CN106517356B - A kind of sheet Cu9Fe9S16The preparation method of nano flower - Google Patents
A kind of sheet Cu9Fe9S16The preparation method of nano flower Download PDFInfo
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- CN106517356B CN106517356B CN201611235813.4A CN201611235813A CN106517356B CN 106517356 B CN106517356 B CN 106517356B CN 201611235813 A CN201611235813 A CN 201611235813A CN 106517356 B CN106517356 B CN 106517356B
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- 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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Abstract
The present invention relates to a kind of sheet Cu9Fe9S16The preparation method of nano flower, including：Molysite and manganese salt are scattered in solvent, stirred, adds two citric acid monohydrate trisodiums, stirring, then adds sodium acetate, is uniformly mixed after 180~240 DEG C of 6~8h of solvent thermal reaction, centrifuges, washing, obtains Fe2MnO4It is nanocrystalline；By Fe2MnO4It is nanocrystalline to be dispersed in water, add (NH4)2S solution, ultrasonic disperse, is dispersed again in water after centrifuge washing, obtains dispersion liquid；Copper salt solution is added in above-mentioned dispersion liquid, ultrasonic disperse, centrifuge washing, to obtain the final product.The method of the present invention is simple, and safety and environmental protection, cost is low, easily operated, obtained sheet Cu9Fe9S16Near infrared light effectively can be converted into heat by nano flower, while have NMR imaging effect, and the photo-thermal therapy and diagnosis to cancer have extremely wide application prospect.
Description
Technical field
Preparation and its application field the invention belongs to optical-thermal conversion material, more particularly to a kind of sheet Cu9Fe9S16Nanometer
Colored preparation method.
Background technology
Photo-thermal ablation, as a kind of new methods for the treatment of cancer, is widely paid close attention in recent years.Selection is suitable
Optical-thermal conversion material it is particularly important that.Current optical-thermal conversion material mainly has four major classes：It is metal matrix photothermal transition material, carbon-based
Optical-thermal conversion material, organic compound optical-thermal conversion material, semiconductor optical-thermal conversion material.And semiconductor optical-thermal conversion material,
The advantages that since its is cheap, stability is good, and photothermal conversion efficiency is high, and absorption spectrum adjusts, is greatly developed.
Especially a kind of ternary compound based on copper sulfide, they can not only have as copper sulfide surface etc. from
Sub-resonance absorbs, and luminous energy effectively can be converted to thermal energy, high heating ablation cancer cell；Meanwhile also have another change
The property of compound.Ferro element, due to its good magnetic characteristic and Biological essentiality, is widely used in Nano medication.Wherein,
A kind of copper sulphide nano of Fe2O3 doping is brilliant, i.e. Cu5FeS4, developed and applied to the imaging and treatment of tumour.However, close
Higher into used pyrolysismethod temperature, obtained product has hydrophobicity, needs further hydrophilic modifying.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of sheet Cu9Fe9S16The preparation method of nano flower, this method
Required raw material are easy to get, are cheap, synthetic method is gentle, further hydrophilic modifying is not required.
A kind of sheet Cu of the present invention9Fe9S16The preparation method of nano flower, including：
(1) molysite and manganese salt are scattered in solvent, stirred (80 DEG C), added two citric acid monohydrate trisodiums, stirred at 80 DEG C
After mixing 1h, sodium acetate is then added, is uniformly mixed (30min), after 180~240 DEG C of 6~8h of solvent thermal reaction, from
The heart, washing, obtains Fe2MnO4It is nanocrystalline；
(2) by the Fe in step (1)2MnO4It is nanocrystalline to be dispersed in water, add (NH4)2S solution, ultrasonic disperse, centrifugation
It is dispersed again in after washing in water, obtains dispersion liquid；
(3) copper salt solution is added in the dispersion liquid in step (2), ultrasonic disperse, centrifuge washing, obtains sheet
Cu9Fe9S16Nano flower.
Molysite in the step (1), manganese salt, the molar ratio of two citric acid monohydrate trisodiums and sodium acetate are 0.67：0.33：
0.4： 3.
The ratio of solvent and molysite is 10ml in the step (1)：0.67mmol；Wherein, solvent is diglycol.
Molysite is FeCl in the step (1)3·6H2O or Fe2(SO4)3；Manganese salt is MnCl2·4H2O or MnSO4·H2O。
Fe in the step (2)2MnO4Nanocrystalline and (NH4)2The ratio of S solution is 2.5mg：10~30 μ L.
(the NH4)2The concentration of S solution is 22wt%, and solvent is water.
The concentration of dispersion liquid is 0.25~0.32mg/ml in the step (2).
The time of ultrasonic disperse is 5~10min in the step (2) and step (3).
Mantoquita and Fe in the step (3)2MnO4Nanocrystalline molar ratio is 1:1.
The concentration of copper salt solution is 5.425mmol/mL in the step (3)；The copper salt solution and dispersion liquid
Volume ratio is 1：5；Wherein, mantoquita CuCl2Or CuSO4。
Sheet Cu in the step (3)9Fe9S16Nano flower is applied to the preparation of photo-thermal therapy reagent.
The sheet Cu9Fe9S16The size of nano flower is 300~600nm.
The sheet Cu9Fe9S16Nano flower has good absorption near infrared region, is treated available for photothermal conversion.
The middle sheet Cu of the present invention9Fe9S16Nano flower has good near infrared absorption, Ke Yizuo due to copper ion defect
For a kind of photo-thermal therapy reagent.Moreover, the presence of ferro element makes it have the effect of NMR imaging in material, available for tumour
Diagnosis and positioning, photo-thermal therapy and diagnosis to cancer have extremely wide application prospect.
In 0.7W cm-2980nm laser irradiation under, deionized water about increases 10 DEG C in 5min；It is and of the invention
Cu9Fe9S16The temperature of dispersion liquid (1mg/mL) is raised to more than 60 DEG C from 20 DEG C, it is sufficient to high heat-killed cancer cell.
Beneficial effect
Sheet Cu prepared by the present invention9Fe9S16Nano flower, can be applied to the diagnose and treat field of cancer；The preparation side
Method have the advantages that environmental-friendly, required raw material be easy to get, be cheap, operating process it is easy.
Brief description of the drawings
Fig. 1 is the Fe prepared in embodiment 12MnO4Nanocrystalline scanning electron microscope (SEM) photograph；
Fig. 2 is the Fe prepared in embodiment 12MnO4Nanocrystalline XRD diagram piece；
Fig. 3 is the sheet Cu prepared in embodiment 19Fe9S16The scanning electron microscope (SEM) photograph of nano flower；
Fig. 4 is the sheet Cu prepared in embodiment 19Fe9The XRD diagram piece of S16 nano flowers；
Fig. 5 is the Fe prepared in embodiment 12MnO4Nanocrystalline and sheet Cu9Fe9S16The ultra-violet absorption spectrum of nano flower；
Fig. 6 is the sheet Cu prepared in embodiment 19Fe9S16Nano flower and water are 0.7W cm in power-2980nm laser
The lower temperature-time curve of device irradiation.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people 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
Scope.
Embodiment 1
Take 0.67mmol FeCl3·6H2O and 0.33mmol MnCl2·4H2O is scattered in 10mL diglycols,
Stir at 80 DEG C, addition 0.4mmol two citric acid monohydrate trisodiums, stirring 1h, addition 3mmol sodium acetates, after 30min, be transferred to
In ptfe autoclave, 6h is reacted at 200 DEG C.Centrifugation is washed with deionized 3 times, obtains Fe2MnO4It is nanocrystalline.Such as Fig. 1
It is shown, it is the scanning electron microscope (SEM) photograph of sample, particle size is 200-400nm.Fig. 2 is the XRD pictures of sample, with Fe2MnO4(PDF
No.10-0319 standard x RD peaks) correspond, and sample prepared by explanation is Fe2MnO4。
Take the obtained Fe of 2.5mg2MnO4It is nanocrystalline, it is dispersed in 10mL water, adds 10 μ L (NH4)2S solution
(22wt%), ultrasonic disperse 5min.Centrifugation is washed with deionized 3 times, is scattered in 10mL water.
Take 2mL CuCl2Dispersion liquid (5.425mmol/L), is added in above-mentioned gained dispersion liquid, ultrasonic disperse 10min.
Centrifugation is washed with deionized 3 times, obtains sheet Cu9Fe9S16Nano flower.Such as the scanning electron microscope (SEM) photograph of Fig. 3, it can be seen that sample becomes
For the nano flower of diameter about 500nm.XRD diagram piece shown in Fig. 4 further proves that obtained product is Cu9Fe9S16。
Fe is taken respectively2MnO4And Cu9Fe9S16Aqueous dispersions (1mg/mL) 3mL, UV absorption is surveyed in ultraviolet spectrometer,
As shown in Figure 5.As can be seen that relative to Fe2MnO4, Cu9Fe9S16There is good absorption near infrared region.Then, by 100 μ
L Cu9Fe9S16Dispersion liquid and water use 0.7W cm respectively-2980nm laser illuminations, and with thermal infrared imaging instrument record supervise
Control solution temperature change, such as Fig. 6.In 5min, the temperature of water increases about 10 DEG C；And under the same terms, Cu9Fe9S16It is scattered
Liquid temperature degree has been increased to 63 DEG C, this high temperature can effectively kill cancer cell.
Embodiment 2
Take 0.67mmol FeCl3·6H2O and 0.33mmol MnCl2·4H2O is scattered in 20mL diglycols,
Stir at 80 DEG C, addition 0.4mmol two citric acid monohydrate trisodiums, stirring 1h, addition 3mmol sodium acetates, after 30min, be transferred to
In ptfe autoclave, 6h is reacted at 240 DEG C.Centrifugation is washed with deionized 3 times, obtains Fe2MnO4It is nanocrystalline.
Take the obtained Fe of 2.5mg2MnO4It is nanocrystalline, it is dispersed in 10mL water, adds 10 μ L (NH4)2S solution
(22wt%), ultrasonic disperse 8min.Centrifugation is washed with deionized 3 times, is scattered in 10mL water.
Take 2mL CuCl2Dispersion liquid (5.425mmol/L), is added in above-mentioned gained dispersion liquid, ultrasonic disperse 8min.From
The heart is washed with deionized 3 times, obtains sheet Cu9Fe9S16Nano flower.
Embodiment 3
Take 0.67mmol FeCl3·6H2O and 0.33mmol MnCl2·4H2O is scattered in 10mL diglycols,
Stir at 80 DEG C, addition 0.4mmol two citric acid monohydrate trisodiums, stirring 1h, addition 3mmol sodium acetates, after 30min, be transferred to
In ptfe autoclave, 6h is reacted at 200 DEG C.Centrifugation is washed with deionized 3 times, obtains Fe2MnO4It is nanocrystalline.
Take the obtained Fe of 2.5mg2MnO4It is nanocrystalline, it is dispersed in 10mL water, adds 20 μ L (NH4)2S solution
(22wt%), ultrasonic disperse 10min.Centrifugation is washed with deionized 3 times, is scattered in 10mL water.
Take 2mL CuCl2Dispersion liquid (5.425mmol/L), is added in above-mentioned gained dispersion liquid, ultrasonic disperse 5min.From
The heart is washed with deionized 3 times, obtains sheet Cu9Fe9S16Nano flower.
Embodiment 4
Take 0.67mmol FeCl3·6H2O and 0.33mmol MnCl2·4H2O is scattered in 10mL diglycols,
Stir at 80 DEG C, addition 0.4mmol two citric acid monohydrate trisodiums, stirring 1h, addition 3mmol sodium acetates, after 30min, be transferred to
In ptfe autoclave, 6h is reacted at 200 DEG C.Centrifugation is washed with deionized 3 times, obtains Fe2MnO4It is nanocrystalline.
Take the obtained Fe of 2.5mg2MnO4It is nanocrystalline, it is dispersed in 10mL water, adds 10 μ L (NH4)2S solution
(22wt%), ultrasonic disperse 10min.Centrifugation is washed with deionized 3 times, is scattered in 10mL water.
Take 2mL CuSO4Dispersion liquid (5.425mmol/L), is added in above-mentioned gained dispersion liquid, ultrasonic disperse 5min.From
The heart is washed with deionized 3 times, obtains sheet Cu9Fe9S16Nano flower.
Claims (9)
- A kind of 1. sheet Cu9Fe9S16The preparation method of nano flower, including：(1) molysite and manganese salt are scattered in solvent, stirred, add two citric acid monohydrate trisodiums, stirring, then adds acetic acid Sodium, is uniformly mixed after 180~240 DEG C of 6~8h of solvent thermal reaction, centrifuges, washing, obtains Fe2MnO4It is nanocrystalline, wherein solvent For diglycol；(2) by the Fe in step (1)2MnO4It is nanocrystalline to be dispersed in water, add (NH4)2S solution, ultrasonic disperse, after centrifuge washing It is dispersed again in water, obtains dispersion liquid, wherein Fe2MnO4Nanocrystalline and (NH4)2The ratio of S solution is 2.5mg：10~30 μ L, (NH4)2The concentration of S solution is 22wt%；(3) copper salt solution is added in the dispersion liquid in step (2), ultrasonic disperse, centrifuge washing, obtains sheet Cu9Fe9S16Nano flower.
- A kind of 2. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (1) molysite in, manganese salt, the molar ratio of two citric acid monohydrate trisodiums and sodium acetate are 0.67：0.33：0.4：3.
- A kind of 3. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (1) ratio of solvent and molysite is 10ml in：0.67mmol.
- A kind of 4. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (1) molysite is FeCl in3·6H2O or Fe2(SO4)3；Manganese salt is MnCl2·4H2O or MnSO4·H2O。
- A kind of 5. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (2) (NH in4)2The solvent of S solution is water.
- A kind of 6. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (2) concentration of dispersion liquid is 0.25~0.32mg/ml in.
- A kind of 7. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (3) mantoquita and Fe in2MnO4Nanocrystalline molar ratio is 1:1.
- A kind of 8. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (3) concentration of copper salt solution is 5.425mmol/L in；Wherein, mantoquita CuCl2Or CuSO4。
- A kind of 9. sheet Cu according to claim 19Fe9S16The preparation method of nano flower, it is characterised in that the step (3) sheet Cu in9Fe9S16Nano flower is applied to the preparation of photo-thermal therapy reagent.
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| CN110101860B (en) * | 2019-04-28 | 2021-09-17 | 上海工程技术大学 | Bismuth-doped metal sulfide nanoflower and preparation method thereof |
| CN110841678A (en) * | 2019-10-11 | 2020-02-28 | 沈阳化工大学 | g-C3N4/Cu5FeS4Preparation method of visible light photocatalyst |
| CN110639016B (en) * | 2019-11-05 | 2021-10-08 | 安徽大学 | Preparation method and application of disulfide SiO 2-packaged Ni-Mn-B nanoflower spherical material |
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