CN111906326B - Photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material and preparation and application thereof - Google Patents
Photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a photomagnetic double-response core-shell type gold-ferroferric sulfide nano material and preparation and application thereof. According to the invention, ferric chloride and a sulfur precursor are used as raw materials, ferroferric sulfide nano particles are synthesized by a secondary hydrothermal method, and then a nano gold shell is wrapped on the surfaces of the ferroferric sulfide particles by utilizing a metal compatibility principle, so that the photomagnetic double-response core-shell type gold-ferroferric sulfide particle material is obtained. The optomagnetic dual-response core-shell type gold-ferroferric sulfide particle material prepared by the invention can still keep stability and magnetism after being placed for a long time at a higher temperature, and can meet the requirement of reducing the formation of colloid scars at the injured parts of the spine.
Description
Technical Field
The invention belongs to the technical field of preparation of materials for treating spinal injuries, and particularly relates to a photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material, and preparation and application thereof.
Background
The regeneration of neurons is blocked, and the function of a wound repair part cannot be completely recovered. There is therefore a need to intervene in the proliferation of astrocytes to reduce glial scar formation and promote axonal and neuronal regeneration. The X-ray has the characteristics of strong penetrating power, short wavelength and large energy, and is applied to reducing the colloid scar formation caused by acute spinal cord injury. However, demyelination, when exposed to X-ray radiation for a prolonged period of time, is prone to ischemic edema, and X-ray radiation can also affect normal human tissue. One of the effective ways to solve this problem is to inject nanomaterials (such as nanogold, thermal release point materials, etc.) with high photothermal conversion efficiency into the spinal cord injury area through photothermal therapy (PTT), and convert light energy into heat energy under the irradiation of an external light source to inhibit astrocyte aggregation and reduce the formation of glial scar. However, photothermal therapy is limited in effectiveness due to the limited penetration of laser light. Magnetocaloric therapy (MHT), generated by an alternating magnetic field, has the ability to penetrate deep tissues and can be used without depth limitation, but nanomaterials have a low rate of magnetocaloric absorption. Therefore, the combined use of photothermal and magnetothermal has significant advantages in improving the thermotherapy effect and treating deep lesions. Currently, there are few reports on the combined use of photothermal and magnetocaloric, and magnetic particles are generally combined with polypyrrole, carbon nanotubes, metal nanoparticles, and the like, which have high conversion efficiency. However, the preparation process is complicated, and the stability can not be maintained for a long time under the high temperature condition, so that the further biological application is limited. Therefore, the development of a photo-thermal and magneto-thermal combined action material which is simple to prepare and good in thermal stability becomes a new research direction.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a photomagnetic double-response core-shell type gold-ferroferric sulfide nano material. The method is simple to operate, ferric chloride is used as a raw material, ferroferric sulfide nano particles are synthesized by a secondary hydrothermal method, and a nano gold shell is wrapped on the surfaces of the ferroferric sulfide particles by utilizing a metal compatibility principle, so that the core-shell type gold-ferroferric sulfide particles are obtained. The core-shell type gold-ferroferric sulfide particles prepared by the method can still maintain the stability and magnetism after being placed for a long time at a higher temperature, and can meet the requirement of reducing the formation of colloid scars at the injured parts of the spine.
The invention also aims to provide the photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material prepared by the method.
The invention further aims to provide application of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a photomagnetic double-response core-shell type gold-ferroferric sulfide nano material comprises the following steps:
(1) taking a solvent as a reaction medium, and carrying out hydrothermal reaction on ferric chloride, trisodium citrate and sodium acetate trihydrate to obtain ferroferric oxide nano-particles;
(2) mixing the ferroferric oxide nanoparticles with a solvent, adding a sulfur precursor, carrying out hydrothermal reaction, centrifuging, and drying to obtain ferroferric sulfide nanoparticles;
(3) and dispersing the ferroferric sulfide nano particles in a chloroauric acid solution, adding a reducing agent, reacting for 2-3 hours, and centrifuging to obtain the magneto-optical dual-response core-shell type gold-ferroferric sulfide nano material.
Preferably, the solvent in step (1) is at least one of water, ethylene glycol and ethanol, and more preferably ethylene glycol.
Preferably, the mass ratio of the ferric chloride, the trisodium citrate and the sodium acetate trihydrate in the step (1) is (5.4-10.8): (1-4): (10-20).
Preferably, the ratio of the ferric chloride to the solvent in the step (1) is (1.08-2.16) g/40 ml.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 100-200 ℃, and the time is 4-12 hours; more preferably, the reaction is carried out at 150 to 200 ℃ for 10 hours.
Preferably, the ratio of the ferroferric oxide nanoparticles to the solvent in the step (2) is (12.5-25 mg): (30-50) ml.
Preferably, the mass ratio of the ferroferric oxide nanoparticles to the sulfur precursor in the step (2) is 1: (9-18).
Preferably, the sulfur precursor in step (2) is at least one of sodium sulfide and thioacetamide. The sulfur precursor is capable of releasing sulfide ions.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 150-200 ℃ and the time is 4-12 hours; more preferably, the reaction is carried out at 160 to 180 ℃ for 10 hours.
Preferably, the drying in the step (2) is conventional vacuum drying, the temperature is 37-80 ℃, and the time is 0.5-3 hours.
Preferably, the solvent in step (2) is at least one of water, ethylene glycol and ethanol, and more preferably ethanol.
Preferably, the solvent used in the centrifugation in the step (2) is a solvent prepared by mixing the components in a volume ratio of 1: 1: 0.5 of ethanol-water-ethylene glycol mixed solution, wherein the volume ratio of the ferroferric sulfide particles to the mixed solution is 1: 2.
preferably, the ferroferric sulfide nano particles in the step (3) are dispersed in the chloroauric acid solution in an ultrasonic mode, the ultrasonic time is 10-30 min, and the ultrasonic frequency is 20-40 Hz.
Preferably, the mol ratio of the ferroferric sulfide nanoparticles in the step (3) to the chloroauric acid in the chloroauric acid solution is 1: 1 to 4.
Preferably, the mass concentration of the chloroauric acid solution in the step (3) is 1-3%, and more preferably 1.5-2%.
Preferably, the molar ratio of the reducing agent in the step (3) to the chloroauric acid in the chloroauric acid solution is 1: 1.
the reducing agent in the step (3) is a substance capable of reducing gold ions into nanogold, and is preferably at least one of sodium borohydride, trisodium citrate and ascorbic acid; when the reducing agent is ascorbic acid, the reduction reaction is carried out under the condition of keeping out light.
Preferably, the reducing agent in the step (3) is added in the form of a solution, and the concentration of the reducing agent is 2-4 mol/L.
Preferably, the temperature of the reaction in step (3) is room temperature.
Preferably, the rotating speed of the centrifugation in the step (3) is 9000-10000 r/min, the time is 10-30 min, and the centrifugation times are 1-5 times.
The photomagnetic double-response core-shell type gold-ferroferric sulfide nano material prepared by the method.
The photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material is applied to the fields of medicine preparation and photo-thermal and magneto-thermal combined action material preparation.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention combines the photo-thermal therapy and the magnetic thermal therapy, is beneficial to effectively treating deep pathological changes, and expands the application of nano materials in the preparation field of spinal injury treatment materials.
(2) The preparation method is simple, and the obtained core-shell type gold-ferroferric sulfide nano-particles overcome the defect that common nano-materials are easy to oxidize and agglomerate due to the existence of a sulfur-gold bond, and have good stability.
(3) The core-shell type gold-ferroferric sulfide nano-particles prepared by the invention benefit from the nano-gold shell, and can realize real-time monitoring through CT radiography.
(4) The core-shell type gold-ferroferric sulfide nano-particles obtained by the method have good biocompatibility.
(5) The invention does not need complex steps, and compared with the existing wet chemical method, the preparation process is simple, and the obtained product has good dispersibility, uniform size and good process repeatability.
Drawings
FIG. 1 is an XRD pattern of ferroferric sulfide obtained in example 1.
FIG. 2 is a UV spectrum of ferroferric sulfide and core-shell gold-ferroferric sulfide nanoparticles and metallic gold obtained in example 1.
Fig. 3 is a particle size distribution diagram of the ferroferric sulfide particles and the core-shell type gold-ferroferric sulfide nanoparticles obtained in example 1, wherein the hydration particle size of the ferroferric sulfide particles is 102.5nm, and the hydration particle size of the core-shell type gold-ferroferric sulfide nanoparticles is 105.7nm, which shows that the nano-material obtained in the invention is basically monodisperse, and the particle size is not greatly influenced after the nano-gold shell is wrapped.
FIG. 4 is a graph showing the hydrated particle size of core-shell gold-ferroferric sulfide nanoparticles obtained in example 1 dispersed in DMEM.
Fig. 5 is a physical diagram of the core-shell type gold-ferroferric sulfide nanoparticle obtained in example 1 (right) and the ferroferric sulfide nanoparticle obtained in comparative example 1 (left).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1)0.54g of ferric chloride, 0.1g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 10ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 150 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment for 3 hours at 37 ℃ in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution is 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: the mixed solution was sonicated at 1,160 w for 10 min. Taking 2ml of 2mol/L sodium borohydride aqueous solution (the molar ratio of sodium borohydride to chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 2 hours, after the reaction is finished, carrying out centrifugation for three times for 20min at 9800r/min, and carrying out vacuum drying after separation to obtain the core-shell type gold-ferroferric sulfide particles.
Example 2
(1)0.54g of ferric chloride, 0.4g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 20ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 175 ℃ to obtain ferroferric oxide particles.
(2)25mg Fe3O4Adding the nanospheres and 450mg of thioacetamide into 50ml of absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle at 160 ℃, and heating the mixture for 10 hours to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment for 3 hours at 37 ℃ in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution was 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: the mixed solution was sonicated for 10min at 2,160 w. Taking 2ml of 2mol/L sodium borohydride aqueous solution (the molar ratio of sodium borohydride to chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 2 hours, after the reaction is finished, carrying out centrifugation for three times for 20min at 9800r/min, and carrying out vacuum drying after separation to obtain the core-shell type gold-ferroferric sulfide particles.
Example 3
(1)1.08g of ferric chloride, 0.4g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 40ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 200 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment for 3 hours at 37 ℃ in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution was 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: 4,160 w sonicate the mixed solution for 10 min. Taking 2ml of 2mol/L sodium borohydride aqueous solution (the molar ratio of sodium borohydride to chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 2 hours, after the reaction is finished, carrying out centrifugation for three times for 20min at 9800r/min, and carrying out vacuum drying after separation to obtain the core-shell type gold-ferroferric sulfide particles.
Example 4
(1)0.54g of ferric chloride, 0.1g of trisodium citrate and 1g of sodium acetate trihydrate are mixed, dissolved in 10ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 150 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment for 1.5 hours at 60 ℃ in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution is 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: the mixed solution was sonicated at 1,160 w for 10 min. Taking 2ml of ascorbic acid aqueous solution (the molar ratio of ascorbic acid to chloroauric acid is 1: 1) of 4mol/L as a reducing agent, stirring and reacting for 2 hours in a dark place, after the reaction is finished, 9800r/min, centrifuging for 20min for three times, separating, and drying in vacuum to obtain the core-shell type gold-ferroferric sulfide particles.
Example 5
(1)1.08g of ferric chloride, 0.4g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 20ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 175 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture at 180 ℃ for 10 hours to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. Vacuum drying the centrifuged ferroferric sulfide particles at 60 ℃ for 1.5 hours for later useThe application is as follows.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution was 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in a 2% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: the mixed solution was sonicated for 10min at 2,160 w. Taking 2ml of ascorbic acid aqueous solution (the molar ratio of ascorbic acid to chloroauric acid is 1: 1) of 4mol/L as a reducing agent, stirring and reacting for 2.5 hours in the dark, after the reaction is finished, 9800r/min, centrifuging for 20min for three times, separating, and drying in vacuum to obtain the core-shell type gold-ferroferric sulfide particles.
Example 6
(1)0.54g of ferric chloride, 0.1g of trisodium citrate and 1g of sodium acetate trihydrate are mixed, dissolved in 10ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 200 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment for 1.5 hours at 60 ℃ in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution is 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in a 2% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: 4,160 w sonicate the mixed solution for 10 min. Taking 2ml of ascorbic acid aqueous solution (the molar ratio of ascorbic acid to chloroauric acid is 1: 1) of 4mol/L as a reducing agent, stirring and reacting for 3 hours in a dark place, after the reaction is finished, 9800r/min, centrifuging for 20min for three times, separating, and drying in vacuum to obtain the core-shell type gold-ferroferric sulfide particles.
Example 7
(1)0.54g of ferric chloride, 0.1g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 10ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 150 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment at 80 ℃ for 0.5 hour in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution is 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: 4,160 w sonicate the mixed solution for 30 min. Taking 1ml of 2mol/L trisodium citrate aqueous solution (the molar ratio of the trisodium citrate to the chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 2 hours, after the reaction is finished, carrying out centrifugation for three times for 20min at 9800r/min, and carrying out vacuum drying after separation to obtain the core-shell type gold-ferroferric sulfide particles.
Example 8
(1)0.54g of ferric chloride, 0.4g of trisodium citrate and 1.5g of sodium acetate trihydrate are mixed, dissolved in 20ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 175 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. Vacuum drying the centrifuged ferroferric sulfide particles at 80 DEG CAfter 0.5 hour, it is ready for use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution was 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(3) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: the mixed solution was sonicated at 1,160 w for 30 min. Taking 2ml of 2mol/L trisodium citrate aqueous solution (the molar ratio of the trisodium citrate to the chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 2.5 hours, after the reaction is finished, carrying out centrifugation for three times for 20min, and carrying out vacuum drying after separation to obtain the core-shell type gold-ferroferric sulfide particles.
Example 9
(1)1.08g of ferric chloride, 0.4g of trisodium citrate and 2g of sodium acetate trihydrate are mixed, dissolved in 40ml of ethylene glycol, transferred to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 200 ℃ to obtain ferroferric oxide particles.
(2)12.5mg Fe3O4Adding the nanospheres and 112.5mg thioacetamide into 30ml absolute ethyl alcohol for uniform dispersion, transferring the mixture into a reaction kettle, sealing the reaction kettle, and heating the mixture for 10 hours at 160 ℃ to obtain ferroferric sulfide particles. And then, adding an ethanol-water-ethylene glycol mixed solution when the prepared ferroferric sulfide particles are cooled to room temperature, washing for many times, and centrifuging until the upper layer centrifugate is colorless. And (4) drying the ferroferric sulfide particles subjected to centrifugal treatment at 80 ℃ for 0.5 hour in vacuum for later use.
Wherein: the volume ratio (mL/mL) of ethanol, water and ethylene glycol in the mixed solution was 1: 1: 0.5, the volume ratio (mL/mL) of the ferroferric sulfide particles to the mixed solution is 1: 2.
(4) suspending a proper amount of ferroferric sulfide particles in 1.5% chloroauric acid aqueous solution, and adjusting the molar ratio of the ferroferric sulfide to the chloroauric acid in the solution to be 1: 2. and (2) carrying out ultrasonic treatment on the mixed solution for 30min at 160w, taking 4ml of 2mol/L trisodium citrate aqueous solution (the molar ratio of the trisodium citrate to the chloroauric acid is 1: 1) as a reducing agent, stirring and reacting for 3 hours, centrifuging for 20min three times at 9800r/min after the reaction is finished, and separating and carrying out vacuum drying to obtain the core-shell type gold-ferroferric sulfide particles.
Example 10
The core-shell type gold-ferroferric sulfide particles obtained in example 1 were dispersed in a DMEM medium (containing 1g/L D-glucose, 1g/L L-glutamine, and 110mg/L sodium pyruvate), and placed in a normal temperature (25 ℃) environment and a high temperature (50 ℃) environment, respectively, to examine the change in the hydrated particle size for one month. As shown in FIG. 4, the average hydrated particle size of the core-shell type gold-ferroferric sulfide nanoparticles obtained at 25 ℃ is 105.3nm, and the average hydrated particle size of the core-shell type gold-ferroferric sulfide nanoparticles obtained at 50 ℃ is 133.7 nm. The hydration particle size of the core-shell type gold-ferroferric sulfide particle dispersion liquid is not obviously changed, which shows that the core-shell type gold-ferroferric sulfide particles have good stability in DMEM culture solution and are beneficial to biological application.
Comparative example 1
Referring to the content of the ferroferric sulfide preparation part in the research on the preparation of ferroferric sulfide nano sheets and the electromagnetic wave absorption performance thereof (university of roman and harabin engineering, 2016), ferroferric sulfide particles are synthesized by a solvothermal method. As shown in FIG. 5, the ferroferric sulfide particles synthesized by the method disclosed by the literature are large, easy to agglomerate, poor in dispersibility in water and capable of keeping magnetism for only two weeks. The core-shell type gold-ferroferric sulfide particles prepared in the embodiment 1 have good dispersibility and uniform particles, and can keep the magnetism for more than 6 months.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a photomagnetic double-response core-shell type gold-ferroferric sulfide nano material is characterized by comprising the following steps:
(1) taking a solvent as a reaction medium, and carrying out hydrothermal reaction on ferric chloride, trisodium citrate and sodium acetate trihydrate to obtain ferroferric oxide nano-particles;
(2) mixing the ferroferric oxide nanoparticles with a solvent, adding a sulfur precursor, carrying out hydrothermal reaction, centrifuging, and drying to obtain ferroferric sulfide nanoparticles;
(3) dispersing ferroferric sulfide nano particles in chloroauric acid solution, adding a reducing agent, reacting for 2-3 hours, and centrifuging to obtain a photo-magnetic double-response core-shell type gold-ferroferric sulfide nano material;
the temperature of the hydrothermal reaction in the step (2) is 150-200 ℃, and the time is 4-12 hours;
the mol ratio of the ferroferric sulfide nano particles in the step (3) to the chloroauric acid in the chloroauric acid solution is 1: 1-4; and (4) the mass concentration of the chloroauric acid solution in the step (3) is 1-3%.
2. The preparation method of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material according to claim 1, wherein the mass ratio of the ferric chloride, the trisodium citrate and the sodium acetate trihydrate in the step (1) is (5.4-10.8): (1-4): (10-20); the mass ratio of the ferroferric oxide nano particles to the sulfur precursor in the step (2) is 1: (9-18); the mol ratio of the reducing agent in the step (3) to the chloroauric acid in the chloroauric acid solution is 1: 1.
3. the preparation method of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material according to claim 1, wherein the hydrothermal reaction in the step (1) is performed at 100-200 ℃ for 4-12 hours.
4. The preparation method of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material according to claim 1, 2 or 3, wherein the ratio of the ferric chloride to the solvent in the step (1) is (1.08-2.16) g/40 ml; the ratio of the ferroferric oxide nanoparticles to the solvent in the step (2) is (12.5-25 mg): (30-50) ml.
5. The preparation method of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material according to claim 3, wherein the temperature of the hydrothermal reaction in the step (1) is 150-200 ℃ and the time is 10 hours; and (3) performing hydrothermal reaction at the temperature of 160-180 ℃ for 10 hours in the step (2).
6. The method for preparing the magneto-optical double-response core-shell type gold-ferroferric sulfide nano material according to claim 5, wherein the sulfur precursor in the step (2) is at least one of sodium sulfide and thioacetamide; and (3) the reducing agent is at least one of sodium borohydride, trisodium citrate and ascorbic acid.
7. The preparation method of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material according to claim 5, wherein the reducing agent in the step (3) is added in the form of solution, and the concentration of the reducing agent is 2-4 mol/L; the reaction temperature in the step (3) is room temperature.
8. The method for preparing the magneto-optical double-response core-shell type gold-ferroferric sulfide nano material according to claim 5, wherein the solvent in the step (1) is at least one of water, ethylene glycol and ethanol;
the drying in the step (2) is vacuum drying, the temperature is 37-80 ℃, and the time is 0.5-3 hours; the solvent in the step (2) is at least one of water, glycol and ethanol; the solvent used for centrifugation is a solvent with a volume ratio of 1: 1: 0.5 of ethanol-water-ethylene glycol mixed solution, wherein the volume ratio of the ferroferric sulfide particles to the mixed solution is 1: 2;
dispersing the ferroferric sulfide nano particles in the chloroauric acid solution in an ultrasonic mode, wherein the ultrasonic time is 10-30 min, and the ultrasonic frequency is 20-40 Hz; the rotating speed of centrifugation is 9000-10000 r/min, the time is 10-30 min, and the centrifugation frequency is 1-5 times.
9. A photomagnetic double-response core-shell type gold-ferroferric sulfide nano material prepared by the method of any one of claims 1 to 8.
10. The application of the photomagnetic double-response core-shell type gold-ferroferric sulfide nano material in the preparation of medicines and photo-thermal and magneto-thermal combined action materials according to claim 9.
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