CN110156066A - A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy - Google Patents
A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy Download PDFInfo
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- CN110156066A CN110156066A CN201910371146.XA CN201910371146A CN110156066A CN 110156066 A CN110156066 A CN 110156066A CN 201910371146 A CN201910371146 A CN 201910371146A CN 110156066 A CN110156066 A CN 110156066A
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- nano
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- copper sulfide
- thermal therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of preparation methods of nano-copper sulfide applied to tumor thermal therapy characterized by comprising step 1: copper chloride dihydrate and polyethylene glycol being dissolved in deionized water, copper chloride solution is obtained；Step 2: nine water vulcanized sodium being dissolved in deionized water and obtain sodium sulfide solution；Step 3: sodium sulfide solution being added in copper chloride solution using peristaltic pump under magnetic stirring, after being added dropwise to complete, continues 20~40min of stirring；The solution that stirring is completed is put into baking oven, sealing thermal insulation, is taken out, separation is obtained by drying to arrive nano-copper sulfide particle by obtained precipitating ethanol washing.Photo-thermal effect of the present invention is fabulous.
Description
Technical field
The present invention relates to field of nanometer material technology and photothermal conversion field, and in particular to a kind of applied to tumor thermal therapy
Nano-copper sulfide preparation method.
Background technique
Copper sulfide is a kind of inorganic mineral existing for nature, is one of the substance of most indissoluble in dark brown.In recent years
Next, research-on-research personnel have found that copper sulphide nano crystalline substance (nano semiconductor material) has extraordinary nearly red absorption, catalysis and resists
The function of bacterium.Therefore the use for copper sulphide nano crystalline substance in oncotherapy has been started.By physics and chemistry institute, the Chinese Academy of Sciences, California, USA
University, branch school, Los Angeles and the Italian Institute of Technology find after studying jointly: the brilliant owned smooth light and heat power of copper sulphide nano
Double effect.It is compared to the photo-thermal therapy of traditional gold nanoparticle, not only price is low for copper sulphide nano crystalline substance, but also close red
Outer absorptance gold nanocrystals are stronger.
The synthesis of nano-copper sulfide specifically includes that hydro-thermal method, ultrasonic, direct precipitation method and template etc..These
The nano-copper sulfide of method synthesis has different morphologies, including flake nano copper sulfide, cage-shaped nano copper sulfide, rod-like nano sulphur
Change copper, ball accommodates grain of rice copper sulfide and hollow shape nano-copper sulfide etc..At present in research using it is more be thiocarbamide hydro-thermal method and
It is brilliant that oleic acid oleyl amine method synthesizes copper sulphide nano.Its synthesis process is in contrast comparatively laborious, and is related in reaction process organic
The use of solvent, nano-copper sulfide unfriendly to environment and final there is pattern unevenly and hydrophily is poor.In
State patent CN201410617810 describes a kind of nano-copper sulfide particle used for photocatalysis, not only needs in the process
Pyroreaction, it is also necessary to right using organic matters such as ether, 1- (2- methoxyl group) imidazoles hydrogen chlorate and iodine ethyl phosphonic acid diethylesters
Environmental pollution is larger, and preparation time is longer at high cost.It is multiple that Chinese patent CN201611023748 describes a kind of copper sulphide nano
The preparation of condensation material has used the materials such as oleyl amine oleic acid in the process and has needed repeatedly growth.
It is to have superpower near-infrared photothermal conversion efficiency because of nano-copper sulfide why nano-copper sulfide, which attracts attention,
The near infrared light of 808nm can be converted to heat under extremely dilute concentration.Also with for human body in tumor thermal therapy
Near infrared light is converted to heat by means of nano-copper sulfide and kills cancer by the preferable near infrared light tumor locus of penetration performance
Cell.
Summary of the invention
It is an object of the present invention to provide a kind of systems of the fabulous nano-copper sulfide applied to tumor thermal therapy of photo-thermal effect
Preparation Method.
In order to achieve the above object, the present invention provides a kind of preparations of nano-copper sulfide applied to tumor thermal therapy
Method characterized by comprising
Step 1: copper chloride dihydrate and polyethylene glycol being dissolved in deionized water, copper chloride solution is obtained；
Step 2: nine water vulcanized sodium being dissolved in deionized water and obtain sodium sulfide solution；
Step 3: sodium sulfide solution being added in copper chloride solution using peristaltic pump under magnetic stirring, is added dropwise to complete
Afterwards, continue 20~40min of stirring；The solution that stirring is completed is put into baking oven, sealing thermal insulation, is taken out, separation will be obtained
Precipitating ethanol washing, it is obtained by drying to arrive nano-copper sulfide particle.
Preferably, in the copper chloride solution copper chloride dihydrate, polyethylene glycol and deionized water mass parts ratio are as follows:
1:3~8:50~80.
Preferably, in the sodium sulfide solution vulcanized sodium and deionized water mass parts ratio are as follows: 1:10~20.
Preferably, the sodium sulfide solution volume in the step 3 and copper chloride solution volume ratio 1:2-3.
Preferably, the rate of addition of the peristaltic pump is in 5-13mL/h.
Preferably, the agitating mode in the step 3 uses magnetic agitation, mixing speed 200r/min.
Preferably, the oven temperature is 45-50 DEG C, and soaking time is 3-5 hours.
Preferably, the separation uses centrifugation, the revolving speed 6000-8000r/min of centrifugation, time 5-10min.
Preferably, the temperature of the drying is 50 DEG C, and the time is 12 hours.
Compared with prior art, the beneficial effects of the present invention are:
1) organic solvent is not used in reaction process, and reacts and is directly reacted using zwitterion, speed is fast.
2) the nano-copper sulfide particle morphology that reaction obtains is uniform, and partial size is between 50-60nm.
3) nano-copper sulfide that reaction obtains possesses very efficient photothermal conversion effect, and 53 can be warming up in 120s
℃。
4) nano-copper sulfide particle uniformity prepared in the present invention is good, and good dispersion, while in preparation process not
It is related to the use of organic solvent, consersion unit requires the photo-thermal effect of low and final nanoparticle fabulous.
Detailed description of the invention
Fig. 1 is the transmission electrograph piece of the nano-copper sulfide of synthesis；
Fig. 2 is the infrared camera screenshot of nano-copper sulfide photothermal conversion；
The nano-copper sulfide that Fig. 3 is 200 μ g/mL is 1w/cm in power2808nm near infrared light under heating it is bent
Line chart；
The X-ray diffraction curve for the nano-copper sulfide that Fig. 4 is.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy, specific steps are as follows: weigh the poly- second of 3g
Glycol (average molecular weight 500), the copper chloride dihydrate of 0.8g are put into the beaker of 100mL, and deionized water 50mL is added, sufficiently stirs
Copper chloride solution is obtained after mixing dissolution.It weighs nine water vulcanized sodium of 12g to be dissolved into the deionized water of 200mL, obtains vulcanized sodium water
The vulcanized sodium of 20mL is added using peristaltic pump in 2 hours at magnetic agitation (200r/min) into copper chloride solution for solution
Solution after being added dropwise to complete, continues to be stirred to react half an hour.45 DEG C of baking oven is put into after then beaker is sealed using preservative film
In, it after keeping the temperature 4 hours, takes out, centrifuge separation, three times with ethanol washing by gained precipitating, centrifugation, by obtained solid at 50 DEG C
Baking oven in overnight dry (12 hours), obtain black bulk nano-copper sulfide particle.According to X-ray diffraction curve in Fig. 4, have
8 different diffraction maximums are right respectively positioned at 10.81,27.68,29.28,31.78,32.85,47.94,52.71 and 59.35 °
(002) is answered, (101), (102), (103), (006), (110), (108) and (116) crystal face, according to (JCPDS No.06-0464)
Standard card show that product is copper sulfide.
The transmission electrograph piece of the nano-copper sulfide of synthesis is as shown in Figure 1, Fig. 2 is the infrared phase of nano-copper sulfide photothermal conversion
Machine screenshot；
Nano-copper sulfide particle is dispersed in water, the nano-copper sulfide dispersion liquid of 200 μ g/mL is obtained, is 1w/ in power
cm2808nm near infrared light under heating curve figure as shown in figure 3, being brought rapidly up in 120 seconds to 54 DEG C.
Embodiment 2
A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy, specific steps are as follows: weigh the poly- second of 5g
Glycol (average molecular weight 500), the copper chloride dihydrate of 0.8g are put into the beaker of 100mL, and deionized water 50mL is added, sufficiently stirs
Copper chloride solution is obtained after mixing dissolution.It weighs nine water vulcanized sodium of 12g to be dissolved into the deionized water of 200mL, obtains vulcanized sodium water
The vulcanized sodium of 20mL is added using peristaltic pump in 2 hours at magnetic agitation (200r/min) into copper chloride solution for solution
Solution after being added dropwise to complete, continues to be stirred to react half an hour.45 DEG C of baking oven is put into after then beaker is sealed using preservative film
In, it after keeping the temperature 4 hours, takes out, centrifuge separation, three times with ethanol washing by gained precipitating, centrifugation, by obtained solid at 50 DEG C
Baking oven in overnight dry (12 hours), obtain black bulk nano-copper sulfide particle
Embodiment 3
A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy, specific steps are as follows: weigh the poly- second of 5g
Glycol (average molecular weight 500), the copper chloride dihydrate of 1.0g are put into the beaker of 100mL, and deionized water 50mL is added, sufficiently stirs
Copper chloride solution is obtained after mixing dissolution.It weighs nine water vulcanized sodium of 12g to be dissolved into the deionized water of 200mL, obtains vulcanized sodium water
The vulcanization of 30mL is added using peristaltic pump in 2.5 hours at magnetic agitation (200r/min) into copper chloride solution for solution
Sodium solution after being added dropwise to complete, continues to be stirred to react half an hour.45 DEG C of baking oven is put into after then beaker is sealed using preservative film
In, it after keeping the temperature 4 hours, takes out, centrifuge separation, three times with ethanol washing by gained precipitating, centrifugation, by obtained solid at 50 DEG C
Baking oven in overnight dry (12 hours), obtain black bulk nano-copper sulfide particle.
Embodiment 4
A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy, specific steps are as follows: weigh the poly- second of 5g
Glycol (average molecular weight 500), the copper chloride dihydrate of 0.8g are put into the beaker of 100mL, and deionized water 60mL is added, sufficiently stirs
Copper chloride solution is obtained after mixing dissolution.It weighs nine water vulcanized sodium of 12g to be dissolved into the deionized water of 200mL, obtains vulcanized sodium water
The vulcanized sodium of 20mL is added using peristaltic pump in 2 hours at magnetic agitation (200r/min) into copper chloride solution for solution
Solution after being added dropwise to complete, continues to be stirred to react half an hour.45 DEG C of baking oven is put into after then beaker is sealed using preservative film
In, it after keeping the temperature 4 hours, takes out, centrifuge separation, three times with ethanol washing by gained precipitating, centrifugation, by obtained solid at 50 DEG C
Baking oven in overnight dry (12 hours), obtain black bulk nano-copper sulfide particle.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow those skilled in the art's energy
The solution contents of the present invention much of that are simultaneously implemented accordingly, and it is not intended to limit the scope of the present invention.It is each cited by the present invention
The bound of raw material and each raw material of the present invention, the bound of section value and technological parameter (such as temperature, time), area
Between value can realize the present invention, embodiment numerous to list herein.
Claims (9)
1. a kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy characterized by comprising
Step 1: copper chloride dihydrate and polyethylene glycol being dissolved in deionized water, copper chloride solution is obtained；
Step 2: nine water vulcanized sodium being dissolved in deionized water and obtain sodium sulfide solution；
Step 3: sodium sulfide solution is added in copper chloride solution using peristaltic pump under magnetic stirring, after being added dropwise to complete,
Continue 20~40min of stirring；The solution that stirring is completed is put into baking oven, sealing thermal insulation, is taken out, separation will be obtained heavy
It forms sediment and uses ethanol washing, it is obtained by drying to arrive nano-copper sulfide particle.
2. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The mass parts ratio of copper chloride dihydrate, polyethylene glycol and deionized water in the copper chloride solution stated are as follows: 1:3~8:50~80.
3. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The mass parts ratio of vulcanized sodium and deionized water in the sodium sulfide solution stated are as follows: 1:10~20.
4. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
Sodium sulfide solution volume and copper chloride solution volume ratio 1:2-3 in the step 3 stated.
5. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The rate of addition for the peristaltic pump stated is in 5-13mL/h.
6. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
Agitating mode in the step 3 stated uses magnetic agitation, mixing speed 200r/min.
7. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The oven temperature stated is 45-50 DEG C, and soaking time is 3-5 hours.
8. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The separation stated uses centrifugation, the revolving speed 6000-8000r/min of centrifugation, time 5-10min.
9. the preparation method applied to the nano-copper sulfide of tumor thermal therapy as described in claim 1, which is characterized in that institute
The temperature for the drying stated is 50 DEG C, and the time is 12 hours.
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Cited By (4)
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| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| CN112142090A (en) * | 2020-09-16 | 2020-12-29 | 上海应用技术大学 | Preparation method of blocky nano copper sulfide |
| CN112174190A (en) * | 2020-09-07 | 2021-01-05 | 湖北大学 | Preparation method of copper sulfide composite material |
| CN113881007A (en) * | 2021-11-03 | 2022-01-04 | 东南大学 | High-heat-conductivity and low-leakage photo-thermal conversion shaping phase-change material and preparation method thereof |
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| CN113881007A (en) * | 2021-11-03 | 2022-01-04 | 东南大学 | High-heat-conductivity and low-leakage photo-thermal conversion shaping phase-change material and preparation method thereof |
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