CN109464665A - A kind of degradable hybrid two-dimensional slice molybdenum carbide nanocomposite and its preparation method and application - Google Patents
A kind of degradable hybrid two-dimensional slice molybdenum carbide nanocomposite and its preparation method and application Download PDFInfo
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
- A61K47/6953—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit the form being a fibre, a textile, a slab or a sheet
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Abstract
The present invention relates to a kind of degradable hybrid two-dimensional slice molybdenum carbide nanocomposites and its preparation method and application, the composite material includes the polymer of two-dimensional slice molybdenum carbide and modification on two-dimensional slice molybdenum carbide surface, and the polymer is hydrophilic organic polymers.
Description
Technical field
The present invention relates to a kind of hybrid two-dimensional slice molybdenum carbide nanocomposite and preparation method thereof and answer
With belonging to nano material and biomedical applications field.
Background technique
In recent years, photo-thermal therapy (Photothermal therapy, PTT) is as a kind of novel cancer therapies because of it
With high security, the features such as toxic side effect is small, precision is high and curative effect is obvious, by favor.The key of PTT is to prepare height
Effect, stable and safety light thermit powder.With the fast development of material science, two-dimension nano materials are with high specific surface area and greatly
The active site of amount then causes the broad interest of researcher.Wherein there is the transition metal carbide of typical layered structure,
Such as molybdenum carbide, it is led because having the near infrared absorption of Qiang Erkuan and good biocompatibility, thus in the photo-thermal therapy of tumour
Great potential in domain.The method of traditional synthesis molybdenum carbide is complex, and the molybdenum carbide typically resulted in is graininess and size mistake
Greatly.It is even more very few known about the report of the molybdenum carbide of synthesis two-dimensional slice structure.Prior synthesizing method is not only related to
Template step is complicated, and the use of mixed atmosphere also has certain risk in synthesis process.So far, no template participates in
The report for synthesizing two-dimensional slice structure molybdenum carbide is very few.
It compares with one area (NIR-I, 750-1000nm) of near-infrared biology window, two area (NIR- of near-infrared biology window
II, 1000-1350nm) light emitting wavelength it is longer, skin can bear light exposure energy the upper limit improve while, can obviously drop
The light scattering or the influence of autofluorescence effect that low light is caused when penetrating biological tissue, make penetration depth deeper, space point
Resolution also significantly improves, and more and more researchers put into the exploitation of the area NIR-II light thermit powder.It there are no so far
It is reported about what organic inorganic hybridization two-dimensional slice molybdenum carbide was used as the open of thermit powder.
Summary of the invention
It is an object of the invention to design a kind of novel hybrid two-dimensional slice molybdenum carbide nanocomposite,
And it is expanded in the photo-thermal potential in the area NIR-II, while crossing over the area NIR-I and the area NIR-II, realize that efficiently highly selective kill is swollen
Oncocyte.
Herein, on the one hand, the present invention provides a kind of degradable nano combined material of hybrid two-dimensional slice molybdenum carbide
Material, the composite material includes the polymer of two-dimensional slice molybdenum carbide and modification on two-dimensional slice molybdenum carbide surface, described
Polymer is hydrophilic organic polymers.
Degradable hybrid two-dimensional slice molybdenum carbide nanocomposite of the invention is surface modification hydrophily
The two-dimensional slice molybdenum carbide nanocomposite of organic polymer, the composite material is with good biocompatibility and efficiently
Photothermal conversion, wherein the photothermal conversion performance in the area NIR-I is 19~22%, the photothermal conversion performance in the area NIR-II is
38~43%, it can be used for the diagnosis and efficiently treatment of human body or other mammal tumors or cancer.
The polymer can be polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, bovine serum albumin(BSA), tire ox blood
Clearly, at least one of gelatin, chitosan, hyaluronic acid, mosanom.
Content of the polymer in the composite material can be 10~80wt.%.
The composite material is in two-dimensional slice stratiform, and lateral dimension can be 50~500nm, and thickness can be 0.5~3nm.
Wherein " lateral dimension " refers to and the size in thickness direction generally perpendicular direction.
Preferably, the hydrodynamic radius of the composite material in deionized water is 50~500nm, the composite material
Hydrodynamic radius in physiological saline is 50~500nm.Degradable hybrid two-dimensional slice molybdenum carbide as a result,
Nanocomposite has good stability in physiological environment in vitro.
The present invention also provides a kind of systems of above-mentioned degradable hybrid two-dimensional slice molybdenum carbide nanocomposite
Preparation Method, comprising:
Fire molybdenum gallium carbon；
The gallium in the molybdenum gallium carbon is removed, multilayer molybdenum carbide presoma is obtained；
The multilayer molybdenum carbide presoma is mixed with fluorine-containing acid etching liquid, keeps the temperature 48~650 hours in 30~50 DEG C, preparation
Multilayer molybdenum carbide；
It removes the multilayer molybdenum carbide to obtain two-dimensional slice molybdenum carbide through sonic oscillation；And
By hydrophilic organic polymers and the two-dimensional slice molybdenum carbide according to molar ratio (1~10): 1 mixing, in vacuum condition
Under, it flows back in 40~70 DEG C, prepares degradable hybrid two-dimensional slice molybdenum carbide nanocomposite.
Firing molybdenum gallium carbon may include: by molybdenum powder, gallium, carbon dust according to mass ratio (10~20): (10~60): 1
Ratio mixes, and fires under inert atmosphere in 750~950 DEG C.Inert atmosphere can be high purity inert gas atmosphere, such as purity is
99.99% or more nitrogen, argon gas.
In the molybdenum gallium carbon, molybdenum, gallium, carbon mass ratio can be (10~20): (8~15): 1.
The gallium in the molybdenum gallium carbon can be removed by acid solution A, hydrionic concentration can be in the acid solution A
For 9~13mol/L, preferably 10~12mol/L.It is also possible to the pH of the acid solution A less than 0.8.
The fluorine-containing acid etching liquid by by lithium fluoride and acid solution B according to (0.8~2.0) g:(15~40) mL
Ratio is obtained by mixing, and hydrionic concentration is 9~13mol/L, preferably 10~12mol/L in the acid solution B.It can also be with
It is that the pH value of the acid solution B is less than 0.8.
Acid solution A and/or acid solution B can be hydrochloric acid solution and hydrofluoric acid etc., and concentration can be 9~13mol/L,
It is preferred that 10~12mol/L.
Can also be washed to multilayer molybdenum carbide to pH is 6.0~7.0.
Sonic oscillation removing may include: by the multilayer molybdenum carbide in deionized deoxygenated water through ultrasound 10~
It 120 minutes, under the conditions of 3000~5000 revs/min, is centrifuged 20~50 minutes, collects supernatant, be not necessarily to drying, deoxygenation is protected
It deposits.
The two-dimensional slice molybdenum carbide is single layer molybdenum carbide, and the lateral dimension of the single layer molybdenum carbide can be 30~200
Nm, thickness can be 0.5~3nm.
The present invention also provides a kind of above-mentioned degradable hybrid two-dimensional slice molybdenum carbide nanocomposites to make
Application in standby light thermit powder.
Above-mentioned degradable hybrid two-dimensional slice molybdenum carbide nanocomposite can be used as light thermit powder use.One
Aspect by preparation process systematically in adjustment and control system molybdenum and carbon ratio, the two-dimensional slice molybdenum carbide prepared because
Its surface plasma resonance effect has higher light absorption hot, therefore can be used as efficient light thermit powder in the area NIR-I and NIR-II
The area NIR-I and NIR-II can be crossed over simultaneously；On the other hand by the surface modification of polymer, increase the stability and biology of system
The introducing of safety, biocompatible hydrophilic polymer can assign molybdenum carbide nanocomposite biological safety and stability.
So far, this field, which is not yet developed to synchronize based on two-dimensional slice molybdenum carbide, realizes what the area NIR-I and NIR-II photo-thermal turned
Efficient light thermit powder, and the present invention has filled up this blank.In addition, preparation method of the invention has apparatus simple, operation
Easy advantage, facilitates industrialized production.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of the carbon molybdenum gallium in embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photo of the carbon molybdenum gallium in embodiment 1；
Fig. 3 is scanning electron microscope (SEM) photo of the multilayer two-dimension molybdenum carbide nanometer sheet in embodiment 1；
Fig. 4 is transmission electron microscope (TEM) photo of the single layer two-dimensional slice molybdenum carbide nanometer sheet in embodiment 1；
Fig. 5 shows the nano combined light thermit powder of organic/inorganic two-dimensional slice molybdenum carbide in embodiment 1 in water, physiological saline and thin
Partial size in born of the same parents' culture solution；
In Fig. 6 (a) and Fig. 6 (b), it is multiple that Fig. 6 (a) shows various concentration organic/inorganic two-dimensional slice molybdenum carbide nanometer in embodiment 2
Light combination thermit powder is 1.0W/cm in power2The area NIR I (808nm) laser emission under fluid temperature with irradiation time variation diagram；
It is 1.0W/ that Fig. 6 (b), which shows in embodiment 2 the nano combined light thermit powder of various concentration organic/inorganic two-dimensional slice molybdenum carbide in power,
cm2The area NIR-II (1064nm) laser emission under fluid temperature with irradiation time variation diagram；
It is 1.0W/cm that Fig. 7 (a), which is shown in embodiment 2 in the area NIR I (808nm) and the area NIR-II (1064nm) power density,2
Under near-infrared laser irradiation, Balb/C tumor bearing nude mice is through 150 μ L physiological saline of tail vein injection or is mixed with organic/inorganic two dimension
Thermal imaging photo in the case of the physiological saline of the nano combined light thermit powder of lamella molybdenum carbide；
Fig. 7 (b) show mice with tumor in embodiment 2 injecting normal saline or be mixed with polyvinyl alcohol modification molybdenum carbide nanometer it is multiple
It is 1.0W/ in the area NIR-I (808nm) and the area NIR-II (1064nm) power density after the normal saline dispersion of light combination thermit powder
cm2Under near-infrared laser irradiation, the temperature variations of tumor region；
The gross tumor volume that Fig. 8 shows the nude mice after different treatments in embodiment 3 change with time relationship (in figure " control
Group ", " 808nm ", " 1064nm ", " molybdenum carbide ", " molybdenum carbide+808nm ", " molybdenum carbide+1064nm " respectively indicate only injection life
Reason salt water laser do not irradiate, uses after injecting normal saline using the area NIR-I (808nm) laser irradiation, after injecting normal saline
The physiological saline dispersion of the area NIR-I (1064nm) laser irradiation, the nano combined light thermit powder of molybdenum carbide of injection polyvinyl alcohol modification
The physiology of the area NIR-I (808nm) laser irradiation and the nano combined light thermit powder of molybdenum carbide for injecting polyvinyl alcohol modification is used after liquid
The area NIR-I (808nm) laser irradiation is used after saline aqueous dispersions)；
Fig. 9 (a)-Fig. 9 (c), which is respectively shown, disperses different pH value for the nano combined light thermit powder of molybdenum carbide of polyvinyl alcohol modification
Organic/inorganic two-dimensional slice molybdenum carbide nano combined light thermit powder when in the normal saline solution of (pH value=3.0,7.0,11.0)
External degradation curve (embodiment 4)；It is nano combined that Fig. 9 (d)-Fig. 9 (f) is respectively the molybdenum carbide for showing and modifying polyvinyl alcohol
Light thermit powder is scattered in the normal saline solution of different pH value to be had after immersion different time (soaking time=0,12,48 hours)
The photo (embodiment 4) of machine/inorganic two-dimensional slice molybdenum carbide nano combined light thermit powder external degradation situation.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention relates to a kind of degradable hybrid two-dimensional slice molybdenum carbide nanocomposite and its preparation sides
Method and application, relate more specifically to the preparation and surface modification of two-dimensional slice molybdenum carbide, which has good
Biocompatibility and efficient photothermal conversion can be used for the diagnosis and efficiently of human body or other mammal tumors or cancer
Treatment.The composite material is to select the polymer of good biocompatibility to carry out surface as matrix by two-dimensional slice molybdenum carbide
After modification, the composite nano plate having a size of 50~500nm is obtained.The preparation method of the nanocomposite includes: to burn out molybdenum
Gallium carbon (carbon molybdenum gallium)；Extra gallium and gallium intercalation are removed, multilayer molybdenum carbide is prepared；Monolayer carbon is prepared by washing, removing
Change molybdenum；And it is modified by the hydrophilic organic polymers of good biocompatibility.The tool of nanocomposite prepared by the present invention
Have the advantages that photothermal conversion effect is good, tumor locus degree of enrichment is high, biological safety is good and oncotherapy significant effect, can use
In the photo-thermal therapy of the tumour or cancer of people or other mammals, have to Development of Novel tumor thermotherapy material particularly significant
Meaning.
Hereinafter, schematically illustrating degradable hybrid two-dimensional slice molybdenum carbide nanocomposite of the invention
Preparation method.
Firstly, burning out molybdenum gallium carbon (carbon molybdenum gallium).The preparation process of molybdenum gallium carbon may include: respectively by molybdenum powder, metal
Gallium, carbon dust mix according to a certain percentage, in 750~950 DEG C of heat preservation a period of times under inert atmosphere.Molybdenum powder, gallium, carbon dust
Mass ratio can be (10~20): (10~60): 1, preferably (10~20): (10~20): 1.The matter of molybdenum powder, gallium, carbon dust
Amount is than being (10~20): (10~60): when 1, wherein gallium is excessive, it can be ensured that the success of gallium intercalation.Select molybdenum powder, gallium, carbon
Powder is that raw material has many advantages, such as that cheap and raw material easily obtains, and wherein the purity of molybdenum powder and gallium can be 99% or more.It can be with
750~950 DEG C are heated to the heating rate of 5~15 DEG C/min.Soaking time can be 50~400 h, preferably 72~120h.
Inert atmosphere can be nitrogen, the argon gas of high purity inert gas atmosphere, such as purity for 99.99% or more.
In molybdenum gallium carbon (carbon molybdenum gallium) preparation process, by regulation, make molybdenum in final product molybdenum gallium carbon (carbon molybdenum gallium), gallium,
The mass ratio of carbon can be (10~20): (8~15): 1.
Then, the gallium in molybdenum gallium carbon is removed, that is, removes extra gallium and gallium intercalation, obtains multilayer molybdenum carbide presoma and (go
Except the carbon molybdenum gallium of extra gallium).The gallium in molybdenum gallium carbon can be removed by acid solution A, such as will be immersed in acidity in molybdenum gallium carbon
In solution A, gallium is removed.The pH of acid solution A can be < 0.8.Acid solution A can be using hydrochloric acid solution, hydrofluoric acid etc..
Hydrionic concentration can be 9~13mol/L, preferably 10~12mol/L in the acid solution A.Molybdenum gallium carbon and acid solution A
Ratio can be (0.5~2) g:(10~30) mL.Soaking time can be 24~72h.It is also possible to the dense of acid solution A
Degree is 9~13mol/L, preferably 10~12mol/L.
Then, the carbon molybdenum gallium for having removed extra gallium is mixed with acid etching liquid, 48~650 is kept in 30~50 DEG C
H keeps 96~240h in preferably 35~45 DEG C, prepares multilayer molybdenum carbide (i.e. multilayer two-dimension molybdenum carbide nanometer sheet).Acidity etching
Liquid can by by lithium fluoride and acid solution B according to (0.8~2.0) g:(15~40) ratio of mL is obtained by mixing.It is acid molten
The hydrogen ion concentration of liquid B can be 9~13mol/L, preferably 10~12mol/L.The pH of acid solution B can be < 0.8.Acid
Property solution B can be using hydrochloric acid solution, hydrofluoric acid etc..The size of multilayer two-dimension molybdenum carbide nanometer sheet can be 30~2000nm.
The concentration for being also possible to acid solution B is 9~13mol/L, preferably 10~12mol/L.
Can be washed to multilayer two-dimension molybdenum carbide nanometer sheet to pH is 6.0~7.0, is deposited to remove in stripping process
Acid and salt.In one example, it is washed respectively with the hydrochloric acid solution and a large amount of deionized deoxygenated waters that concentration is 0.5~1.5M
It washs, being washed till pH is 6.0~7.0.The ratio of hydrochloric acid solution and multilayer two-dimension molybdenum carbide nanometer sheet can be (30~150) mL:
(0.5~5) g.
Then, it is stripped multilayer two-dimension molybdenum carbide nanometer sheet to obtain two-dimensional slice molybdenum carbide.Stripping process may include:
By multilayer two-dimension molybdenum carbide nanometer sheet through ultrasound 10~120 minutes in deionized deoxygenated water, at 3000~5000 revs/min
Under the conditions of, it is centrifuged 20~50 minutes, collects supernatant, deoxygenation saves.Obtained two-dimensional slice molybdenum carbide be single layer molybdenum carbide (with
Under, otherwise referred to as " single layer two dimension molybdenum carbide nanometer sheet " or " degradable single layer two-dimensional slice molybdenum carbide nanometer sheet "), single layer two
The lateral dimension for tieing up molybdenum carbide nanometer sheet can be 30~200nm, and thickness can be 0.5~3nm, the single layer two of the size range
Dimension molybdenum carbide nanometer sheet has the advantages that partial size is more uniform, can recycle and may be implemented in blood tumour efficiently concentrating.
The lateral dimension of preferred single layer two dimension molybdenum carbide nanometer sheet is 50~150nm, with a thickness of 0.5~2nm.
By polymer and two-dimensional slice molybdenum carbide according to molar ratio (1~10): 1 mixing, wherein polymer is excessive, polymer
It is added as an aqueous solution, 5~30wt.% of concentration range, under vacuum conditions, flows back, polymerize in 40~70 DEG C
Object modification.Polymer can be the hydrophilic organic polymers of good biocompatibility.Polymer can be used for example polyvinyl alcohol,
In polyethylene glycol, polyvinylpyrrolidone, bovine serum albumin(BSA), fetal calf serum, gelatin, chitosan, hyaluronic acid, mosanom etc.
One or more, preferably one or more of polyvinyl alcohol, polyvinylpyrrolidone and bovine serum albumin(BSA).It can also
To be, organic polymer and two-dimensional slice molybdenum carbide are according to mass ratio (10~150): 1 mixing.Polymer and two-dimensional slice carbonization
The mass ratio of molybdenum is (10~150): when 1, polymer phase is to excessive, it can be achieved that abundant modification to two-dimensional slice molybdenum carbide.In
40~70 DEG C carry out reflux and have the advantages that ensure to accelerate reaction rate while polymer active.Before and after the polymer reflow
Ingredient or activity do not change.
Polymer-modified rear progress centrifuge washing etc. can be being carried out, to remove the extra polymer for having neither part nor lot in reaction.
Degradable hybrid two-dimensional slice molybdenum carbide nanocomposite is prepared as a result,.Polymer is in nanometer
Content in composite material can be 10~80wt.%, preferably 40~60wt.%.The introducing of biocompatible hydrophilic polymer
Assign molybdenum carbide nanocomposite biological safety and stability.Degradable hybrid two-dimensional slice of the invention
Molybdenum carbide nanocomposite is nano-lamellar structure, is in two-dimensional slice stratiform, and lateral dimension can be 50~500nm, and thickness can
Think 0.5~5nm.
After cement-based powder material modification, the hydrodynamic radius of above-mentioned nanocomposite in deionized water is 50~500nm,
It is preferred that 50~200nm, the hydrodynamic radius in physiological saline is 50~500nm, preferably 50~200.It is degradable as a result, to have
Machine/inorganic hybridization two-dimensional slice molybdenum carbide nanocomposite has good stability in physiological environment in vitro.
Above-mentioned degradable hybrid two-dimensional slice molybdenum carbide nanocomposite can be used as multifunctional nano diagnosis and treatment
Agent uses, such as can be used as light thermit powder and use (in this case, can be described as " degradable hybrid two-dimensional slice molybdenum carbide
Nano combined light thermit powder "), it can be used for the photo-thermal therapy application in the area NIR I and NIR II of tumour.By good biocompatibility
, it can be achieved that the efficient photo-thermal therapy of tumour under one area of near-infrared and two area's laser irradiations after hydrophilic organic polymers modification.
In the nano combined light thermit powder of above-mentioned molybdenum carbide, molybdenum carbide can be by the area NIR I (such as 808nm) and the area NIR II (such as 1064
Nm) luminous energy of laser is changed into thermal energy to ablation tumour.
Advantages of the present invention:
(1) preparation method of the present invention is simple, and operation is relatively simple, and properties of product are stablized, beneficial to producing in enormous quantities；
(2) hybrid two-dimensional slice molybdenum carbide nanocomposite prepared by the present invention has NIR I and NIR II light
The characteristics of heat cure, realizes the efficient photo-thermal therapy of tumour；
(3) nanocomposite prepared by the present invention, tumor locus degree of enrichment is high, biological safety is high and degradability, is expected to
Realize the green treatment of tumour.
To test degradable hybrid two-dimensional slice molybdenum carbide nanocomposite of the invention, such as will gather
The nano combined light thermit powder of molybdenum carbide (polymer content 60%) of vinyl alcohol modification is scattered in normal saline solution, is taken
150 uL are injected into the tumour of the Balb/c tumor bearing nude mice of lotus 4T1 breast cancer tumour model.It is 1 W/ by power density
cm2, select the near-infrared laser that wavelength is the area NIR I (such as 808nm) or the area NIR II (such as 1064nm) to irradiate tumour 10 respectively
Minute.The experimental results showed that the only control group of injecting normal saline, only laser irradiation group and only mice with tumor in injection material group
Tumour increases obvious (Fig. 8).Inject the physiological saline of the nano combined light thermit powder containing molybdenum carbide and with can be in the group of laser irradiation
Effectively inhibit the growth of mouse tumor.It is worth noting that the effect of the area NIR II laser irradiation is better than NIR I area's laser photograph
Penetrate it is i.e. more obvious to the growth inhibition of tumour, this experimental results showed that the functional development in the area NIR II and chemical kinetics association
The curative effect of radiotherapy can be significantly improved with the introducing for the treatment of.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
Firstly, burning out molybdenum gallium carbon (carbon molybdenum gallium).I.e. respectively by molybdenum powder, gallium, carbon dust according to mass ratio 16:40:1 ratio
Example is uniformly mixed, and is placed in quartz tube furnace, in high purity inert gas (nitrogen or argon gas) atmosphere, with the liter of 12 DEG C/min
Warm rate is heated to 800 DEG C, and keeps 380h at such a temperature, passes through inductively coupled plasma atomic emission spectrometry and energy
Spectrometer measures in the molybdenum gallium carbon burnt out, molybdenum, gallium, carbon mass ratio be 16:12:1.Then, the preparation of multilayer carbonization molybdenum sheet, i.e.,
It is to impregnate 48h in the aqueous hydrochloric acid solution of 11mol/L by the concentration that the carbon molybdenum gallium of 1g is immersed in 25mL, it, will after removing extra gallium
1.2g lithium fluoride is added in the hydrochloric acid solution that 20mL concentration is 12mol/L after mixing, and the carbon molybdenum for having removed extra gallium is added
Gallium keeps 600h in 45 DEG C.The hydrochloric acid solution for being respectively later 1.2M with the concentration of 80mL and a large amount of deionized deoxygenated waters are washed
It washs, being washed till pH is 6.5.Next prepare single layer molybdenum carbide nanometer sheet, i.e., through ultrasonic 80min in deionized deoxygenated water,
Under the conditions of 4500 revs/min, it is centrifuged 30min, collects supernatant, deoxygenation saves, and obtains the lateral ruler of single layer molybdenum carbide nanometer sheet
Very little is 200nm, with a thickness of 5nm.Finally, select concentration be 10% polyvinyl alcohol aqueous solution, and lamella molybdenum carbide according to
Molar ratio 5:1, under vacuum conditions, temperature are maintained at 40~70 DEG C, flow back, and finally pass through centrifuge washing, have prepared
Machine/nano combined the light thermit powder of inorganic hybridization two-dimensional slice molybdenum carbide.Composite material is measured by dynamic light scattering granularmetric analysis instrument
Hydrodynamic radius in deionized water is 150nm, and the hydrodynamic radius in physiological saline is 160nm.
Fig. 1 is transmission electron microscope (TEM) photo of carbon molybdenum gallium in embodiment 1.Carbon molybdenum gallium crystal form is arranged as can be seen from Figure 1
Column are neat.
Fig. 2 is scanning electron microscope (SEM) photo of carbon molybdenum gallium in embodiment 1.Carbon molybdenum gallium structure is complete as can be seen from Figure 2
It is whole.
Fig. 3 is scanning electron microscope (SEM) photo of multilayer two-dimension molybdenum carbide nanometer sheet in embodiment 1.It is more as can be seen from Figure 3
The lamellar structure of the two-dimentional molybdenum carbide nanometer sheet of layer is obvious.
Fig. 4 is transmission electron microscope (TEM) photo of single layer two-dimensional slice molybdenum carbide nanometer sheet in embodiment 1.It can be with from Fig. 4
Find out that two-dimentional molybdenum carbide nanometer sheet is single layer, size uniformity, thinner thickness.
Fig. 5 be in embodiment 1 the nano combined light thermit powder of organic/inorganic two-dimensional slice molybdenum carbide in water, physiological saline and thin
Partial size in born of the same parents' culture solution.The complex light thermit powder has good stability and dispersion in physiological environment as can be seen from Figure 5
Property.
Embodiment 2
The nano combined light thermit powder of molybdenum carbide that polyvinyl alcohol is modified is dispersed in deionized water, is placed in cuvette, is examined
The suspension that molybdenum element concentration in agent is respectively 25,50,100 and 200 μ g/mL is treated, takes distilled water as control.Power is used respectively
Density is 1.0W/cm2NIR I (808nm) and NIR II (1064nm) wavelength near-infrared laser irradiation, pass through infrared camera
Record water temperature changes with time.
Tumor bearing nude mice (diameter of tumor is about 0.6-1cm) is taken, is modified respectively by the polyvinyl alcohol of 150 μ L of tail vein injection
The nano combined light thermit powder of molybdenum carbide normal saline dispersion and physiological saline.It then, is 1.0W/cm in power density2's
Under the conditions of, tumor locus is irradiated with the near-infrared laser of NIR I (808nm) and NIR II (1064nm) wavelength respectively, by red
Outer cameras record tumor temperature changes with time situation.
From Fig. 6 (a) and Fig. 6 (b) as can be seen that at low concentrations under the conditions of such as 25 μ g/mL, the carbonization of polyvinyl alcohol modification
The nano combined light thermit powder of molybdenum can effectively absorb the near infrared light of NIR I (808nm) and NIR II (1064nm), and with heat
Form conversion, and then embody its light thermal property.It is 1.0 W/cm that Fig. 6 (a) and Fig. 6 (b), which is power density,2NIR I 808nm
Under the irradiation of NIR II 1064nm near-infrared laser, concentration is respectively the polyvinyl alcohol modification of 25,50,100 and 200 μ g/mL
The nano combined light thermit powder dispersion liquid temperature of molybdenum carbide situation of change.It is obvious that gathering under the laser irradiation of equal-wattage density
The nano combined light thermit powder of molybdenum carbide of vinyl alcohol modification can convert light energy into thermal energy more efficiently to increase system temperature.
And deionized water itself does not have the ability of photothermal conversion, and after irradiation in 10 minutes, NIR II (1064nm) irradiation gathers
The nano combined light thermit powder of molybdenum carbide of vinyl alcohol modification can make distillation coolant-temperature gage be increased to 63 DEG C.And under same concentrations, NIR
The photothermal conversion ability of the nano combined light thermit powder of molybdenum carbide of the polyvinyl alcohol modification of I (808nm) irradiation is slightly below the area NIR I.
Fig. 7 (a) and (b) be mice with tumor injecting normal saline or be mixed with polyvinyl alcohol modification molybdenum carbide it is nano combined
It is 1.0 W/cm in the area NIR I (808nm) and the area NIR II (1064nm) power density after the physiological saline of light thermit powder2It is close red
Under outer laser irradiation, the temperature change instruction figure of tumor region and corresponding temperature variation curve.Similarly, physiology salt is injected
Do not have photothermal conversion ability in water control mice with tumor body, and the molybdenum carbide that polyvinyl alcohol is modified under laser irradiation is nano combined
Light thermit powder then can effectively increase the temperature of tumor region, what is particularly worth mentioning is that, NIR II (1064 nm) laser irradiation
Tumor region temperature can be increased to 49 DEG C after ten minutes, and 10 minutes temperature of NIR I (808nm) laser irradiation rise to 45
DEG C, further demonstrate that the nano combined light thermit powder of molybdenum carbide of polyvinyl alcohol modification has good photo-thermal in the area NIR I and NIR II
Transfer capability, especially in the area NIR II.
Embodiment 3
It disperses the nano combined light thermit powder of molybdenum carbide that polyvinyl alcohol is modified in normal saline solution, 150uL is taken to pass through tail
It is injected intravenously in lotus 4T1 breast cancer tumour model Balb/c nude mice.It is 1W/cm by power density2, wavelength NIR-I
The near-infrared laser of (808nm) or NIR II (1064nm) irradiate tumour 10 minutes.The tumour body of Fig. 8 nude mice after different treatments
The long-pending relationship that changes with time.The experimental results showed that molybdenum carbide nano combined photo-thermal of the mice with tumor in injection polyvinyl alcohol modification
After agent cooperates laser irradiation, the growth of gross tumor volume is obviously inhibited.It is worth noting that, compared with NIR-I, NIR-II
The nano combined light thermit powder of molybdenum carbide that polyvinyl alcohol is modified under area's laser irradiation can more thoroughly inhibit the tumour growth of mouse,
This is the experimental results showed that the functional development in the area NIR II can significantly improve the curative effect of radiotherapy.
Embodiment 4
It disperses the nano combined light thermit powder of molybdenum carbide that polyvinyl alcohol is modified in the normal saline solution of different pH value.Fig. 9
(a)-Fig. 9 (c) respectively show by the nano combined light thermit powder of molybdenum carbide of polyvinyl alcohol modification be scattered in different pH value (pH value=
3.0, the nano combined light thermit powder of organic/inorganic two-dimensional slice molybdenum carbide is external when 7.0,11.0) in normal saline solution
Degradation curve；Fig. 9 (d)-Fig. 9 (f), which is respectively to show, disperses the nano combined light thermit powder of molybdenum carbide of polyvinyl alcohol modification in not
With impregnating different time (soaking time=0,12,48 hours) organic/inorganic two-dimensional slice afterwards in the normal saline solution of pH value
The photo of the external degradation situation of the layer nano combined light thermit powder of molybdenum carbide.From Fig. 9 (a)-Fig. 9 (f) as can be seen that with pH value
It increases and the extension of time, the degradation rate of the molybdenum carbide of polyvinyl alcohol modification is accelerated, when pH value is greater than 7.0 and impregnates 48h
It afterwards, can be degradable.It is then different in acidic environment, it is faintly acid in view of tumor region pH value, thus the complex light thermit powder can
The long period is maintained in tumor region, is realized while improving biological safety to efficient treatment.
Product of the present invention preparation process is simple；Two-dimensional slice molybdenum carbide nanometer light thermit powder has very in the area NIR I and NIR II
Good absorption can synchronize and realize efficient oncotherapy, be of great significance to Development of Novel biological safety light thermit powder.
Embodiment 5:
Firstly, burning out molybdenum gallium carbon (carbon molybdenum gallium).I.e. respectively by molybdenum powder, gallium, carbon dust according to mass ratio 16:40:1 ratio
Example is uniformly mixed, and is placed in quartz tube furnace, in high purity inert gas (nitrogen or argon gas) atmosphere, with 12 DEG C/min's
Heating rate is heated to 800 DEG C, and keeps 380h at such a temperature.Then, the preparation of multilayer carbonization molybdenum sheet, i.e., by the carbon of 1 g
The concentration that molybdenum gallium is immersed in 25mL is to impregnate 48h in the aqueous hydrochloric acid solution of 11mol/L and be fluorinated 1.2g after removing extra gallium
Lithium is added in the hydrochloric acid solution that 40mL concentration is 12mol/L after mixing, the carbon molybdenum gallium for having removed extra gallium is added, at 45 DEG C
Middle holding 600h.The hydrochloric acid solution for being respectively later 1.2M with the concentration of 80mL and a large amount of deionized deoxygenated waters wash, and are washed till pH
It is 6.5.Next single layer molybdenum carbide nanometer sheet is prepared, i.e., through ultrasonic 80min in deionized deoxygenated water, at 4500 revs/min
Under the conditions of, it is centrifuged 30min, collects supernatant, isolation air saves.Finally, polymer selects bovine serum albumin(BSA), and lamella
Molybdenum carbide is according to molal weight ratio 10:1, and under vacuum conditions, temperature is maintained at 40~70 DEG C, flows back, finally by from
Heart washing, prepares the nano combined light thermit powder of hybrid two-dimensional slice molybdenum carbide, wherein polymer content is
80wt.%.
Embodiment 6:
Firstly, burning out molybdenum gallium carbon (carbon molybdenum gallium).I.e. respectively by molybdenum powder, gallium, carbon dust according to mass ratio 16:40:1 ratio
Example is uniformly mixed, and is placed in quartz tube furnace, in high purity inert gas (nitrogen or argon gas) atmosphere, with 12 DEG C/min's
Heating rate is heated to 800 DEG C, and keeps 380h at such a temperature.Then, the preparation of multilayer carbonization molybdenum sheet, i.e., by the carbon of 1 g
The concentration that molybdenum gallium is immersed in 25mL is to impregnate 48h in the aqueous hydrochloric acid solution of 11mol/L and be fluorinated 1.2g after removing extra gallium
Lithium is added in the hydrochloric acid solution that 20mL concentration is 12mol/L after mixing, the carbon molybdenum gallium for having removed extra gallium is added, at 45 DEG C
Middle holding 600h.The hydrochloric acid solution for being respectively later 1.2M with the concentration of 80mL and a large amount of deionized deoxygenated waters wash, and are washed till pH
It is 6.5.Next single layer molybdenum carbide nanometer sheet is prepared, i.e., through ultrasonic 80min in deionized deoxygenated water, at 4500 revs/min
Under the conditions of, it is centrifuged 30min, collects supernatant, it is dry.Finally, polymer selects hyaluronic acid, and lamella molybdenum carbide according to rubbing
You are mass ratio 5:1, and under vacuum conditions, temperature is maintained at 40~70 DEG C, flows back, and finally passes through centrifuge washing, prepares
The nano combined light thermit powder of hybrid two-dimensional slice molybdenum carbide, wherein polymer content is 45wt.%.
Claims (11)
1. a kind of degradable hybrid two-dimensional slice molybdenum carbide nanocomposite, which is characterized in that the composite wood
Material includes the polymer of two-dimensional slice molybdenum carbide and modification on two-dimensional slice molybdenum carbide surface, and the polymer is hydrophily
Organic polymer.
2. degradable hybrid two-dimensional slice molybdenum carbide nanocomposite according to claim 1, feature
Be, the polymer be polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, bovine serum albumin(BSA), fetal calf serum, gelatin,
At least one of chitosan, hyaluronic acid, mosanom, content of the polymer in the composite material are 10~80
wt. %。
3. degradable hybrid two-dimensional slice molybdenum carbide nanocomposite according to claim 1 or 2,
It is characterized in that, the hydrodynamic radius of the composite material in deionized water is 50~500 nm, and the composite material is in life
Managing the hydrodynamic radius in salt water is 50~500 nm.
4. degradable hybrid two-dimensional slice molybdenum carbide described in a kind of any one of claims 1 to 3 is nano combined
The preparation method of material characterized by comprising
Fire molybdenum gallium carbon；
The gallium in the molybdenum gallium carbon is removed, multilayer molybdenum carbide presoma is obtained；
The multilayer molybdenum carbide presoma is mixed with fluorine-containing acid etching liquid, keeps the temperature 48 ~ 650 hours in 30 ~ 50 DEG C, preparation
Multilayer molybdenum carbide；
It removes the multilayer molybdenum carbide to obtain two-dimensional slice molybdenum carbide through sonic oscillation；And
By hydrophilic organic polymers and the two-dimensional slice molybdenum carbide according to molar ratio (1~10): 1 mixing, in vacuum condition
Under, it flows back in 40~70 DEG C, prepares degradable hybrid two-dimensional slice molybdenum carbide nanocomposite.
5. the preparation method according to claim 4, which is characterized in that firing molybdenum gallium carbon includes: by molybdenum powder, gallium, carbon
Powder is according to mass ratio (10~20): (10~60): 1 ratio mixes, and fires under inert atmosphere in 750~950 DEG C.
6. preparation method according to claim 4 or 5, which is characterized in that in the molybdenum gallium carbon, molybdenum, gallium, carbon mass ratio
For (10~20): (8~15): 1.
7. the preparation method according to any one of claim 4 to 6, which is characterized in that by described in acid solution A removal
Gallium in molybdenum gallium carbon, hydrionic concentration is 9 ~ 13 mol/L in the acid solution A.
8. preparation method according to any one of claims 4 to 7, which is characterized in that the fluorine-containing acid etching liquid is logical
Cross lithium fluoride and acid solution B according to (0.8 ~ 2.0) g:(15 ~ 40) ratio of mL is obtained by mixing, in the acid solution B
Hydrionic concentration is 9 ~ 13 mol/L.
9. preparation method according to any one of claims 4 to 8, which is characterized in that the sonic oscillation, which is removed, includes:
By the multilayer molybdenum carbide through ultrasound 10~120 minutes in deionized deoxygenated water, in 3000~5000 revs/min of conditions
Under, it is centrifuged 20~50 minutes, collects supernatant, deoxygenation saves.
10. the preparation method according to any one of claim 4 to 9, which is characterized in that the two-dimensional slice molybdenum carbide is
The lateral dimension of single layer molybdenum carbide, the single layer molybdenum carbide is 30~200 nm, with a thickness of 0.5~3 nm.
11. degradable hybrid two-dimensional slice molybdenum carbide nanometer described in a kind of any one of claims 1 to 3 is multiple
Application of the condensation material in preparation light thermit powder.
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