CN107029251B - Single-layer molybdenum disulfide-zinc ferrite nanocomposite and preparation method and application thereof - Google Patents
Single-layer molybdenum disulfide-zinc ferrite nanocomposite and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a single-layer molybdenum disulfide-zinc ferrite nanocomposite and a preparation method and application thereof, and particularly relates to the field of novel nanocomposites. The molybdenum disulfide nano-sheet is composed of a molybdenum disulfide nano-sheet and zinc ferrite nano-particles, wherein the zinc ferrite nano-particles are uniformly modified on the surface of the molybdenum disulfide nano-sheet, and the molybdenum disulfide nano-sheet is of a layered stripping structure. The invention utilizes the reaction of amido bond formed by amino and carboxyl to assemble zinc ferrite nano particles on the surface of the molybdenum disulfide nano sheet, the method has the advantages of low energy consumption, low cost and high yield, the obtained composite material can be simultaneously used as a magnetic resonance imaging contrast agent and a controllable drug carrier, the drug can reach and be enriched at a focus part under the guidance of a magnetic field, the intelligent drug release and the real-time curative effect evaluation under the guidance of the magnetic resonance imaging are realized, and the controllable adjustment of the magnetic resonance imaging effect and the drug loading capacity can be realized by changing the relative content of molybdenum disulfide and zinc ferrite in the composite material.
Description
Technical Field
The invention relates to the field of novel nano composite materials, in particular to a single-layer molybdenum disulfide-zinc ferrite nano composite material and a preparation method and application thereof.
Background
Magnetic resonance imaging has biological safety without radiation damage, can be applied to the technical flexibility of tomography in any direction, and has become one of the most powerful detection means in modern clinical diagnosis by covering multi-parameter characteristics such as proton density, relaxation, chemical shift and the like and the technical advantages of high spatial resolution and high contrast. The magnetic resonance imaging is mainly to realize the space positioning of hydrogen protons in human tissues through a gradient magnetic field with space position dependency, and then realize the human imaging through the acquisition and processing of hydrogen proton magnetic resonance signals and image reconstruction. The difference in signal intensity between human tissues creates an imaging contrast, and in order to highlight the differences between different tissues, particularly between normal and diseased tissues, the use of agents known as "contrast agents" in addition to the design of special pulse sequences is considered an effective method to improve magnetic resonance imaging contrast and sharpness. The zinc ferrite nano-particle has the advantages of unique superparamagnetism, low cytotoxicity, magnetic resonance signal sensitivity and the like, and shows good application prospect in the aspect of magnetic resonance imaging contrast agents.
Since the Nobel prize for physics gained by Andre Geim 2010 and Konstantin Novoselov research on graphene, graphene-like transition metal sulfide MS2(M ═ Mo, W, Nb, Ta, and the like) has attracted considerable attention because of its unique physicochemical properties. The monolayer molybdenum disulfide has a large specific surface area and remarkable electronic characteristics, and has a wide application space in the aspects of catalysts, field effect transistors and lithium ion batteries, but research reports in the biomedical field are less common. The molybdenum disulfide has a close-packed hexagonal structure similar to graphene, layers are connected through weak van der waals force, and a stable single-layer or few-layer molybdenum disulfide dispersion liquid can be prepared through a simple liquid phase stripping method, an ultrasonic-assisted stripping method or a lithium ion intercalation stripping method, so that an important foundation is laid for applying the molybdenum disulfide nanosheets to the field of biomedicine. In addition, Teo et al investigated the toxic effects of molybdenum disulfide nanoplates on human alveolar epithelial cells (A549) using the WST-8 method and the MTT method. The result shows that the cell survival rate of the A549 cells is still kept above 80% after the A549 cells are cultured for 24 hours at the maximum concentration of 400 mu g/mL of the sample, and the low cytotoxicity of the monolayer molybdenum disulfide on the A549 cells is still shown under the high sample concentration. Importantly, the molybdenum disulfide has a large specific surface area, and has a good application prospect in the aspect of efficient drug carriers due to the combination of good aqueous solution dispersibility and low cytotoxicity, which is proved by the research work of the polyethylene glycol functionalized molybdenum disulfide nanosheet applied to phototherapy and chemotherapy of tumors, which is first reported by Liuzhu topic groups in Advanced Materials journal in 2014.
Modern biomedicine requires image diagnosis and simultaneous treatment of diseases, and the zinc ferrite nanoparticles used as drug carriers need further research and development in the aspects of improving drug loading capacity, improving drug treatment effect, prolonging retention time in vivo and the like. The novel molybdenum disulfide-zinc ferrite nanocomposite material is designed and constructed, and can combine the good drug loading capacity of a single layer of molybdenum disulfide and the obvious magnetic resonance imaging effect of zinc ferrite nanoparticles. The prepared nano composite material can load high-dose anti-cancer drugs, can track the transportation and distribution of the drugs in vivo in real time and evaluate the diagnosis and treatment effects of the drugs on diseases, and has important theoretical significance and clinical value for early diagnosis and timely treatment of cancers and other major diseases.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a monolayer molybdenum disulfide-zinc ferrite nanocomposite, wherein magnetic zinc ferrite nanoparticles with the particle size of 4-15nm are uniformly modified on the surface of a monolayer molybdenum disulfide nanosheet, so that the prepared nanocomposite has good aqueous solution dispersibility, proper saturation magnetization and controllable transverse relaxation efficiency, and can be simultaneously used as a magnetic resonance imaging contrast agent and a controllable drug carrier to realize drug targeted release and real-time curative effect evaluation under the guidance of magnetic resonance imaging.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a monolayer molybdenum disulfide-zinc ferrite nanocomposite is characterized in that: the composite material is composed of molybdenum disulfide nanosheets and zinc ferrite nanoparticles, wherein the zinc ferrite nanoparticles are uniformly modified on the surfaces of the molybdenum disulfide nanosheets, and the molybdenum disulfide nanosheets are of layered stripping structures.
The further technology is that the diameter of the zinc ferrite nano particle is 4-15nm, the zinc ferrite nano particle is spherical or hexahedral, the thickness of the molybdenum disulfide nano sheet is 0.3-50nm, the size of the molybdenum disulfide nano sheet is 0.5-5 mu m, and the mass percentage of the molybdenum disulfide nano sheet is 0.5-90%.
A further technique is that the monolayer molybdenum disulfide-zinc ferrite nanocomposite has low cytotoxicity in a wide concentration range.
The technology further comprises the following steps:
(1) preparation of aminated molybdenum disulfide
Adding molybdenum disulfide powder into deionized water, and carrying out ultrasonic oscillation for 0.5-12 h; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet; dispersing the vacuum-dried molybdenum disulfide nanosheets in deionized water, adding an amino modifier which is metered in proportion to the molybdenum disulfide nanosheets, mechanically stirring or ultrasonically oscillating for 1-4h, then centrifugally separating, washing the reaction product with absolute ethyl alcohol for three times, and drying in a vacuum drying oven for 24h to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
Dissolving a trivalent ferric salt and a divalent zinc salt which are metered in proportion into deionized water, uniformly stirring by using a nitrogen bubbling method, heating to 60 ℃, gradually dropwise adding an alkaline regulator to enable the pH value of a reaction system to be 10-14, heating to 90 ℃ after reacting for 0.5-2h, continuously reacting for 1-4h, respectively washing reaction products for three times by using the deionized water and ethanol, placing the reaction products in a vacuum drying box for drying for 24h to obtain zinc ferrite nano particles, dispersing the vacuum-dried zinc ferrite nano particles in the deionized water, then adding a carboxyl modifier which is metered in proportion to the zinc ferrite nano particles, mechanically stirring or ultrasonically oscillating for 1-4h, washing the reaction products for three times by using absolute ethyl alcohol, and placing in the vacuum drying box for drying for 24h to obtain carboxylated zinc ferrite nano particles;
(3) preparation of monolayer molybdenum disulfide-zinc ferrite nanocomposite
Dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nano particles which are measured in proportion into an ethanol/water mixed solvent, adding a catalyst which is measured in proportion with molybdenum disulfide nano sheets, then mechanically stirring or ultrasonically oscillating for 2-12h, washing the reaction product with absolute ethanol for three times, and drying in vacuum for 24h to obtain the monolayer molybdenum disulfide-zinc ferrite nano composite material.
The further technology is that the amino modifier used in the step (1) is one of gamma-aminopropyltriethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, L-cysteine, polymethacrylamide, polyethyleneimine or polyasparagine, wherein the mass ratio of the molybdenum disulfide nanosheet to the amino modifier is 1-20: 1.
The further technology is that the ferric iron salt used in the step (2) is one of nitrate, chloride, sulfate, oxalate, acetate, nitrate hydrate, chloride hydrate, sulfate hydrate, oxalate hydrate and acetate hydrate of iron, the divalent zinc salt used is one of nitrate, chloride, sulfate, oxalate, acetate, nitrate hydrate, chloride hydrate, sulfate hydrate, oxalate hydrate and acetate hydrate of zinc, and the molar ratio of the ferric iron salt to the divalent zinc salt is 1:0.5-1.9
The further technique is that the alkaline regulator used in the step (2) is one of ammonia water, ethanolamine aqueous solution, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
The further technology is that the carboxyl modifier used in the step (2) is one of polyacrylic acid, dimercaptosuccinic acid, carboxymethyl cellulose, carboxymethyl chitin, carboxymethyl chitosan, sodium alginate and syringic acid, wherein the mass ratio of the zinc ferrite nanoparticles to the carboxyl modifier is 1-20: 1.
The further technology is that the catalyst used in the step (3) is one of N, N' -dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/4-dimethylaminopyridine, wherein the mass ratio of the molybdenum disulfide nanosheets to the catalyst is 1-10: 1.
The further technology is that the single-layer molybdenum disulfide-zinc ferrite nanocomposite can be used as a magnetic resonance imaging contrast agent and a controllable drug carrier at the same time, intelligent drug release and real-time curative effect evaluation under the guidance of magnetic resonance imaging can be realized, and a drug delivery system based on the nanocomposite can reach and be enriched at a focus part under the guidance of a magnetic field, so that the drug concentration of a lesion part is improved, and the diagnosis and treatment effect is improved.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the invention has the advantages of low energy consumption, low cost and high yield; respectively carrying out surface functionalization modification on molybdenum disulfide and zinc ferrite by utilizing an amino modifier and a carboxyl modifier, and controllably assembling zinc ferrite nano particles on the surfaces of molybdenum disulfide nano sheets through the reaction of amide bonds formed by amino groups and carboxyl groups, wherein the molybdenum disulfide nano sheets are in a single-layer stripping structure in a composite system and are free from serious stacking and laminating phenomena; the nano composite material can be used as a magnetic resonance imaging contrast agent and a controllable drug carrier at the same time, so that intelligent drug release and real-time curative effect evaluation under the guidance of magnetic resonance imaging are realized, and the controllable adjustment of the magnetic resonance imaging effect and the drug loading capacity can be realized by changing the relative contents of molybdenum disulfide and zinc ferrite in the composite material; meanwhile, a drug delivery system based on the nano composite material can reach and be enriched at a focus part under the guidance of a magnetic field, so that the aims of improving the drug concentration of a pathological change part and improving the diagnosis and treatment effect are fulfilled.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a transmission electron microscope image of a composite material according to a first embodiment of the present invention;
FIG. 2 is an X-ray diffraction pattern of a composite material according to a first embodiment of the present invention;
FIG. 3 is a hysteresis loop at room temperature of a composite material according to a first embodiment of the present invention;
FIG. 4-a is the drug loading of the composite material in accordance with one embodiment of the present invention;
FIG. 4-b is a graph showing the drug release profile of the composite material according to the first embodiment of the present invention;
FIG. 5 is a graph of MRI images and T2 relaxation rate versus Fe ion concentration for a composite material according to an embodiment of the present invention;
FIG. 6 is a graph of MTT cytotoxicity data for composites according to the first embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
(1) Preparation of aminated molybdenum disulfide
Adding 10g of commercial molybdenum disulfide powder and 750mL of deionized water into a 1000mL three-neck flask, placing the flask in a low-power ultrasonic tank, and ultrasonically oscillating for 6 hours; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet; 0.25g of vacuum-dried molybdenum disulfide nanosheet is taken and redispersed in 200mL of deionized water, 0.25g of gamma-aminopropyltriethoxysilane is added, centrifugal separation is carried out after 2 hours of ultrasonic oscillation, absolute ethyl alcohol is washed for three times, and the mixture is placed in a vacuum drying oven for drying for 24 hours to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
In a 1000mL three-necked flask, 12.12g Fe (NO) is added3)3·9H2O and 4.46gZn (NO)3)2·6H2Dissolving O in 750mL of deionized water, bubbling with nitrogen for 30min, uniformly stirring, heating to 60 ℃, gradually dropwise adding 150mL2.5M sodium hydroxide solution to enable the pH value of a reaction system to be 12, heating to 90 ℃ after reacting for 1h, continuing to react for 2h, separating a black suspension by a magnet after the reaction is finished, respectively washing the product with deionized water and ethanol for three times, and drying in a vacuum drying oven for 24h to obtain zinc ferrite nanoparticles; dispersing 0.25g of vacuum-dried zinc ferrite nanoparticles in 100mL of deionized water, adding 0.25g of polyacrylic acid, ultrasonically oscillating for 2h, separating with magnet, washing with absolute ethanol for three times, and vacuum-drying in a vacuum drying ovenDrying for 24h to obtain carboxylated zinc ferrite nanoparticles;
(3) preparation of molybdenum disulfide-zinc ferrite nano composite material
And dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nanoparticles obtained in the steps into 200mL of ethanol/water mixed solvent, adding 0.5g of N, N' -dicyclohexylcarbodiimide, mechanically stirring for 6h, carrying out magnet separation, washing with absolute ethanol for three times, and carrying out vacuum drying for 24h to obtain the molybdenum disulfide-zinc ferrite nanocomposite. Wherein the mass percentage of the molybdenum disulfide in the composite material is 50%.
Example 2
(1) Preparation of aminated molybdenum disulfide
Adding 5.0g of commercial molybdenum disulfide powder and 750mL of deionized water into a 1000mL three-neck flask, placing the flask in a low-power ultrasonic tank, and ultrasonically oscillating for 6 hours; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet; 0.25g of vacuum-dried molybdenum disulfide nanosheet is taken and redispersed in 200mL of deionized water, 0.25g of gamma-aminopropyltriethoxysilane is added, centrifugal separation is carried out after 2 hours of ultrasonic oscillation, absolute ethyl alcohol is washed for three times, and the mixture is placed in a vacuum drying oven for drying for 24 hours to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
In a 1000mL three-necked flask, 12.12g Fe (NO) is added3)3·9H2O and 4.46gZn (NO)3)2·6H2Dissolving O in 750mL of deionized water, bubbling with nitrogen for 30min, uniformly stirring, heating to 60 ℃, gradually dropwise adding 150mL2.5M sodium hydroxide solution to enable the pH value of a reaction system to be 12, heating to 90 ℃ after reacting for 1h, continuing to react for 2h, separating a black suspension by a magnet after the reaction is finished, respectively washing the product with deionized water and ethanol for three times, and drying in a vacuum drying oven for 24h to obtain zinc ferrite nanoparticles; dispersing 0.5g of vacuum-dried zinc ferrite nanoparticles into 1000mL of deionized water, adding 0.5g of polyacrylic acid, ultrasonically oscillating for 2h, then carrying out magnetic separation, washing with absolute ethyl alcohol for three times, placing in a vacuum drying oven, and drying for 24h to obtain the carboxylated zinc ferrite nanoparticlesZinc ferrite nanoparticles;
(3) preparation of molybdenum disulfide-zinc ferrite nano composite material
And dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nanoparticles obtained in the steps into 300mL of ethanol/water mixed solvent, adding 0.75g of N, N' -dicyclohexylcarbodiimide, mechanically stirring for 4h, carrying out magnet separation, washing with absolute ethanol for three times, and carrying out vacuum drying for 24h to obtain the molybdenum disulfide-zinc ferrite nanocomposite. Wherein the mass fraction of the molybdenum disulfide in the composite material is 33.3 percent.
Example 3
(1) Preparation of aminated molybdenum disulfide
Adding 5g of commercial molybdenum disulfide powder and 750mL of deionized water into a 1000mL three-neck flask, placing the flask in a low-power ultrasonic tank, and ultrasonically oscillating for 6 hours; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet; 0.25g of vacuum-dried molybdenum disulfide nanosheet is taken and redispersed in 200mL of deionized water, 0.25g of gamma-aminopropyltriethoxysilane is added, centrifugal separation is carried out after 2 hours of ultrasonic oscillation, absolute ethyl alcohol is washed for three times, and the mixture is placed in a vacuum drying oven for drying for 24 hours to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
In a 1000mL three-necked flask, 12.12g Fe (NO) is added3)3·9H2O and 4.46gZn (NO)3)2·6H2Dissolving O in 750mL of deionized water, bubbling with nitrogen for 30min, uniformly stirring, heating to 60 ℃, gradually dropwise adding 150mL2.5M sodium hydroxide solution to enable the pH value of a reaction system to be 12, heating to 90 ℃ after reacting for 1h, continuing to react for 2h, separating a black suspension by a magnet after the reaction is finished, respectively washing the product with deionized water and ethanol for three times, and drying in a vacuum drying oven for 24h to obtain zinc ferrite nanoparticles; dispersing 2.25g of vacuum-dried zinc ferrite nanoparticles into 450mL of deionized water, adding 2.25g of polyacrylic acid, ultrasonically oscillating for 2h, then carrying out magnetic separation, washing with absolute ethyl alcohol for three times, and drying in a vacuum drying oven for 24h to obtain carboxylated zinc ferrite nanoparticles;
(3) preparation of molybdenum disulfide-zinc ferrite nano composite material
And dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nanoparticles obtained in the steps into 400mL of ethanol/water mixed solvent, adding 0.5g of N, N' -dicyclohexylcarbodiimide, mechanically stirring for 6h, carrying out magnet separation, washing with absolute ethanol for three times, and carrying out vacuum drying for 24h to obtain the molybdenum disulfide-zinc ferrite nanocomposite. Wherein the mass fraction of the molybdenum disulfide in the composite material is 10 percent.
Example 4
(1) Preparation of aminated molybdenum disulfide
Adding 5g of commercial molybdenum disulfide powder and 750mL of deionized water into a 1000mL three-neck flask, placing the flask in a low-power ultrasonic tank, and ultrasonically oscillating for 6 hours; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet; dispersing 0.25g of vacuum-dried molybdenum disulfide nanosheet in 200mL of deionized water, adding 0.25g of gamma-aminopropyltriethoxysilane, mechanically stirring for 2h, then centrifugally separating, washing with absolute ethanol for three times, and drying in a vacuum drying oven for 24h to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
In a 1000mL three-necked flask, 12.12g Fe (NO) is added3)3·9H2O and 4.46gZn (NO)3)2·6H2Dissolving O in 750mL of deionized water, bubbling with nitrogen for 30min, uniformly stirring, heating to 60 ℃, gradually dropwise adding 150mL2.5M sodium hydroxide solution to enable the pH value of a reaction system to be 12, heating to 90 ℃ after reacting for 1h, continuing to react for 2h, separating a black suspension by a magnet after the reaction is finished, respectively washing the product with deionized water and ethanol for three times, and drying in a vacuum drying oven for 24h to obtain zinc ferrite nanoparticles; dispersing 5g of vacuum-dried zinc ferrite nanoparticles into 1000mL of deionized water, adding 5.25g of polyacrylic acid, ultrasonically oscillating for 2h, then carrying out magnetic separation, washing with absolute ethyl alcohol for three times, and placing in a vacuum drying oven for drying for 24h to obtain carboxylated zinc ferrite nanoparticles;
(3) preparation of molybdenum disulfide-zinc ferrite nano composite material
And dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nanoparticles obtained in the steps into 500mL of ethanol/water mixed solvent, adding 5.25g of N, N' -dicyclohexylcarbodiimide, mechanically stirring for 6h, carrying out magnet separation, washing with absolute ethanol for three times, and carrying out vacuum drying for 24h to obtain the molybdenum disulfide-zinc ferrite nanocomposite. Wherein the mass fraction of the molybdenum disulfide in the composite material is 4.76%.
The performance characterization of the molybdenum disulfide-zinc ferrite nanocomposite material is as follows:
FIG. 1 is a transmission electron micrograph of a single layer of a molybdenum disulfide-zinc ferrite nanocomposite material in example 1. As can be seen from the figure, the nearly transparent molybdenum disulfide nanosheets were completely exfoliated and no free-stacking and stacking phenomena occurred. The average size of the zinc ferrite nano particles is 4-15nm, the zinc ferrite nano particles are uniformly modified on the surface of the molybdenum disulfide nano sheet, and no serious agglomeration and free falling particles are seen.
FIG. 2 is an X-ray diffraction pattern of a single layer of the molybdenum disulfide-zinc ferrite nanocomposite material of example 1. It can be observed from the figure that strong characteristic diffraction peaks appear at 2 θ of 30.1 °, 35.0 °, 42.6 °, 53.9 °, 56.8 ° and 62.7 °, corresponding to the (220), (311), (400), (422), (511) and (440) crystal planes in the zinc ferrite standard data (jcpdsnos. 22-1012), respectively. In addition, the molybdenum disulfide-zinc ferrite nanocomposite basically shows a characteristic diffraction peak of zinc ferrite, but no diffraction peak of molybdenum disulfide is observed, which is mainly because in the chemical self-assembly process, the ordered stacking of molybdenum disulfide nanosheets is destroyed by the attachment and growth of zinc ferrite nanoparticles on the surface of the molybdenum disulfide nanosheets, so that the molybdenum disulfide nanosheets are in a disordered stripping state in the composite system.
FIG. 3 is a room temperature hysteresis curve of a single layer of molybdenum disulfide-zinc ferrite nanocomposite in example 1. As can be seen from the figure, no obvious hysteresis loop appears on the magnetization curve of the prepared nanocomposite, and the remanence and the coercive force are basically zero, which shows that the molybdenum disulfide-zinc ferrite nanocomposite has superparamagnetism at room temperature, and the saturation magnetization is 38.9 emu/g.
FIGS. 4-a and 4-b are graphs showing drug loading and drug release of a single layer of the molybdenum disulfide-zinc ferrite nanocomposite in example 1. As can be seen from the figure, the drug loading of the prepared nanocomposite material has concentration dependence, and the saturated drug loading reaches 1.18 mg/mg. In addition, the prepared nano composite material has two stages of burst release and slow release in drug release behavior and has typical pH sensitivity, which indicates that the prepared molybdenum disulfide-zinc ferrite nano composite material is a good intelligent drug carrier.
Fig. 5 is a magnetic resonance image of a single layer of the molybdenum disulfide-zinc ferrite nanocomposite material in embodiment 1 and a graph of the corresponding relaxation rate and the iron ion concentration. As can be seen from the figure, the magnetic resonance imaging effect of the prepared nanocomposite material is related to the concentration of iron ions, and the magnetic resonance imaging capability of the sample gradually becomes stronger with the gradually increasing concentration of iron ions in the solution. Transverse relaxation rate r of sample269.36FemM is achieved-1s-1The prepared nano composite material is proved to be good T2A contrast agent.
FIG. 6 is a cytotoxicity chart of a single-layer molybdenum disulfide-zinc ferrite nanocomposite material in example 1. As can be seen from the figure, after the MG-63 cells are incubated in the sample dispersion liquid with the maximum concentration of 150 mug/mL for 24 hours, the cell survival rate is still over 80 percent, and the prepared composite material is proved to have smaller cytotoxicity and good biocompatibility, so that a theoretical reference is provided for further clinical application.
Claims (7)
1. A preparation method of a monolayer molybdenum disulfide-zinc ferrite nanocomposite is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of aminated molybdenum disulfide
Adding molybdenum disulfide powder into deionized water, and carrying out ultrasonic oscillation for 0.5-12 h; washing the reaction product with deionized water for three times, centrifugally collecting, and then placing in a vacuum drying oven for drying for 24 hours to obtain a molybdenum disulfide nanosheet;
dispersing the vacuum-dried molybdenum disulfide nanosheets in deionized water, adding an amino modifier which is metered in proportion to the molybdenum disulfide nanosheets, mechanically stirring or ultrasonically oscillating for 1-4h, then centrifugally separating, washing the reaction product with absolute ethyl alcohol for three times, and drying in a vacuum drying oven for 24h to obtain aminated molybdenum disulfide;
(2) preparation of carboxylated zinc ferrite nanoparticles
Dissolving trivalent ferric salt and divalent zinc salt which are measured in proportion into deionized water, uniformly stirring the mixture by using a nitrogen bubbling method, heating the mixture to 60 ℃, gradually dropwise adding an alkaline regulator to enable the pH value of a reaction system to be 10-14, heating the mixture to 90 ℃ after reacting for 0.5-2h, continuously reacting for 1-4h, respectively washing the reaction product for three times by using the deionized water and ethanol, and drying the reaction product in a vacuum drying box for 24h to obtain zinc ferrite nano particles; dispersing vacuum-dried zinc ferrite nanoparticles into deionized water, adding a carboxyl modifier which is metered in proportion to the zinc ferrite nanoparticles, mechanically stirring or ultrasonically oscillating for 1-4h, washing a reaction product with absolute ethyl alcohol for three times, and drying in a vacuum drying oven for 24h to obtain carboxylated zinc ferrite nanoparticles;
(3) preparation of monolayer molybdenum disulfide-zinc ferrite nanocomposite
Dispersing the aminated molybdenum disulfide and carboxylated zinc ferrite nano particles which are measured in proportion into an ethanol/water mixed solvent, adding a catalyst which is measured in proportion with molybdenum disulfide nano sheets, then mechanically stirring or ultrasonically oscillating for 2-12h, washing the reaction product with absolute ethanol for three times, and drying in vacuum for 24h to obtain the monolayer molybdenum disulfide-zinc ferrite nano composite material.
2. The method for preparing a monolayer molybdenum disulfide-zinc ferrite nanocomposite material according to claim 1, wherein the method comprises the following steps: the amino modifier used in the step (1) is one of gamma-aminopropyltriethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, L-cysteine, polymethacrylamide, polyethyleneimine or polyasparagine, wherein the mass ratio of the molybdenum disulfide nanosheet to the amino modifier is 1-20: 1.
3. The method for preparing a monolayer molybdenum disulfide-zinc ferrite nanocomposite material according to claim 1, wherein the method comprises the following steps: the ferric salt used in the step (2) is one of nitrate, chloride, sulfate, oxalate, acetate, nitrate hydrate, chloride hydrate, sulfate hydrate, oxalate hydrate and acetate hydrate of iron, and the used divalent zinc salt is one of nitrate, chloride, sulfate, oxalate, acetate, nitrate hydrate, chloride hydrate, sulfate hydrate, oxalate hydrate and acetate hydrate of zinc, wherein the molar ratio of the ferric salt to the divalent zinc salt is 1: 0.5-1.9.
4. The method for preparing a monolayer molybdenum disulfide-zinc ferrite nanocomposite material according to claim 1, wherein the method comprises the following steps: the alkaline regulator used in the step (2) is one of ammonia water, ethanolamine aqueous solution, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
5. The method for preparing a monolayer molybdenum disulfide-zinc ferrite nanocomposite material according to claim 1, wherein the method comprises the following steps: the carboxyl modifier used in the step (2) is one of polyacrylic acid, dimercaptosuccinic acid, carboxymethyl cellulose, carboxymethyl chitin, carboxymethyl chitosan, sodium alginate and syringic acid, wherein the mass ratio of the zinc ferrite nano particles to the carboxyl modifier is 1-20: 1.
6. The method for preparing a monolayer molybdenum disulfide-zinc ferrite nanocomposite material according to claim 1, wherein the method comprises the following steps: the catalyst used in the step (3) is one of N, N' -dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/4-dimethylaminopyridine, wherein the mass ratio of the molybdenum disulfide nanosheet to the catalyst is 1-10: 1.
7. The use of a monolayer molybdenum disulfide-zinc ferrite nanocomposite prepared according to the method of claim 1, wherein: the monolayer molybdenum disulfide-zinc ferrite nanocomposite is applied to preparation of magnetic resonance imaging contrast agents and controllable drug carriers.
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