CN107961375A - A kind of nano metal sulfide material and its preparation method and application - Google Patents
A kind of nano metal sulfide material 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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Abstract
The invention discloses a kind of nano metal sulfide material and its preparation method and application, the nano metal sulfide material includes bismuth sulfide nano-rod and the high molecular material and nitric oxide donors that are coated on the bismuth sulfide nano-rod surface, the high molecular material is polyoxyethylene sorbitan laurate Tween 20, and the nitric oxide donors include BNN.The nano metal sulfide material can convert light energy into heat; nitric oxide donors are promoted to decompose release nitric oxide using photothermal conversion process; nitric oxide production controlled release and photo-thermal therapy can be realized at the same time; nitric oxide can reduce the self-protection effect of tumour cell in hyperthermia process, can significantly improve oncotherapy effect.Therefore, the present invention overcomes the deficiency of traditional tumour thermotherapy method, it is suitably applied the oncotherapy of complicated needs.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of nano metal sulfide material and preparation method thereof
And application.
Background technology
From 1992 nitric oxide (NO) annual star molecule is chosen as by Science magazines after, people expand NO
A series of research.It was discovered by researchers that NO can serve as messenger molecule in vivo, played during a variety of Physiological effects
Extremely important effect, such as neurotransmission, vasodilation, hormone secretion, platelet aggregation, injury repair, immunological regulation
Deng.Clinically, nitric oxide donors medicine is usually used in treating sudden angina pectoris and coronary heart disease etc..
The donor of currently used releasable NO mainly has following a few classes：Sodium nitroprussiate, nitric acid nitrous acid ester, S-nitrosoglutathione
Mercaptan, N- azo enediol classes.The common feature of this few widely used NO donor of class is can spontaneous release in vivo
NO.But nitric oxide itself chemical property is active, half-life period only has 5s or so, and its physiological action and concentration are closely related.
Therefore, spontaneous slow-release NO donor medicines need strictly to control usage amount in practical applications, and curative effect is subject to many factors shadow
It is loud and unstable.The defects of to overcome spontaneous slow-release NO donors, researcher have developed a series of controlled release type NO donors,
Such as nano particle of Lu Sen salt (RBS), metal NO complexs, NO modification etc..This kind of controlled release type NO donor majorities are
Light responsive material, can discharge nitric oxide molecule under specific wavelength irradiation.But this kind of material ultraviolet/visible light multipair greatly is quick
Sense, and ultraviolet/visible light irradiates penetration depth deficiency in vivo and there may be certain side effect.Comparatively speaking, closely
Infrared light (NIR) has stronger penetration capacity and relatively low phototoxicity in vivo.Thus, study near infrared light realizing controlled-release
Type NO donors tool is put to have very important significance.
With the development of nitric oxide donors, there is researcher that nitric oxide is used for therapeutic field of tumor.Nitric oxide is certainly
Body is also a kind of free radical, can make bioactive molecule that nitration/nitrozation reaction occur, destroy its 26S Proteasome Structure and Function.
Meanwhile nitric oxide also assists in cell-signaling pathways adjusting, the life of the various kinds of cell such as cell proliferation, Apoptosis, autophagy take part in
Reason process.Certain density nitric oxide can be with direct killing tumour cell or increase tumour cell to other treatment method
Susceptibility.Wherein, it is of specific interest be nitric oxide and traditional tumour therapeutic strategy synergistic effect, such as nitric oxide
With the conspiracy relation between chemotherapy, radiotherapy, thermotherapy.Therefore, it is expected to obtain one kind and can carry out tumor photo-thermal in the art to control
Treat again can the nitric oxide production nano material of controlled release, and its oncotherapy effect is furtherd investigate.
The content of the invention
It is an object of the invention to provide metal that is a kind of while having the function of photothermal conversion and nitric oxide releasing to vulcanize
Thing nano material and preparation method thereof and the application in oncotherapy.
The technical solution adopted in the present invention is：
A kind of nano metal sulfide material, including bismuth sulfide nano-rod and it is coated on the bismuth sulfide nano-rod surface
High molecular material and nitric oxide donors, the high molecular material is polyoxyethylene sorbitan laurate Tween-
20, the nitric oxide donors include BNN.
The length of the bismuth sulfide nano-rod is 10~100nm, and the draw ratio of the bismuth sulfide nano-rod is 5~20.
The hydration particle diameter of the nano metal sulfide material is 20~150nm.
The potential of the aqueous systems of the nano metal sulfide material is -5~-30mV.
The invention also discloses a kind of preparation method of nano metal sulfide material as described above, this method is included such as
Lower step：
Step 1, using bismuth salt as presoma, organic solvent is added, heating reaction a period of time, obtains solution；
Step 2, the sulphur powder for being dissolved in oleyl amine is added into the solution obtained by step 1, continues heating reaction certain time,
Cool, bismuth sulfide nano-rod is made；
Step 3, the bismuth sulfide nano-rod obtained by step (2) is dissolved in hexamethylene, add Tween-20 and go from
Sub- water, heating evaporation remove hexamethylene, obtain the bismuth sulfide nano-rod of Tween-20 modifications；
Step 4, select nitric oxide donors to be uniformly mixed in ethanol with the bismuth sulfide nano-rod obtained by step (3), stir
Mix, obtain nano metal sulfide material.
In the step (1), the bismuth salt is bismuth nitrate, bismuth chloride or 12 Bismuth Octoates；The organic solvent for oleic acid,
One or more in oleyl amine and octadecylene；The molar concentration of bismuth element is 0.05~0.5mol/ in the solution of the step (1)
L；Heating-up temperature in the step (1) is 100~200 DEG C；Reaction time in the step (1) is 10~30min.
In the reaction of the step (2), the molar ratio of bismuth element and element sulphur is 1:(1~5)；In the step (2)
Heating-up temperature is 150~200 DEG C；Reaction time in the step (2) is 1~10min.
In the step (3), the ratio between the concentration of the bismuth sulfide nano-rod and the volume of Tween-20 are 1:2 to 1:5；Institute
The volume ratio for stating reaction cyclohexane and deionized water is 1:2 to 1:5.
Nitric oxide donors in the step (4) are any one or more in BNN and its derivative, by an oxidation
After nitrogen donor is added in the ethanol, the concentration of nitric oxide donors is 0.1~4.0mmol/L；Stirring in the step (4)
It is 4~24h to mix the time.
The invention also discloses a kind of application process of nano metal sulfide material as described above, this method pass through by
The nano metal sulfide material is combined with treating the method for tumour, to suppress the growth of tumour cell.
By adopting the above-described technical solution, having the beneficial effect that acquired by the present invention：
1st, nano metal sulfide material of the present invention, can respond near infrared light release nitric oxide, breach
The light-operated release nitric oxide material of tradition can only respond ultraviolet or visible ray limitation.Use the nano metal sulfide material
Material, moves to infrared window by absworption peak, can effectively increase the penetration depth of laser in vivo, reduce live body group
The absorption to laser is knitted, reduces the damage of normal tissue.
2nd, nano metal sulfide material of the invention has the function of good photothermal conversion, it is possible to achieve thermotherapy and an oxygen
Change effective combination of nitrogen, play the effect of synergy, substantially increase traditional photo-thermal therapy efficiency, obtain optimal tumour and control
Therapeutic effect.
Brief description of the drawings
Fig. 1 is the structure diagram of the nano metal sulfide material of the present invention.
Fig. 2 is the transmission electron microscope picture of the nano metal sulfide material of the present invention.
Fig. 3 is the X-ray diffraction spectrogram of the nano metal sulfide material of the present invention.
Fig. 4 is the UV absorption spectrogram of the nano metal sulfide material of the present invention.
Fig. 5 is the infrared absorption spectra of the nano metal sulfide material of the present invention.
Fig. 6 is temperature variation of the nano metal sulfide material of various concentrations under near-infrared laser illumination.
Fig. 7 discharges nitric oxide production concentration schematic diagram for nano metal sulfide material in the present invention.
Fig. 8 is influence schematic diagram of the nano metal sulfide material to BEL-7402 cell viabilities in the present invention.
Fig. 9 for the present invention in nano metal sulfide material under near-infrared laser illumination condition to BEL-7402 cells
Promote apoptosis necrosis effect schematic diagram.
Figure 10 is in illumination bar to tumor locus after the nano metal sulfide material of the present invention is given in tumor
Infrared thermal imaging figure and temperature changing curve diagram under part.
Figure 11 is to combining thermotherapy and an oxidation after the nano metal sulfide material of the present invention is given in tumor
The tumor suppression result figure of nitrogen.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited to
These embodiments.Reagent or test equipment used in following embodiments, are that commercially available can obtain unless otherwise instructed.
As depicted in figs. 1 and 2, a kind of nano metal sulfide material, including bismuth sulfide nano-rod and be coated on described
The high molecular material and nitric oxide donors on bismuth sulfide nano-rod surface, the high molecular material are polyoxyethylene sorbitan
Laurate Tween-20, the nitric oxide donors are bis-N-nitroso compound (referred to as, BNN) and its derivative
In any one or more..
The draw ratio of the bismuth sulfide nano-rod is 5~20, such as 5,8,10,15,20.
The length of the bismuth sulfide nano-rod is 10~100nm, for example, 10nm, 20nm, 40nm, 55nm, 65nm, 80nm,
90nm or 100nm.
On the basis of the weight of nano metal sulfide material, the load capacity of the nitric oxide donors is 5% to 100%
(mass percent), such as 5%, 10%, 20%, 40%, 50%, 65%, 80%, 90% or 100%.
The hydration particle diameter of the nano metal sulfide material is 20~150nm, for example, 20nm, 23nm, 35nm, 48nm,
50nm, 63nm, 75nm, 88nm, 100nm, 123nm, 135nm, 140nm or 150nm.
The potential of the aqueous systems of the nano metal sulfide material is -5~-30mV, for example, -5mV, -8mV, -11mV, -
14mV, -17mV, -20mV, -23mV, -26mV or -30mV.
The invention also discloses a kind of preparation method of nano metal sulfide material as described above：This method is included such as
Lower step：
Step 1, using bismuth salt as presoma, organic solvent is added, heating reaction a period of time, obtains solution；In the step,
The bismuth salt is bismuth nitrate, bismuth chloride or 12 Bismuth Octoates；The organic solvent be oleic acid, oleyl amine and octadecylene in one kind or
It is several；The molar concentration of bismuth element is 0.05~0.5mol/L in the solution obtained by the step, for example, 0.05mol/L,
0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L；Heating-up temperature in the step is 100~200 DEG C,
Such as 100 DEG C, 120 DEG C, 140 DEG C, 170 DEG C, 180 DEG C or 200 DEG C；Reaction time in the step is 10~30min, such as
10min, 20min or 30min；
Step 2, the sulphur powder for being dissolved in oleyl amine is added into the solution obtained by step 1, continues heating reaction certain time,
Cool, bismuth sulfide nano-rod is made；In the reaction of the step, the molar ratio of bismuth element and element sulphur is 1:(1~5), example
Such as 1:1、1：2、1:3、1：4 or 1:5；Heating-up temperature in the step is 150~200 DEG C, for example, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C or 200 DEG C；Reaction time in the step (2) is 1~10min, such as 1min, 3min, 6min, 8min or 10min.
Step 3, the bismuth sulfide nano-rod obtained by step (2) is dissolved in hexamethylene, add Tween-20 and go from
Sub- water, heating evaporation remove hexamethylene, obtain the bismuth sulfide nano-rod of Tween-20 modifications；In the step (3), the bismuth sulfide
The ratio between the concentration (mg/mL) of nanometer rods and the volume (μ L) of Tween-20 are 1:2 to 1:5, such as 1:2、1:3、1:4 or 1:5；Institute
The volume ratio for stating reaction cyclohexane and deionized water is 1:2 to 1:5, such as 1:2、1:3、1:4 or 1:5；
Step 4, select nitric oxide donors to be uniformly mixed in ethanol with the bismuth sulfide nano-rod obtained by step (3), stir
Mix, obtain nano metal sulfide material；Nitric oxide donors in the step (4) are BNN and its derivative, by nitric oxide
After donor is added in the ethanol, the concentration of nitric oxide donors is 0.1~4.0mmol/L, such as 0.1mmol/L,
1.5mmol/L, 3.3mmol/L or 4.0mmol/L；Mixing time in the step (4) is 4~24h, for example, 4h, 6h, 15h,
20h or 24h.
The preparation method of the nano metal sulfide material is done with specific embodiment below further specifically
It is bright.
Embodiment 1：
(1) by the BiCl of 3mmol3It is added in the three neck round bottom flask of 100mL, adds the oleic acid and 10mL of 10mL
Oleyl amine, adds stirrer stirring, is warming up to 170 DEG C and reacts 30min and obtain reaction system A afterwards；
(2) sulphur simple substance of 10mmol is dissolved in the oleyl amine of 5mL, ultrasound makes it fully dissolve, and obtains solution I；
(3) solution I is added rapidly in reaction system A, continues to react 10min under conditions of 170 DEG C, reacted
System B；
(4) stop reaction, after question response system B is cooled to room temperature, system B is transferred in centrifuge tube, using 8000 turns/
The rotating speed centrifugation 3min of minute, takes precipitation to be resuspended in obtained solution II in the hexamethylene of 20mL afterwards；
(5) solution II of 10mL is taken, adds the Tween-20 of 100 μ L, adds the deionized water of 30mL, ultrasonic 30min
Afterwards, heating water bath is to 70 DEG C, and stirring is until solution is clarified；Afterwards, 10min is centrifuged using 12000 revs/min of rotating speed, then
The bismuth sulfide nano-rod of Tweeen-20 modifications is collected, is freezed spare；
(6) the BNN ethanol solutions III of 2mmol/L is configured.The bismuth sulfide nano-rod of the Tweeen-20 modifications of 10mg is weighed,
The solution III of 10mL is added, lucifuge stirring 12h, is then precipitated using collection after 12000 revs/min of rotating speed centrifugation 10min,
The nano metal sulfide material is made.
The structure diagram of the nano metal sulfide material being prepared by above-described embodiment 1 as shown in Figure 1, including
The bismuth sulfide nano-rod of Tweeen-20 modifications, and absorption is in the nitric oxide donors BNN on its surface.
Using transmission electron microscope (FEI Tecnai G2F20) to the nano metal sulfide material that is obtained by embodiment 1 into
Row characterization, the results are shown in Figure 2, and as can be seen from the figure material is in bar-shaped, and length is about 70nm, and width is about 7nm.
The nano metal sulfide material obtained by embodiment 1 is carried out using X-ray diffractometer (Bruker D8)
XRD characterization, the results are shown in Figure 3, and as seen from the figure, the diffraction maximum of the diffraction maximum and bismuth sulfide standard spectrogram of the nano material is coincide
(JCPDS 17-0320 in Fig. 3 represent be database Plays bismuth sulfide crystal XRD diffracting spectrums), thus can sentence
Obtained nano material of breaking contains bismuth sulfide.
Using ultraviolet-visual spectrometer (Hitachi U-3900) to the nano metal sulfide material that is obtained by embodiment 1
Material is characterized, and the results are shown in Figure 4, is absorbed it can be seen from the figure that material has at 808nm wavelength, this explanation material
The light of 808nm wavelength can be absorbed.Using the property, the fuel factor of material can be analyzed with reference to 808nm lasers.
Using infrared spectrometer (Nicolet iN10, Thermo Fisher) to the metal sulfide that is obtained by embodiment 1
Nano material is characterized, and the results are shown in Figure 5,1512cm-1The peak of corresponding O=N keys；1454cm-1Corresponding O=N-N keys shake
Dynamic peak, it can be seen that the characteristic peak of BNN is appeared in infrared spectrum.
It can show that the present invention has been prepared by result is characterized as above to be loaded with the bismuth sulfide of nitric oxide donors BNN and receive
Rice material.
The photothermal conversion effect for the nano metal sulfide material that embodiment 1 is prepared below is measured, method
It is as follows：
The nano metal sulfide material of 1mL various concentrations is put into the cuvette of 1cm, uses 1W/cm2's
Nano material in 808nm continuous wave lasers (the vast space connet types in Shanghai) irradiation cuvette 10 minutes, while use near-infrared
Solution temperature change in imager (FLIR ThermaCAM E40) contrastive colours ware is monitored.
As shown in fig. 6, as seen from the figure, the laser of the nano material aqueous solutions of various concentrations in 808nm irradiates measurement result
Lower temperature is gradually increasing, and illustrates the nano metal sulfide material of the present invention and has the function of good photothermal conversion.
The oxidation of release one under near infrared light NIR irradiations to the nano metal sulfide material prepared by embodiment 1 below
The performance of nitrogen is assessed, and method is as follows：
The nano metal sulfide material of 3mL is put into the cuvette of 1cm, it is continuous using the 808nm of different capacity
Nano material in laser (the vast space connet types in Shanghai) irradiation cuvette 15 minutes, takes out 200 μ L's at regular intervals
Solution centrifuges to obtain supernatant, utilizes NO fluorescence probes 2,3-Diaminonaphthalene (DAN, Sigma) measurement supernatants
In nitric oxide production concentration.
Measurement result is as shown in fig. 7, as shown in Figure 7, photograph of the nano metal sulfide material in 808nm continuous wave lasers
Nitric oxide can be effectively discharged under penetrating.
Influence of the nano metal sulfide material of the present invention to cell viability is measured below, to pass through reality
Exemplified by applying the nano metal sulfide material that example 1 is prepared, method is as follows：
(1) cell culture
By BEL-7402 cells (people source liver cancer cells) and the DMEM fluid nutrient mediums containing 10% hyclone, it is placed on
Temperature is 37 DEG C, CO2Concentration is in 5% cell incubator.
(2) cell viability measures
With 5000 cells/well density, by cell inoculation in 96 orifice plates.It is adherent 12 it is small when after, add containing concentration as 0,10,
20th, 40, the DMEM fluid nutrient mediums (containing 10% hyclone) of the nano material of 80ppm (with bismuth element).When processing 24 is small
Afterwards, remove culture medium, per hole add 100 μ L the cell culture fluid containing 10%CCK-8, in the incubator be incubated 1 it is small when after,
The light absorption value at 450nm is measured in microplate reader, using 600nm as reference wavelength, every group of absorbance deducts blank solution extinction
Angle value, the absorbance of value divided by control group per hole is as cell viability, 6 parallel holes of every group of setting.
Fig. 8 shows influence of the nano metal sulfide material of the present invention to BEL-7402 cell viabilities, different dense
The lower cell viability of degree is all higher than 90%, and illustrating the nano metal sulfide material of the present invention does not have BEL-7402 cells
Toxicity.
Thermotherapy and nitric oxide synergistic treatment are used for people source liver cancer to the nano metal sulfide material of the present invention below
The lethal effect of cell BEL-7402 is measured, and specific assay method is as follows：
(1) cell culture
By BEL-7402 cells and the DMEM fluid nutrient mediums containing 10% hyclone, it is 37 DEG C, CO to be placed on temperature2
Concentration is in 5% cell incubator.
(2) Apoptosis detects
By the cell inoculation of culture in step (1) in 6 orifice plates, per 100000 cell of hole.It is adherent 12 it is small when after, add containing dense
The DMEM fluid nutrient mediums (containing 10% hyclone) of the nano metal sulfide material of 80ppm (with bismuth element) are spent, are incubated 12
Hour.Culture medium is removed, with trypsin digestion and cell, supernatant is abandoned with 1200 revs/min of rotating speed centrifugation, is buffered using PBS
Cell is resuspended in liquid (phosphate buffered saline solution), and repetition is washed three times, is respectively 1.0W cm with power density-2Laser irradiating cell
Agglomerate 8min, then washed three times with PBS buffer, contaminated with Annexin V-FITC/PI kits (cell apoptosis detection kit)
Color, then uses flow cytomery.Gather 10,000 cells and carry out subregion, count the cell percentages in each region.
Such as Fig. 9 as can be seen that nano metal sulfide material of the present invention can cause Apoptosis and necrosis, and
And effect is better than the heat-therapeutic action using simple bismuth sulfide material.
The influence of change of the nano metal sulfide material of the present invention to tumor-bearing mice tumor locus temperature is investigated below,
By taking the nano metal sulfide material being prepared by embodiment 1 as an example, method is as follows：
To giving nano metal sulfide material in tumor, then using the laser of 808nm with 0.3W/cm2's
Power illumination tumor locus 10min, only not carry out the tumor-bearing mice of laser irradiation to nano material as a control group, observation
The ramp case at mouse tumor position.The results are shown in Figure 10, gives nano metal sulfide in knurl as we can clearly see from the figure
The tumor locus of the tumor-bearing mice of material has obvious temperature rise effect, and the tumor locus temperature of control group mice is substantially not
Become.
The invention also discloses a kind of pharmaceutical composition, including the nano metal sulfide material and it is supported on institute
State the medicine on nano metal sulfide material.On the basis of the weight of the nano metal sulfide material, the medicine group
The carrying drug ratio of compound is 5~100 percentage by weights, such as 5,10,40,65,80 or 100.The medicine is nitric oxide donors,
The nitric oxide donors include any one or more in BNN and its derivative.
The invention also discloses a kind of application process of nano metal sulfide material as described above, this method pass through by
The nano metal sulfide material is combined with treating the method for tumour, to suppress the growth of tumour cell.
The tumor killing effect of the nano metal sulfide material of the present invention is investigated below, to be prepared by embodiment 1
Exemplified by obtained nano metal sulfide material, method is as follows：
(1) by tumor inoculation in the right rear leg of nude mice, cell number needed for each tumor inoculation is 5 × 106A BEL-
7402 cells.When gross tumor volume reaches 100mm3During left and right, Experiment on therapy is carried out.
(2) nano metal sulfide material is prepared into the PBS solution of 4mg/mL, then 20 μ L of intratumor injection, used
The laser of 808nm is with 0.3W/cm2Power illumination tumor locus 10min.Begin to use vernier calliper within second day after laser irradiation
Ruler measures the size of tumour, uses the size of vernier caliper measurement tumour every three days backward, monitors two weeks always.Then put to death old
Mouse, takes out tumour and weighs, take pictures, set PBS buffer group, single laser irradiation group (NIR), single bismuth sulfide nano material
Material group (Bi2S3), single nano metal sulfide material group (BNN-Bi2S3), thermotherapy group (Bi2S3+ NIR) and thermotherapy and one
Nitrogen oxide coordinated groups (BNN-Bi2S3+NIR)。
Figure 11 shows the gross tumor volume result figure of different treatment groups, and the metal that can be seen that the present invention by the figure vulcanizes
Thing nano material can be used for thermotherapy and nitric oxide production synergistic treatment, and tumour growth is substantially inhibited, its effect is better than list
Only bismuth sulfide material thermotherapy group.
Specific embodiment described herein is only the spiritual example explanation to the present invention.Belonging to the present invention
Those skilled in the art can do described specific embodiment various modifications or additions or using similar
Mode substitutes, but without departing from spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of nano metal sulfide material, it is characterised in that including bismuth sulfide nano-rod and be coated on the bismuth sulfide
The high molecular material and nitric oxide donors of nanorod surfaces, the high molecular material are polyoxyethylene sorbitan laurate
Ester Tween-20, the nitric oxide donors include BNN.
2. a kind of nano metal sulfide material according to claim 1, it is characterised in that the bismuth sulfide nano-rod
Length is 10~100nm, and the draw ratio of the bismuth sulfide nano-rod is 5~20.
A kind of 3. nano metal sulfide material according to claim 1, it is characterised in that the nano metal sulfide
The hydration particle diameter of material is 20~150nm.
A kind of 4. nano metal sulfide material according to claim 1, it is characterised in that the nano metal sulfide
The potential of the aqueous systems of material is -5~-30mV.
5. a kind of preparation method of nano metal sulfide material as described in any one of Claims 1-4 claim, the party
Method includes the following steps：
Step 1, using bismuth salt as presoma, organic solvent is added, heating reaction a period of time, obtains solution；
Step 2, the sulphur powder for being dissolved in oleyl amine is added into the solution obtained by step 1, continues heating reaction certain time, cooling
Cooling, is made bismuth sulfide nano-rod；
Step 3, the bismuth sulfide nano-rod obtained by step (2) is dissolved in hexamethylene, adds Tween-20 and deionized water,
Heating evaporation removes hexamethylene, obtains the bismuth sulfide nano-rod of Tween-20 modifications；
Step 4, select nitric oxide donors to be uniformly mixed in ethanol with the bismuth sulfide nano-rod obtained by step (3), stir, obtain
To nano metal sulfide material.
A kind of 6. preparation method of nano metal sulfide material according to claim 5, it is characterised in that the step
(1) in, the bismuth salt is bismuth nitrate, bismuth chloride or 12 Bismuth Octoates；The organic solvent is in oleic acid, oleyl amine and octadecylene
It is one or more of；The molar concentration of bismuth element is 0.05~0.5mol/L in the solution of the step (1)；In the step (1)
Heating-up temperature be 100~200 DEG C；Reaction time in the step (1) is 10~30min.
A kind of 7. preparation method of nano metal sulfide material according to claim 5, it is characterised in that the step
(2) in reaction, the molar ratio of bismuth element and element sulphur is 1:(1~5)；Heating-up temperature in the step (2) for 150~
200℃；Reaction time in the step (2) is 1~10min.
A kind of 8. preparation method of nano metal sulfide material according to claim 5, it is characterised in that the step
(3) in, the ratio between the concentration of the bismuth sulfide nano-rod and the volume of Tween-20 are 1:2 to 1:5；It is described reaction cyclohexane with
The volume ratio of deionized water is 1:2 to 1:5.
A kind of 9. preparation method of nano metal sulfide material according to claim 5, it is characterised in that the step
(4) nitric oxide donors in are any one or more in BNN and its derivative, and nitric oxide donors are added the second
After in alcohol, the concentration of nitric oxide donors is 0.1~4.0mmol/L；Mixing time in the step (4) is 4~24h.
10. a kind of application process of nano metal sulfide material as described in any one of Claims 1-4 claim, its
It is characterized in that, this method is by the way that the nano metal sulfide material is combined with treating the method for tumour, to suppress tumour
The growth of cell.
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