length of the gold nanobipyramids AuNBPs is about 105nm and the horizontal diameter is about 35nm. Figure 2 This is a transmission electron microscopy image of the AuNBPs@Ag nanorods prepared in Example 1. Figure 2 It can be seen that the AuNBPs@Ag nanorods are composed of two parts: the AuNBPs core and the Ag nanorod shell with obvious contrast difference. The longitudinal length of the AuNBPs@Ag nanorods is about 196nm and the transverse diameter is about 25nm.
[0076] Figure 3 This is a transmission electron microscope image of the AuNBPs@Ag nanorod with one end hollowed out obtained by preliminary etching in Example 1. As can be seen from the left image, after asymmetric etching, there is a clear contrast difference at both ends of the AuNBPs@Ag nanorod, one end is obviously hollow, and the other end presents a solid structure, which lays the asymmetric structural foundation for subsequent processing. Figure 4 This is a transmission electron microscope image of the solid bullet-shaped AuNBPs@Ag nanorods obtained by further etching in Example 1. Figure 4 It can be seen that the AuNBPs@Ag nanorods are hollowed at one end and then further etched to obtain solid bullet-shaped AuNBPs@Ag nanorods.
[0077] Figure 5 This is a transmission electron microscope image of the bullet-shaped AuNBPs@Ag nanomaterial obtained by opening the tail of the solid bullet-shaped AuNBPs@Ag nanorod in Example 1. Figure 5 It can be seen that the contrast of the Ag rod shell is significantly reduced compared with that before treatment, indicating that the interior of the Ag rod shell is successfully hollowed out; and the tail of the Ag rod presents a smooth cut compared with the rounded arc before treatment, indicating that the hollowed tail of the Ag rod is successfully opened. Figure 6This is a transmission electron microscope image of a bullet-shaped nanomotor obtained by loading Cu2O on the tail opening of the bullet-shaped AuNBPs@Ag nanomaterial in Example 1. Figure 6 As can be seen in the figure, Cu2O is in situ synthesized inside the Ag rod shell, indicating the successful fabrication of the bullet-shaped nanomotor. Furthermore, the Cu2O inside the Ag rod shell can be replaced with MnO2, CeO2, TiO2, etc.
[0078] Figure 7 The trajectory of the bullet-shaped nanomotor prepared in Example 1 in 5 mM H2O2 is shown in Figure 1. Figure 7 It can be seen that the Cu2O loaded on the tail of the bullet-shaped nanomotor can efficiently decompose H2O2 to generate O2, thereby generating power. And from the motion trajectory, it can be seen that the bullet-shaped nanomotor has strong guidance and can efficiently convert chemical energy into kinetic energy.
[0079] Figure 8 is the cumulative movement distance of the bullet-shaped nanomotor in different H2O2 concentrations within 60s, Figure 8 It can be seen that the bullet-shaped nanomotor can move efficiently even in 0.1mM H2O2, with a movement speed of up to 3.3mm / s. As the H2O2 concentration gradually increases, the movement performance of the bullet-shaped nanomotor also gradually improves, showing a dose-dependent improvement. When the H2O2 concentration increases to 10mM, the speed of the bullet-shaped nanomotor increases to 6.3mm / s, showing high dynamic performance and application potential.
[0080] In summary, the present invention innovatively prepares Au nanoseeds through chloroauric acid reduction; subsequently, it induces the growth of gold nanobipyramids (AuNBPs) in a seed-mediated manner; further, a layer of Ag nanorods is grown on the AuNBPs; then, through asymmetric etching, half of the Ag rods on the AuNBPs' surface are etched away, leaving the other half with an open tail; finally, through in situ synthesis of Cu2O at the open tail end, a bullet-shaped nanomotor with excellent dynamic performance is obtained. The unique bullet-shaped morphology imparts good directionality and excellent dynamic performance. Furthermore, the open tail end can also be loaded with various specific targets according to research needs.
[0081] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be construed as limiting the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. Persons skilled in the art will appreciate that improvements and modifications may be made without departing from the spirit and scope of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A bullet-shaped nanomotor with a hole at the tail, characterized in that: The bullet-shaped nanomotor includes a bullet-shaped AuNBPs@Ag nanomaterial and a power source, wherein the bullet-shaped AuNBPs@Ag nanomaterial is composed of gold nanobipyramids AuNBPs and Ag nanorods; one end of the gold nanobipyramids AuNBPs is exposed to form a tip structure, and the other end is wrapped by the Ag nanorod to form a rod-shaped structure; the tail of the Ag nanorod has an opening, and the power source is loaded on the opening.
2. The bullet-shaped nanomotor with a hole at the tail according to claim 1, characterized in that: The power source includes a metal oxide.
3. The bullet-shaped nanomotor with a hole at the tail according to claim 2, characterized in that: The metal oxide includes any one of manganese dioxide, titanium dioxide, cerium dioxide and cuprous oxide.
4. A method for preparing a bullet-shaped nanomotor with a hole at the tail, characterized in that: The preparation method comprises: preparing Au seeds; Using the Au seeds to induce growth and form gold nanobipyramids AuNBPs; A layer of silver nanomaterial is coated and grown on the surface of the gold nanobipyramid AuNBPs to form AuNBPs@Ag nanorods; Asymmetrically etching the AuNBPs@Ag nanorod to make one end of the nanorod hollow, and then opening a hole at the other end to obtain a bullet-shaped AuNBPs@Ag nanomaterial with an opening at the tail; A hole is opened at the tail of the bullet-shaped AuNBPs@Ag nanomaterial to load a power source, and finally a bullet-shaped nanomotor is obtained.
5. The method for preparing a bullet-shaped nanomotor with a hole at the tail according to claim 4, characterized in that: The preparation of the gold nanobipyramid AuNBPs includes: In a solution containing hexadecyltrimethylammonium bromide, chloroauric acid, silver nitrate, hydrochloric acid and ascorbic acid, Au seeds were added to form gold nanobipyramids AuNBPs through a self-assembly and growth process.
6. The method for preparing a bullet-shaped nanomotor with a hole at the tail according to claim 4, characterized in that: The preparation of the AuNBPs@Ag nanorods comprises: Gold nanobipyramids AuNBPs were mixed with hexadecyltrimethylammonium chloride, silver nitrate and ascorbic acid, and a silver nanolayer was grown on the surface of the gold nanobipyramids AuNBPs through a reduction reaction of silver ions.
7. The method for preparing a bullet-shaped nanomotor with a hole at the tail according to claim 4, characterized in that: The asymmetric etching step comprises: A mixed solution containing chloroauric acid, ascorbic acid, sodium hydroxide and hexadecyltrimethylammonium bromide is prepared and stirred evenly at room temperature; the AuNBPs@Ag nanorods are added to the mixed solution and reacted in a water bath at 25-35° C. for 5-8 hours to hollow one end of the nanorods, and purified after the reaction is completed; The purified AuNBPs@Ag nanorods were redispersed in a solution containing hexadecyltrimethylammonium bromide, and sodium bicarbonate, hydrogen peroxide, potassium thiocyanate and cobalt nitrate were added in sequence. The reaction was carried out in a water bath at 70-90°C for 20-30 minutes to open a hole at the other end. After the reaction was completed, the nanorods were purified to obtain a bullet-shaped AuNBPs@Ag nanomaterial with a hole at the tail.
8. The method for preparing a bullet-shaped nanomotor with a hole at the tail according to claim 4, characterized in that: The step of opening a hole at the tail of the bullet-shaped AuNBPs@Ag nanomaterial to load a power source comprises: The bullet-shaped AuNBPs@Ag nanomaterial with an opening at the tail is dispersed in a solution containing a ligand, and then a solution containing a power source precursor is added and mixed and stirred. Then, sodium hydroxide solution and hydroxylamine hydrochloride solution are added and reacted at 50-80°C for 90-150 minutes to obtain a bullet-shaped nanomotor with a power source loaded on the opening at the tail.
9. The method for preparing a bullet-shaped nanomotor with a hole at the tail according to claim 8, characterized in that: The ligand includes any one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride and polyvinylpyrrolidone.
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