Magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nano-particle with gas curative effect and photothermal effect and preparation method of magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nano-particle

Abstract

The invention relates to the technical field of preparation of nano devices, in particular to a magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nano particle with a gas curative effect and a photothermal effect and a preparation method of the magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nano particle. Rod-shaped Fe3O4 particles are used as a magnetic base material, the outer side of the magnetic base material is coated with a photo-thermal agent, and the magnetic base material is modified with a thermally triggered nitric oxide donor for gas therapy. The magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nanoparticles with the gas curative effect and the photothermal effect, prepared by the preparation method disclosed by the invention, are relatively small in size, good in biocompatibility, uniform in particle size and high in magnetic saturation intensity, and have a wide application prospect in the field of biomedicine. By virtue of the excellent magnetism of the Fe3O4 particles, the nano-particles can easily realize the movement guided by the magnet; meanwhile, after being modified by a photo-thermal agent, the nano-particles can be subjected to photo-thermal conversion under the irradiation of near-infrared light, so that local temperature rise is realized. The magnetic rod-shaped Fe3O4 (at) PDA (at) BNN6 nano-particles with the gas curative effect and the photothermal effect, prepared by the method, are simple in preparation process and low in production cost, and can be applied to the fields of magnetic nano-motors, magnetic photothermal conversion materials and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of nanodevice preparation, and in particular to a magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle having gas therapeutic effect and photothermal effect and a preparation method thereof. Background Art

[0002] In recent years, gas therapy has gained widespread application as an emerging biomedical therapeutic strategy in disease treatment. Nitric oxide (NO), a key gaseous signaling molecule, plays a crucial role in regulating physiological processes such as vasodilation, neurotransmission, and immune responses. NO molecules are highly diffusible and unstable, making targeted release difficult. Consequently, numerous studies have developed composite systems based on photothermal materials and thermosensitive NO donors, achieving controlled NO release through temperature-responsive mechanisms and providing effective solutions for improving NO delivery efficiency. While some photothermal materials, such as gold nanoparticles and carbon nanotubes, exhibit moderate photothermal conversion efficiency, they suffer from high cost, poor biocompatibility, and complex preparation processes. Most traditional magnetic nanomaterials exhibit relatively weak photothermal performance, making them difficult to independently meet the demands of high-efficiency photothermal conversion applications. Common spherical Fe₃O₄ nanoparticles, due to their lack of the unique optical anisotropy associated with their aspect ratio, exhibit slightly inferior light absorption and thermal energy conversion performance compared to rod-shaped nanoparticles. Furthermore, the unique morphology of rod-shaped Fe₃O₄ nanoparticles facilitates magnetic moment alignment, thereby enhancing their magnetic properties. In recent years, despite some research on magnetic rod-shaped nanomaterials, there are still deficiencies in the preparation of rod-shaped nanoparticles that can effectively combine magnetism with photothermal effects. In summary, it is extremely necessary to develop nanoparticles that simultaneously possess gas therapy, photothermal effects, and magnetic properties, and to explore a simple, efficient, and large-scale method for preparing such particles. Based on the above background, the present invention proposes a magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle with gas therapy and photothermal effects and a preparation method thereof. Summary of the Invention

[0003] The present invention belongs to the field of nanotechnology, and specifically relates to a magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle with gas therapeutic effect and photothermal effect and a preparation method thereof.

[0004] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0005] In a first aspect, the present invention provides a magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle with gas therapy and photothermal effect based on a hydrothermal synthesis method and an alkaline polymerization method and a preparation method thereof, comprising the following steps:

[0006] (1) Preparation of uniformly sized magnetic rod-shaped Fe3O4 particles by hydrothermal synthesis;

[0007] (2) Polydopamine (PDA)-coated Fe3O4 composite particles were obtained by alkaline polymerization;

[0008] (3) Using the abundant functional groups of PDA to modify the thermosensitive nitric oxide donor drug BNN6;

[0009] Preferably, step (1) comprises the following steps: preparing a mixture of 0.02M FeCl3·6H2O and 0.45mM NaH2PO4 in an aqueous solution to form a total volume of 75mL, and magnetically stirring the mixture until the solution exhibits a transparent lemon yellow color. The solution is transferred to a hydrothermal reactor, sealed, and placed in a constant temperature furnace. The constant temperature furnace parameters are set to heat continuously at 160°C for 12 hours. After the constant temperature furnace is naturally cooled to room temperature, the hydrothermal reactor is removed, and the precipitate remaining in the reactor after sintering is collected. Subsequently, ultrapure water is used as a cleaning liquid, and the precipitate is washed multiple times using an ultrasonic centrifugal device. The washed precipitate is placed in a drying oven and dried at 60°C to obtain Fe2O3 particles. Subsequently, the dried Fe2O3 is uniformly ground and placed in a tube furnace for reduction treatment at 350°C for 1 hour in an atmosphere of ethanol and N2, ultimately obtaining magnetic rod-shaped Fe3O4 particles.

[0010] Preferably, step (2) comprises the following steps: 40 mg of magnetic rod-shaped Fe3O4 particles are weighed and ultrasonically dispersed in a 10 mM Tris-HCl solution with a pH of 8.5. After the particles are evenly dispersed, 40 mg of dopamine hydrochloride is weighed and poured into the mixture. The mixture is mechanically stirred at 350 rpm in the dark for 12 hours. The Fe3O4@PDA product is collected with a magnet and then vacuum dried.

[0011] Preferably, step (3) comprises the following steps: grinding the Fe3O4@PDA, weighing 20 mg of Fe3O4@PDA, and evenly dispersing the mixture in 20 mL of ultrapure water; at the same time, weighing 20 mg of BNN6 in a dark environment and evenly dispersing the mixture in 10 mL of ethanol. The BNN6 solution is slowly dripped into the Fe3O4@PDA dispersion, and mechanically stirred at 350 rpm for 12 hours in a dark environment. The reaction product is washed with ultrapure water and vacuum dried to obtain the final Fe3O4@PDA@BNN6 particles.

[0012] SEM electron microscopy analysis showed that the particle size of the magnetic rod-shaped Fe3O4 nanoparticles was relatively uniform, about 300 nm; the particle size of the magnetic rod-shaped Fe3O4 nanoparticles coated with the photothermal agent PDA was relatively uniform.

[0013] The present invention has the following advantages and beneficial effects:

[0014] 1. The preparation process is simple and efficient. The produced magnetic rod-shaped Fe3O4 has uniform size and good photothermal conversion ability and temperature-controlled NO release ability.

[0015] 2. The magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles prepared in this invention exhibit both gas therapy and photothermal effects, demonstrating excellent magnetic responsiveness and photothermal conversion capabilities. Future applications of this material include photothermal conversion materials, magnetically or thermally driven nanomotors, and biomedical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is a scanning electron microscope photograph of the magnetic rod-shaped Fe3O4 nanoparticles of the present invention;

[0017] Figure 2 This is a scanning electron microscope photograph of rod-shaped Fe3O4 nanoparticles coated with the photothermal agent PDA in the present invention;

[0018] Figure 3 This is a graph showing the temperature rise test results of Fe3O4@PDA@BNN6 nanoparticles of different concentrations under near-infrared light irradiation;

[0019] Figure 4 This is a concentration curve of NO gas released from Fe3O4@PDA@BNN6 nanoparticles in the present invention as the laser irradiation time increases. DETAILED DESCRIPTION

[0020] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. The following embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention shall be considered equivalent replacement methods and are included in the scope of protection of the present invention.

[0021] Example 1: Preparation of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapy and photothermal effects

[0022] A 0.02M aqueous solution of FeCl₃·6H₂O and a 0.45mM aqueous solution of NaH₂PO₄ were prepared to a total volume of 75mL and magnetically stirred until the solution exhibited a transparent lemon-yellow color. The solution was transferred to a hydrothermal reactor, sealed, and placed in a thermostatic furnace. The furnace was set to heat continuously at 160°C for 12 hours. After the furnace cooled naturally to room temperature, the hydrothermal reactor was removed and the precipitate remaining after sintering was collected. The precipitate was then rinsed multiple times with ultrapure water using an ultrasonic centrifuge. The rinsed precipitate was then dried in a drying oven at 60°C to obtain Fe₂O₃ particles. The dried Fe₂O₃ was then uniformly ground and reduced in a tube furnace at 350°C for 1 hour under an atmosphere of ethanol and nitrogen, yielding magnetic rod-shaped Fe₃O₄ particles.

[0023] Step 2: Weigh 40 mg of magnetic rod-shaped Fe₃O₄ particles and ultrasonically disperse them in a 10 mM Tris-HCl solution with a pH of 8.5. Once the particles are evenly dispersed, weigh 40 mg of dopamine hydrochloride and add it to the mixture. Mechanically stir at 350 rpm in the dark for 12 hours. The resulting Fe₃O₄@PDA is collected with a magnet and then vacuum-dried.

[0024] Step 3: Grind the Fe3O4@PDA. Weigh 20 mg of Fe3O4@PDA and evenly disperse it in 20 mL of ultrapure water. Simultaneously, weigh 20 mg of BNN6 and evenly disperse it in 10 mL of ethanol in a dark environment. Slowly drip the BNN6 solution into the Fe3O4@PDA dispersion and mechanically stir at 350 rpm for 12 hours in the dark. Rinse the reaction product with ultrapure water and vacuum dry it to obtain the final Fe3O4@PDA@BNN6 particles.

[0025] Test Example 1: Photothermal Conversion Performance Test of Magnetic Rod-Shaped Fe3O4@PDA@BNN6 Nanoparticles with Gas Therapeutic Effect and Photothermal Effect

[0026] To test the photothermal conversion performance of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapy and photothermal effects, the nanoparticles were first dispersed in ultrapure water to prepare dispersions of different concentrations. Subsequently, 2 mL of each dispersion was measured and placed in a centrifuge tube. Finally, the centrifuge tube containing the dispersion was placed under a near-infrared laser with a wavelength of 793 nm for irradiation testing. The test results are shown in Figure 2. Figure 3 (Gas therapy and photothermal effect of different concentrations of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle dispersion at a power density of 3.0W / cm 2, the temperature rise curve under laser irradiation with a wavelength of 793nm).

[0027] Different concentrations of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles, which exhibit both gas therapy and photothermal effects, all exhibited a favorable temperature increase, with the magnitude of the temperature increase positively correlated with irradiation time. A dispersion of particles with a concentration of 100 μg / mL experienced an 8°C temperature increase after 10 minutes of irradiation, while a dispersion with a concentration of 500 μg / mL reached approximately 53°C after 10 minutes of irradiation. This demonstrates the excellent photothermal conversion properties of these magnetic nanoparticles.

[0028] Test Example 2: NO gas release test of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapy and photothermal effects

[0029] In order to further explore the light-controlled NO release performance of magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapeutic effects and photothermal effects, the test first dispersed the Fe3O4@PDA@BNN6 nanoparticles with ultrapure water to prepare a dispersion. Subsequently, 2 mL of the dispersion with a concentration of 150 μg / mL was taken and placed in a centrifuge tube, and irradiated with a near-infrared laser with a wavelength of 808 nm for 60 minutes. The supernatant was collected every 10 minutes for Griess reagent detection, and the absorbance of the sample at a wavelength of 540 nm was detected by an enzyme marker, which can indirectly reflect the NO gas release performance of the magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapeutic effects and photothermal effects. The test results are as follows Figure 4 (Magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle dispersion with gas therapy and photothermal effect at a power density of 1.0 W / cm 2 , as shown in the NO gas release curve over time under irradiation of near-infrared laser with a wavelength of 808nm).

[0030] As the laser irradiation time increases, the dispersion temperature gradually rises. During this process, BNN6 releases NO gas due to the heat. Figure 4 The results show that the cumulative concentration of NO gas continues to rise with the increase of irradiation time. This phenomenon fully proves that the magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles have the ability to release NO gas by light triggering, and also verifies the feasibility of NO gas therapy.

Claims

1. A magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticle with gas therapy and photothermal effect based on hydrothermal synthesis and alkaline polymerization method and its preparation method, characterized in that: The following steps are involved: (1) Preparation of uniformly sized magnetic rod-shaped Fe3O4 particles by hydrothermal synthesis; (2) Polydopamine (PDA)-coated Fe3O4 composite particles were obtained by alkaline polymerization; (3) The rich functional groups of PDA were used to modify the thermosensitive nitric oxide donor drug BNN6.

2. The method according to claim 1, characterized in that The specific steps of step (1) are as follows: a mixture of 0.02M FeCl3·6H2O and 0.45mM NaH2PO4 in water is prepared into a total volume of 75mL, and magnetically stirred until the solution turns transparent lemon yellow. The above solution is transferred to a hydrothermal reactor, sealed, and placed in a constant temperature furnace. The constant temperature furnace parameters are set and heating is continued at 160°C for 12 hours. After the constant temperature furnace is naturally cooled to room temperature, the hydrothermal reactor is removed and the precipitate remaining in the reactor after sintering is collected. Subsequently, ultrapure water is used as a cleaning liquid and the precipitate is washed multiple times by ultrasonic centrifugation. The washed precipitate is placed in a drying oven and dried at 60°C to obtain Fe2O3 particles. Subsequently, the dried Fe2O3 particles are uniformly ground and placed in a tube furnace for reduction treatment at 350°C for 1 hour under an atmosphere of ethanol and N2 to finally obtain magnetic rod-shaped Fe3O4 particles.

3. The method according to claim 1, characterized in that Step (2) specifically involves the following steps: 40 mg of magnetic rod-shaped Fe₃O₄ particles were weighed and ultrasonically dispersed in a 10 mM Tris-HCl solution with a pH of 8.

5. After the particles were evenly dispersed, 40 mg of dopamine hydrochloride was added to the mixture and mechanically stirred at 350 rpm in the dark for 12 h. The Fe₃O₄@PDA product was collected with a magnet and then vacuum dried.

4. The method according to claim 1, characterized in that Step (3) is as follows: Grind the Fe3O4@PDA, weigh 20 mg of Fe3O4@PDA, and evenly disperse it in 20 mL of ultrapure water. Simultaneously, weigh 20 mg of BNN6 in a dark environment and evenly disperse it in 10 mL of ethanol. Slowly drip the BNN6 solution into the Fe3O4@PDA dispersion and mechanically stir at 350 rpm for 12 hours in the dark. Wash the reaction product with ultrapure water and vacuum dry it to obtain the final Fe3O4@PDA@BNN6 particles.

5. The preparation method of claims 1 to 4 produces magnetic rod-shaped Fe3O4@PDA@BNN6 nanoparticles with gas therapy and photothermal effects.

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