CN109650449A - The preparation method and product of a kind of molybdenum oxide nano material and application - Google Patents
The preparation method and product of a kind of molybdenum oxide nano material and application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of molybdenum oxide nano material and product and applications, preparation method includes: 1) to be dissolved in acetyl acetone in the mixed solution of octadecylene, oleic acid and hexadecylamine, is stirred to react at 90~150 DEG C and generates molybdenum oxide nanostructure intermediate;2) mixed solution containing molybdenum oxide nanostructure intermediate in step 1) is continued into hydro-thermal reaction, obtains sea urchin shape hollow molybdenum nano material.Obtained molybdenum oxide nano material not only can realize that specific toxicities activation is efficiently imaged and be treated for tumour in tumor locus, but can in the normal tissue fast degradation to ensure good biological safety.
Description
Technical field
The present invention relates to the preparation fields of molybdenum oxide, and in particular to a kind of preparation method and product of molybdenum oxide nano material
And application.
Background technique
Tumour, which has become, seriously threatens one of principal disease of human health.The state of the World Health Organization (WHO) subordinate
Border Agency for Research on Cancer (IARC) research report statistics, it is 18,100,000 person-times that global cancer in 2018, which increases confirmed cases newly, new
Increase Asia in cancer patient and accounts for the 48.4% of the whole world.
Currently, the cancer target efficiency of anti-tumor nano material is still lower (usually less than 1%), tumor-killing is caused to be imitated
Fruit is poor, and more obvious to the toxic side effect of normal cell.Even if administration mode is intratumor injection, surrounding normal is diffused to
The anti-tumor nano material of tissue can also cause the toxicity problem for being difficult to estimate.Anti-tumor nano material (especially inorganic nano
Material) it need to be excreted within a certain period of time by renal route or liver and gallbladder approach, to ensure that it in the normal tissue can be fast
Speed is removed, and then is avoided because of toxicity problem caused by accumulating for a long time in vivo.But this to the size of nano material, pattern and
Surface chemistry etc. is more demanding.
Therefore, many researchers are dedicated to studying new antitumoral nano material, improve tumor by local cytotoxicity
While guarantee safety in the normal tissue.A kind of Template-free method, quickly and effectively water as disclosed in 10142541 B of CN
Process for thermosynthesizing, using molybdenum trioxide and the peroxidating molybdic acid of aqueous hydrogen peroxide solution reaction preparation as presoma, at 80~180 DEG C
The a- molybdenum trioxide hydrate that hydrothermal synthesis is dispersed.The molybdenum oxide hydration of oxygen modification is obtained in hydrothermal synthesis at 65~75 DEG C
Object.Hydrate is Multi-scale model, and nano flake, micron prism and nano bar-shape structural unit diversity are assembled into micron order height
Density sea urchin shape structure.However, this biggish size of micron order molybdenum oxide limits its biologic applications.In addition, CN
108451932 A disclose the molybdenum oxide nanometer sheet and preparation method and application of a kind of modification of pluronic, with good
The biological degradability that biological safety, strong photothermal conversion effect, high drug load and pH are relied on can combine near infrared light can
To realize tumor thermal therapy or chemotherapy-photo-thermal combination therapy, improves the therapeutic effect of tumour and reduce toxic side effect.However,
The tissue attenuation characteristic and poor patient adaptability of near infrared light limit the extensive use of photo-thermal therapy.
As it can be seen that needing to develop the anti-tumor nano material that a kind of tumor cytotoxicity is high-efficient, vivo biodistribution safety is good.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of preparation method of molybdenum oxide nano material is provided,
Obtained molybdenum oxide nano material, can also be in tumor locus specificity in addition to having strong photothermal conversion effect and carrying pharmacological property matter
Realize that toxicity activation to realize that tumour is efficiently imaged and treats, is furthermore kept by the pH fast degradation relied in the normal tissue
Good biological safety.
Technical solution provided by the present invention are as follows:
A kind of preparation method of molybdenum oxide nano material, comprising:
1) acetyl acetone is dissolved in the mixed solution of octadecylene, oleic acid and hexadecylamine, at 90~150 DEG C
It is stirred to react and generates molybdenum oxide nanostructure intermediate;
2) mixed solution containing molybdenum oxide nanostructure intermediate in step 1) is continued into hydro-thermal reaction, obtains sea urchin shape
Hollow molybdenum nano material.
Acetyl acetone is reacted with oleic acid, hexadecylamine in the present invention generates molybdenum oxide nanostructure intermediate, then in water
In thermal response, molybdenum oxide nanostructure intermediate continues to be etched and restored by oleic acid and hexadecylamine, obtains sea urchin shape hollow
Molybdenum nano material (MoO3-xNUs).The partial size of sea urchin shape hollow molybdenum nano material is 100~1000nm.Sea urchin thorn-like point
Branch and hollow cavity all have biggish specific surface area, not only make the distribution of sea urchin shape hollow molybdenum nano-material surface a large amount of
Defect active site, while the pentavalent molybdenum of a large amount of reducing property being promoted to expose on the surface of the material, it is that it is special in tumor locus
Property toxicity activation establish materials chemistry basis.
The particle size range of sea urchin shape hollow molybdenum nano material is convenient for tumour cell intake, after being absorbed by tumour cell,
It, can be with the H of (pH < 7.4) high concentration intracellular due to the special appearance structure of sea urchin shape hollow molybdenum nano material2O2Instead
The superoxide anion (˙ O of high poison should be formed2 -), activating cytotoxic, and then lead to apoptosis of tumor cells.And in normal physiology
In environment (pH~7.4), sea urchin shape hollow molybdenum nano material can preferentially and OH-Reaction, is degraded to safe and non-toxic
MoO4 2-, realize good biological safety.
Heretofore described acetyl acetone, oleic acid, hexadecylamine and octadecylene feed ratio be 10~400mg:0.2
~20ml:0.02~2g:1~80ml.
Preferably, the acetyl acetone, oleic acid, hexadecylamine and octadecylene feed ratio be 10~250mg:1
~20ml:0.05~1.0g:4~40ml.
The heretofore described time being stirred to react is 5min~4h.Preferably, be stirred to react in the step 1)
Temperature is 90~120 DEG C, and mixing time is 0.5~2h.
The temperature of heretofore described hydro-thermal reaction is 120~260 DEG C, and the reaction time is 0.5~48h.
Preferably, sea urchin shape hollow molybdenum nano material is precipitated to obtain by poor solvent in the step 2).It is preferred that
, the poor solvent is selected from acetone, ethyl alcohol, ethyl acetate, methanol, methyl pyrrolidone, middle chain alcohol, acetonitrile, dimethyl methyl
One of amide, dimethyl sulfoxide are a variety of.
The preparation method of heretofore described molybdenum oxide nano material includes: to the sea urchin shape hollow molybdenum nanometer
Material carries out the load of the small-molecule drug for the treatment of tumour.Sea urchin shape hollow molybdenum nanometer material structure is hollow, hollow cavity
Body has biggish specific surface area, can load small-molecule drug, and collaboration significantly improves oncotherapy effect.
Preferably, the small-molecule drug be selected from adriamycin, cisplarin, vincaleukoblastinum, vincristine, vinblastine,
Vinorelbine, vinorelbine, taxol, docetaxel, Cabazitaxel, Etoposide, Teniposide, gemcitabine, Yi Li
For health, camptothecine, hydroxycamptothecin, D actinomycin D, cytarabine, Nimustine, Carmustine, lomustine, Semustine,
One of fluorouracil, amide, ifosfamide, brave and fierce, cis-platinum, carboplatin, methotrexate (MTX) are a variety of.
The preparation method of heretofore described molybdenum oxide nano material includes: to the sea urchin shape hollow molybdenum nanometer
The modification of material progress amphipathy macromolecule.Repair sea urchin shape hollow molybdenum nano material using amphipathy macromolecule
Decorations, make it switch to hydrophily by lipophilicity, obtain the sea urchin shape hollow molybdenum nano material dispersed in water.
Preferably, the amphipathy macromolecule is selected from phosphatide-polyethylene glycol, poloxamer, polyvinylpyrrolidone, gathers
Vinyl alcohol, vitamin E polyethylene glycol succinic acid ester, poly lactide-glycolide acid, polylactic acid, sapn, phosphatide, gathers tween
Ethylene glycol, lauryl sodium sulfate, cetyl trimethylammonium bromide, albumin, lipoprotein, castor oil polyoxyethylene ether, rouge
One of fat acid polyoxyethylene ester, aliphatic acid polyethenoxy ether, alkyl phenol polyoxyethylene ether, polyol ester are a variety of.
As further preferred, the amphipathy macromolecule is selected from phosphatide-polyethylene glycol, poloxamer, polyvinyl pyrrole
One of alkanone, polyvinyl alcohol, tween, phosphatide, vitamin E polyethylene glycol succinic acid ester, poly lactide-glycolide acid
Or it is several.
Preferably, the quality feed ratio of the sea urchin shape hollow molybdenum nano material and amphipathy macromolecule is 1:1
~50.
The modification of heretofore described amphipathy macromolecule uses film dispersion method or emulsion-solvent evaporation method.
Preferably, the film dispersion method includes: that sea urchin shape hollow molybdenum nano material is dispersed in good solvent,
Amphipathy macromolecule is stirred and be added at room temperature, is evaporated under reduced pressure, and aquation obtains the sea urchin shape hollow molybdenum nanometer dispersed in water
Material.
Preferably, the emulsion-solvent evaporation method include: sea urchin shape hollow molybdenum nano material is dispersed in it is good molten
It in agent, stirs and is added in amphipathy macromolecule aqueous solution at room temperature, ultrasound is evaporated under reduced pressure, obtains the sea urchin dispersed in water
Shape hollow molybdenum nano material.
Preferably, the good solvent is selected from tetrahydrofuran, methylene chloride, chloroform, n-hexane, hexamethylene, dioxy
One of six rings are a variety of.
The present invention also provides a kind of molybdenum oxide nano materials being prepared such as above-mentioned preparation method.The hollow oxygen of sea urchin shape
The partial size for changing molybdenum nano material is 100~1000nm.
The present invention also provides a kind of such as above-mentioned molybdenum oxide nano material application in preparation of anti-tumor drugs.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) reaction system of preparation method is mild in the present invention, and condition is controllable, and cost is very low, has good clinical turn
Change possibility.
(2) present invention in obtained molybdenum oxide nano material both can tumor locus realize specific toxicities activation with
Realize tumour efficiently treat (without introduce outside laser), and can in the normal tissue fast degradation to ensure good biology
Safety.
(3) photoacoustic imaging performance of obtained molybdenum oxide nano material weakens with degradation in the present invention, can pass through
The oncotherapy effect and safety of photoacoustic imaging monitoring sea urchin shape hollow molybdenum nano material.
(4) present invention in obtained molybdenum oxide nano material have preferable drug loading performance, hollow cavity have compared with
The small-molecule drug for treating tumour can be supported on the inside of sea urchin shape nano material, further to mention by big specific surface area
High oncotherapy effect.In addition, obtained molybdenum oxide nano material still has strong photothermal conversion property, Ke Yitong in the present invention
Cross photo-thermal therapy synergistic treatment tumour.
Detailed description of the invention
Fig. 1 is the TEM figure of sea urchin shape hollow molybdenum nano material prepared by embodiment 1;
Fig. 2 is the TEM figure of molybdenum oxide nanostructure intermediate prepared by embodiment 3;
Fig. 3 is the XPS figure of molybdenum oxide nanostructure intermediate prepared by embodiment 3;
Fig. 4 is the TEM figure of sea urchin shape hollow molybdenum nano material prepared by embodiment 3;
Fig. 5 is the XPS figure of sea urchin shape hollow molybdenum nano material prepared by embodiment 3;
Fig. 6 is that the drug carrying ability of sea urchin shape hollow molybdenum nano material prepared by embodiment 6 evaluates figure;
Fig. 7 is that the sea urchin shape hollow molybdenum nano material in embodiment 3 generates superoxide anion efficiency rating figure;
Fig. 8 is that the catabolite generation superoxide anion efficiency of the sea urchin shape hollow molybdenum nano material in comparative example is commented
Valence figure;
Fig. 9 is that the sea urchin shape hollow molybdenum nano material in embodiment 3 is thin to tumour under pH6.0 and pH7.4 environment
The Cytotoxic evaluation figure of born of the same parents;
Figure 10 is the catabolite of the sea urchin shape hollow molybdenum nano material in comparative example in pH6.0 and pH7.4 environment
Under to the Cytotoxic evaluation figure of tumour cell;
Figure 11 is that the internal tumor killing effect of sea urchin shape hollow molybdenum nano material in embodiment 3 evaluates figure.
Specific embodiment
The present invention is elaborated below with reference to specific embodiment and Figure of description.
Embodiment 1
(1) it disperses 80mg acetyl acetone, 0.2g hexadecylamine and 2ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 10min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 200 DEG C, reaction
After 12h, water heating kettle taking-up is cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nanometer material
Expect (MoO3-xNUs it), and after washing 3 times with dehydrated alcohol is dispersed in chloroform.
Morphology characterization is carried out with TEM to sea urchin shape hollow molybdenum nano material, as a result as shown in Fig. 1, partial size is 300
~500nm.
Embodiment 2
(1) it disperses 100mg acetyl acetone, 0.2g hexadecylamine and 2ml oleic acid in 8ml octadecylene, 120 DEG C
Heating stirring reacts 10min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 180 DEG C, reaction
After 12h, water heating kettle taking-up is cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nanometer material
Expect (MoO3-xNUs it), and after washing 3 times with dehydrated alcohol is dispersed in chloroform, obtained sea urchin shape hollow molybdenum nanometer material
Expect size in 300~600nm.
Embodiment 3
(1) it disperses 120mg acetyl acetone, 0.2g hexadecylamine and 4ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 20min, generates molybdenum oxide nanostructure intermediate.
TEM and XPS is carried out to intermediate product molybdenum oxide nanostructure intermediate respectively to characterize.TEM characterization is as described in Figure 2, it was demonstrated that
Intermediate product is nano-scale particle, and partial size is 200~400nm.XPS characterization is as shown in Figure 3, it was demonstrated that heating process part sexavalence molybdenum
It has been reduced to pentavalent molybdenum.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 160 DEG C, reaction
After 12h, water heating kettle taking-up is cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nanometer material
Material, and be dispersed in chloroform after washing 3 times with dehydrated alcohol.
It carries out TEM and XPS to sea urchin shape hollow molybdenum nano material respectively to characterize, TEM is characterized as shown in figure 4, obtaining
Sea urchin shape hollow molybdenum nano material size in 300~600nm.XPS is characterized as shown in figure 5, obtained sea urchin shape is hollow
Pentavalent molybdenum content has up to 47% in molybdenum oxide nano material.
(3) sea urchin shape hollow molybdenum nano material and phosphatide-polyethylene glycol polymer (1:10, g/g) are dispersed in chlorine
In imitative.It rotates 1h and removes organic solvent, physiological saline is added later and disperses to obtain sea well dispersed in water in water bath sonicator
Gallbladder shape hollow molybdenum nano material, high speed centrifugation remove extra surfactant.
Embodiment 4
(1) it disperses 120mg acetyl acetone, 0.2g hexadecylamine and 4ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 20min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 160 DEG C, react 6h
Afterwards, water heating kettle taking-up being cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nano material,
And it is dispersed in chloroform after with dehydrated alcohol washing 3 times.
(3) by sea urchin shape hollow molybdenum nano material and polyethylene glycol 1000 vitamin E succinic acid ester (1:10, g/g)
It is dispersed in chloroform.It rotates 1h and removes organic solvent, physiological saline is added later and disperses to obtain dispersing in water in water bath sonicator
Good sea urchin shape hollow molybdenum nano material, high speed centrifugation remove extra surfactant.
Embodiment 5
(1) it disperses 120mg acetyl acetone, 0.2g hexadecylamine and 4ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 20min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 160 DEG C, react 6h
Afterwards, water heating kettle taking-up being cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nano material,
And it is dispersed in chloroform after with dehydrated alcohol washing 3 times.
(3) sea urchin shape hollow molybdenum nano material and polyvinyl alcohol (1:10, g/g) are dispersed in chloroform.Rotate 1h
Organic solvent is removed, physiological saline is added later and disperses to obtain sea urchin shape hollow well dispersed in water in water bath sonicator
Molybdenum nano material, high speed centrifugation remove extra surfactant.
Embodiment 6
(1) it disperses 40mg acetyl acetone, 0.2g hexadecylamine and 4ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 10min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 180 DEG C, react 6h
Afterwards, water heating kettle taking-up being cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nano material,
And be dispersed in chloroform after with dehydrated alcohol washing 3 times, obtained sea urchin shape hollow molybdenum nano material size 200~
400nm。
(3) adriamycin (1:5, g/g) after sea urchin shape hollow molybdenum nano material and desalination acid is dispersed in chloroform,
Room temperature is protected from light stirring and is centrifuged off free adriamycin afterwards for 24 hours.
(4) then, by load adriamycin sea urchin shape hollow molybdenum nano material and polyvinylpyrrolidone 5000 (1:
10, g/g) it is dispersed in chloroform, revolving 1h removes organic solvent, and physiological saline is added later, disperses to obtain in water bath sonicator
The sea urchin shape hollow molybdenum nano material (MoO of well dispersed load adriamycin in water3-xNUs/DOX), high speed centrifugation removes
Remove extra surfactant.
By passing through ultraviolet-visible spectrophotometer to MoO3-xNUs/DOX is characterized, as shown in Figure 6, it is known that will
DOX is successfully loaded in sea urchin shape hollow molybdenum nano material.
Comparative example
(1) it disperses 120mg acetyl acetone, 0.2g hexadecylamine and 4ml oleic acid in 8ml octadecylene, 100 DEG C
Heating stirring reacts 20min, generates molybdenum oxide nanostructure intermediate.
(2) mixture in step (1) is transferred in the high pressure water heating kettle of 15ml volume, is heated to 160 DEG C, reaction
After 12h, water heating kettle taking-up is cooled to room temperature, precipitating is collected by centrifugation in ethyl alcohol, and centrifugation obtains sea urchin shape hollow molybdenum nanometer material
Material, and be dispersed in chloroform after washing 3 times with dehydrated alcohol.Obtained sea urchin shape hollow molybdenum nano material size is 200
~400nm.
(3) sea urchin shape hollow molybdenum nano material and phosphatide-polyethylene glycol polymer (1:10, g/g) are dispersed in chlorine
In imitative, revolving 1h removes organic solvent, and NaOH solution (1M) is added later, and dispersion obtains well dispersed in water in water bath sonicator
Sea urchin shape hollow molybdenum nano material, high speed centrifugation removes extra surfactant.
(4) the sea urchin shape hollow molybdenum nano material that will be dispersed in NaOH solution is placed on 60 DEG C of baking ovens additions for 24 hours, with
Completely, freeze-drying obtains catabolite powder for degradation.
Performance test
(1) superoxide anion in-vitro evaluation
(1.1) by 20 μ l DPBF ethanol solutions (10mM), 1 μ l H2O2Solution (2M), sea urchin shape hollow molybdenum nanometer material
Material (prepared by embodiment 3,20 μ g) is dispersed in water/alcohol mixed solution (water: ethyl alcohol=4:6, v/v).
The hollow oxygen of sea urchin shape is studied at different time (0,2,5,10,20 and 30min) by ultraviolet-visible spectrophotometer
Change molybdenum nano material ˙ O2-Yield, as a result as shown in Fig. 7, the absorbance rapid decrease of DPBF show sea urchin shape hollow
Molybdenum nano material has compared with Gao ˙ O2-Yield.
(1.2) by 20 μ l DPBF ethanol solutions (10mM), 1 μ l H2O2Solution (2M), sea urchin shape hollow molybdenum nanometer material
The catabolite (comparative example preparation, 20 μ g) of material is dispersed in water/alcohol mixed solution (water: ethyl alcohol=4:6, v/v).
The hollow oxygen of sea urchin shape is studied at different time (0,2,5,10,20 and 30min) by ultraviolet-visible spectrophotometer
Change the catabolite ˙ O of molybdenum nano material2-Yield, as a result as shown in Fig. 8, the absorbance of DPBF, which is basically unchanged, to be shown to degrade
Product does not have Chan Sheng ˙ O2-Ability.
(1.3) since attached drawing 7 and 8 compares it is found that the sea urchin shape structure of sea urchin shape hollow molybdenum nano material is (rich in more
Defect sites) and valence state (pentavalent molybdenum) to H2O2React simultaneously Chan Sheng ˙ O2-Process it is very crucial.
(2) to the Cytotoxic evaluation of melanoma cancer cell line
The black cancer cell (B16 cell) of logarithmic growth phase, cell density is adjusted to 1 with fresh culture medium ×
104Cells/ml, be inoculated in 96 holes pull in (200 μ l/well), in 37 DEG C, 5%CO2Incubator in culture.
Changed into after cell adhere-wall culture 12h under different pH (pH6.0 and pH7.4), Mo concentration 0,1.56,3.13,6.25,
The sea urchin shape hollow molybdenum nano material (being made according to 3 method of the present embodiment) of 12.50 μ g/ml, sea urchin shape hollow molybdenum
The catabolite (being made according to this comparative example method) of nano material.Continue culture for 24 hours, culture solution is sucked out and with 200 μ l PBS
It washes.Then interior addition MTT solution (200 μ l/well) is pulled to 96 holes, is incubated for 1~4h jointly at 37 DEG C, culture solution is sucked out, adds
Enter 200 μ l DMSO and measures its optical density OD value after concussion shakes up.
Data processing carries out data processing using microplate reader corresponding software, calculates being averaged for 5 hole OD values of each sample
Value, is calculated as follows cell survival rate (Cell Viability%) using average value.
Average value/blank control group OD value average value × 100% (Cell of cell survival rate %=sample sets OD value
Viability%=ODsample/ODcontrol× 100%)
The results are shown in attached figure 9 and attached drawing 10.Sea urchin shape hollow molybdenum nano material has height in pH6.0 known to attached drawing 9
Cytotoxicity, and in pH7.4 without obvious cytotoxicity;Catabolite is without obvious cytotoxicity known to attached drawing 10.As it can be seen that sea urchin
Shape hollow molybdenum nano material has high toxicity in the slightly sour environment of tumour cell, can be degraded in neutral environment safe and non-toxic
Product.
(3) to the Cytotoxic evaluation of melanoma cancer cell line
12 nude mices are randomly divided into 2 groups, every group 6.Respectively physiological saline group and sea urchin shape hollow molybdenum is received
Rice material (MoO3-xNUs) group (being made according to 3 method of the present embodiment).It is administered twice in tumor weekly.Every other day measure tumour
Volume (V), calculation formula are as follows: V=L × W2/ 2, W and L are respectively the most wide and longest diameter line length of tumour.Use gross tumor volume
Tumor volume change is monitored with initial volume comparison.
As a result such as attached drawing 11, it is known that sea urchin shape hollow molybdenum nano material is without outer source laser or carry medicine in the case where can
Significantly inhibit tumour growth.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that with
Upper described is only specific embodiments of the present invention, be not intended to restrict the invention, all to be done in spirit of the invention
Any modification, supplement and equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of molybdenum oxide nano material characterized by comprising
1) acetyl acetone is dissolved in the mixed solution of octadecylene, oleic acid and hexadecylamine, is stirred at 90~150 DEG C
Reaction generates molybdenum oxide nanostructure intermediate;
2) mixed solution containing molybdenum oxide nanostructure intermediate in step 1) is continued into hydro-thermal reaction, it is hollow obtains sea urchin shape
Molybdenum oxide nano material.
2. the preparation method of molybdenum oxide nano material according to claim 1, which is characterized in that the acetyl acetone,
The feed ratio of oleic acid, hexadecylamine and octadecylene is 10~400mg:0.2~20ml:0.02~2g:1~80ml.
3. the preparation method of molybdenum oxide nano material according to claim 1, which is characterized in that it is described be stirred to react when
Between be 5min~4h.
4. the preparation method of molybdenum oxide nano material according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction
Degree is 120~260 DEG C, and the reaction time is 0.5~48h.
5. the preparation method of molybdenum oxide nano material according to claim 1 characterized by comprising to the sea urchin
Shape hollow molybdenum nano material carries out the load of the small-molecule drug for the treatment of tumour.
6. the preparation method of molybdenum oxide nano material according to claim 1 or 5 characterized by comprising to the sea
The modification of gallbladder shape hollow molybdenum nano material progress amphipathy macromolecule.
7. the preparation method of molybdenum oxide nano material according to claim 6, which is characterized in that the hollow oxygen of sea urchin shape
The quality feed ratio for changing molybdenum nano material and amphipathy macromolecule is 1:1~50.
8. the preparation method of molybdenum oxide nano material according to claim 6, which is characterized in that the amphipathy macromolecule
Modification use film dispersion method or emulsion-solvent evaporation method.
9. a kind of molybdenum oxide nano material that the preparation method as described in claim 1~8 is any is prepared.
10. a kind of molybdenum oxide nano material application in preparation of anti-tumor drugs as claimed in claim 9.
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