CN103803632B - The preparation method of the coated photothermal deformation nano material of a kind of carbon - Google Patents
The preparation method of the coated photothermal deformation nano material of a kind of carbon Download PDFInfo
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- CN103803632B CN103803632B CN201410070626.XA CN201410070626A CN103803632B CN 103803632 B CN103803632 B CN 103803632B CN 201410070626 A CN201410070626 A CN 201410070626A CN 103803632 B CN103803632 B CN 103803632B
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Abstract
The invention discloses the preparation method of the coated photothermal deformation nano material of a kind of carbon, it comprises: step 1, to CuCl
22H
2tensio-active agent and Na is added in the distilled water solution of O
2s9H
2the distilled water solution of O, at room temperature stirs after 5 minutes and is warming up to 80-90 DEG C, stirs after 20-30 minute and obtains product, then with distilled water and methanol solution centrifugation washing several, after seasoning, obtains the coated CuS nano particle of organism part; Step 2, distilled water solution is adopted to dilute the coated CuS nano particle of above-mentioned organism part, after ultrasonic disperse, pour in hydrothermal reaction kettle, pyroreaction 4 ~ 6 hours at 195 ~ 215 DEG C, again with distilled water and methanol solution centrifugation washing several, after seasoning, obtain the coated CuS nano particle of carbon.Carbon coating layer prepared by the present invention significantly reduces the bio-toxicity of CuS, improves its biocompatibility, photo-thermal conversion efficiency, and can nanoparticle agglomerates be prevented, prevent the oxidation of nano particle, improve stability, and preparation technology is simple, can be used for photo-thermal therapy.
Description
Technical field
The invention belongs to photothermal deformation technical field of nanometer material preparation, relate to a kind of photothermal deformation nano composite material, specifically, relate to a kind of preparation method with the coated photothermal deformation nano material of carbon of near-infrared absorption function and photothermal deformation performance.
Background technology
Photothermal deformation nano material is a kind of Absorbable rod near infrared light, maybe can be produced the new function material of heat by plasma resonance with transition.As a new study hotspot, Chinese scholars is devoted to the synthesis of this material, it has purposes extremely widely at biomedical aspect, as medicament slow release, photo-thermal therapy and medical imaging etc., the research of association area also has greater advance, as: Xiamen University Zheng Nan peak teach problem group prepares a kind of novel nano palladium material of blueness, realizes photothermal, can directly apply to the near infrared light heat cure of tumour.AdvancedMaterials periodical is reported: near-infrared laser light energy conversion can be heat energy by nanometer gold shell material, and high-efficiency low-toxicity kills tumour cell.
Cupric sulfide, as a kind of important transient metal sulfide, is the multi-functional synthetic materials that a kind of chemical stability is good.Nano level CuS particle diameter is little, specific surface area large, has good optical absorption, can be used for photo-thermal therapy etc.When medium temperature is elevated to 42 DEG C, cancer cells just can be killed effectively, therefore metal Nano structure material noted in people to tumour or by intravenous injection, the nanostructure with targeting be transported in tumour, again by laser radiation tumor locus, just effectively can destroy tumor tissues, and very little to the healthy tissues wound of surrounding.It is reported, the CuS nano particle prepared by ligand exchange (ACS nanometer (Nano), 2011,5,9761-9771) efficiently solves the problem of its biocompatibility, but toxicity is large, and complicated process of preparation, limit its biologic applications.Therefore, explore a kind of CuS nano composite material of exploitation, while there is high light thermal conversion efficiency, effectively reduce bio-toxicity, significant at biomedical sector.
Summary of the invention
The object of the invention is to overcome above existing technological deficiency, develop a kind of photothermal deformation nano composite material, that is: carbon coated CuS photothermal deformation nano material, it has higher near-infrared absorption function and photo-thermal conversion efficiency, and significantly reduces bio-toxicity.
For achieving the above object, the invention provides the preparation method of the coated photothermal deformation nano material of a kind of carbon, the method comprises following steps:
Step 1, the CuS nano particle that precipitator method synthesis of organic substance part is coated: to CuCl
22H
2tensio-active agent and Na is added in the distilled water solution of O
2s9H
2the distilled water solution of O, at room temperature stirs after 5 minutes and is warming up to 80-90 DEG C, stirs after 20-30 minute and obtains product, then with distilled water and methanol solution centrifugation washing several, after seasoning, obtains the coated CuS nano particle of organism part;
Step 2, hydrothermal synthesis of carbon coated CuS nano particle: adopt the coated CuS nano particle of organism part that the distilled water solution dilution step 1 of sodium sulphite obtains, after ultrasonic disperse, pour in hydrothermal reaction kettle, pyroreaction 4 ~ 6 hours at 195 ~ 215 DEG C, again with distilled water and methanol solution centrifugation washing several, after seasoning, obtain the coated CuS nano particle of carbon.
The preparation method of the coated photothermal deformation nano material of above-mentioned carbon, wherein, described tensio-active agent adopts more than any one in sodium dimercaptosuccinate, glucose.Wherein, sodium dimercaptosuccinate reacts obtained by dimercaptosuccinic acid (DMSA) and sodium hydroxide.
The preparation method of the coated photothermal deformation nano material of above-mentioned carbon, wherein, in step 1, described tensio-active agent and CuCl
22H
2the mol ratio of O is 4-7:1, is preferably 5:1; The mol ratio of Cu and S element is 1:1 ~ 2.
The preparation method of the coated photothermal deformation nano material of above-mentioned carbon, wherein, in step 2, the coated CuS nano particle of the organism part that dilution step 1 obtains adopts in distilled water solution containing sodium sulphite; Further, the pH value of described sodium sulfide solution is 11-12.5; Be preferably 12.This sodium sulfide solution pH value is weakly alkaline, the CuS making DMSA coated disperse in the solution evenly, prevent the reunion of nano particle in carbonization process.
The present invention employs tensio-active agent in preparation process, after tensio-active agent adds, in solution, there occurs chemical reaction, defines the CuS nano particle that organism part is coated; In hydrothermal reaction process, the at high temperature carbonization of coated organic ligand, at the coated one deck carbon of spherical CuS nano grain surface, thus be converted to the coated CuS of carbon, significantly reduce the bio-toxicity of CuS, improve its biocompatibility, photo-thermal conversion efficiency, and can nanoparticle agglomerates be prevented, improve stability etc.Moreover, carbon coating layer also reduces the size of particle, solves a difficult problem for nanoparticle agglomerates, and prevents the oxidation of nano particle, improves stability.This carbon coated CuS nano material has higher near-infrared absorption performance and photo-thermal conversion efficiency, and biocompatibility is also fine, and preparation technology is simple, can be used for photo-thermal therapy etc.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the coated CuS nano material of carbon prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the coated CuS nano material of carbon prepared by the embodiment of the present invention 1.
Fig. 3 is the uv-visible absorption spectra figure of the coated CuS nano material of carbon prepared by the embodiment of the present invention 1.
Fig. 4 is the heating curve figure of the coated CuS nano material of carbon under 808nm laser radiation prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is further described.
Embodiment 1
CuCl is added in beaker
22H
2o (0.17g, 1mmol), and dissolve with 1000ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (0.9g, 5mmol), NaOH (0.4g, 10mmol), Na
2s9H
2o (0.24g, 1mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, be warming up to 85 DEG C, magnetic agitation obtains deep green product in 25 minutes, after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=12, after ultrasonic disperse, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 6 hours at 210 DEG C, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
High-resolution-ration transmission electric-lens (TEM) figure of the coated CuS nano particle of this carbon as shown in Figure 1, carbon coated CuS nano particle presents obvious globose nucleus shell structure, carbon coating layer thickness is about 1.6nm, this structure effectively improves photo-thermal conversion efficiency and the stability of CuS nano particle, and reduces its bio-toxicity.
As shown in Figure 2, the CuS standard spectrum collection of illustrative plates of (101), (102), (103) wherein, (006), (108) and (116) diffraction crystal face and hexagonal structure is substantially identical for the XRD spectra of the coated CuS nano particle of this carbon.In addition, do not observe as Cu
2the existence of the impurity peaks such as S, CuO and S, but cause diffraction peak intensity slightly to weaken due to the nanometer of CuS crystal, and there is relative broadening phenomenon.On the whole, carbon coated CuS nano particle still has higher purity and crystallinity.
As shown in Figure 3, carbon coated CuS nano particle has stronger absorption peak to the uv-visible absorption spectra figure of the coated CuS nano particle of this carbon near 920nm and 1070nm of near-infrared region, illustrates that it has good near-infrared absorption performance.
The heating curve figure of the coated CuS nano particle of this carbon under 808nm laser radiation as shown in Figure 4, under 808nm laser radiation, the coated CuS nano particle of carbon increases about 23 DEG C after 600 seconds, have higher photo-thermal conversion efficiency, and the temperature of control group distilled water does not change substantially.The concrete testing method of this heating curve figure is: be 1W/cm with power
2wavelength 808nm laser irradiation device irradiate the quartz container filling 1ml distilled water and the coated CuS nano particle of 2mg carbon (with the dispersion of 1ml distilled water) respectively, strength of current is 1.14A, and irradiation time is 600 seconds, records the temperature value of rising respectively.
Embodiment 2
CuCl is added in beaker
22H
2o (0.25g, 1.5mmol), and dissolve with 1000ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (1.25g, 7mmol), NaOH (0.4g, 10mmol), Na
2s9H
2o (0.36g, 1.5mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, be warming up to 90 DEG C, magnetic agitation obtains deep green product in 20 minutes, after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=11, after ultrasonic disperse, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 5 hours at 210 DEG C, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
Embodiment 3
CuCl is added in beaker
22H
2o (0.08g, 0.5mmol), and dissolve with 500ml distilled water, constantly stir and obtain light blue solution.Again by DMSA (0.45g, 2.5mmol), NaOH (0.2g, 5mmol), Na
2s9H
2o (0.12g, 0.5mmol) add successively in 5ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, be warming up to 85 DEG C, magnetic agitation obtains deep green product in 20 minutes, after distilled water and methanol solution centrifugation for several times, obtain the coated CuS nano particle of DMSA.Above-mentioned particle is joined in the 35ml sodium sulfide solution of pH=12.5, after ultrasonic disperse, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 5 hours at 210 DEG C, finally use distilled water and methanol solution centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
Embodiment 4
CuCl is added in beaker
22H
2o (0.17g, 1mmol), and dissolve with 1000ml distilled water, constantly stir and obtain light blue solution.Again by glucose (1.25g, 7mmol) and Na
2s9H
2o (0.24g, 1mmol) add successively in 10ml distilled water, after stirring, mixed solution is poured in above-mentioned light blue solution, and at room temperature stir after 5 minutes, be warming up to 90 DEG C, magnetic agitation obtains deep green product in 20 minutes, after distilled water centrifugation for several times, obtain the coated CuS nano particle of glucose.Dissolve above-mentioned particle with distilled water, after ultrasonic disperse, pour the hydrothermal reaction kettle of 50ml into, pyroreaction 5 hours at 190 DEG C, finally use distilled water centrifugation for several times, after seasoning, obtain the coated CuS nano particle of carbon.
The CuS nano particle that the carbon of embodiment 2-4 is coated also obtains TEM, XRD, uv-visible absorption spectra figure and the heating curve figure under 808nm laser radiation respectively, and its result is all similar with Fig. 1-4 respectively.
To sum up, the coated CuS nano particle of carbon provided by the invention significantly reduces the bio-toxicity of CuS, improves its biocompatibility, photo-thermal conversion efficiency, and can prevent nanoparticle agglomerates, improves stability.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (8)
1. a preparation method for the coated photothermal deformation nano material of carbon, it is characterized in that, the method comprises following steps:
Step 1, the CuS nano particle that precipitator method synthesis of organic substance part is coated: to CuCl
22H
2tensio-active agent and Na is added in the distilled water solution of O
2s9H
2the distilled water solution of O, at room temperature stirs after 5 minutes and is warming up to 80-90 DEG C, stirs after 20-30 minute and obtains product, then with distilled water and methanol solution centrifugation washing several, after seasoning, obtains the coated CuS nano particle of organism part;
Step 2, hydrothermal synthesis of carbon coated CuS nano particle: adopt the coated CuS nano particle of organism part that distilled water solution dilution step 1 obtains, after ultrasonic disperse, pour in hydrothermal reaction kettle, pyroreaction 4 ~ 6 hours at 195 ~ 215 DEG C, again with distilled water and methanol solution centrifugation washing several, after seasoning, obtain the coated CuS nano particle of carbon; Described tensio-active agent adopts sodium dimercaptosuccinate or glucose.
2. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 1, is characterized in that, described sodium dimercaptosuccinate reacts obtained by dimercaptosuccinic acid and sodium hydroxide.
3. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 1, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 4 ~ 7:1; The mol ratio of Cu and S element is 1:1 ~ 2.
4. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 3, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 4.5 ~ 6.5:1.
5. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 4, is characterized in that, in step 1, and described tensio-active agent and CuCl
22H
2the mol ratio of O is 5:1.
6. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 1, is characterized in that, in step 2, the coated CuS nano particle of the organism part that dilution step 1 obtains adopts in distilled water solution containing sodium sulphite.
7. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 6, it is characterized in that, in step 2, the pH value of described sodium sulfide solution is 11 ~ 12.5.
8. the preparation method of the coated photothermal deformation nano material of carbon as claimed in claim 7, it is characterized in that, in step 2, the pH value of described sodium sulfide solution is 12.
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| CN105036179A (en) * | 2015-04-29 | 2015-11-11 | 金华职业技术学院 | Method of preparing CdS nano particles through room-temperature solid-phase reaction |
| CN110156066A (en) * | 2019-05-06 | 2019-08-23 | 上海应用技术大学 | A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy |
| CN110713203B (en) * | 2019-11-20 | 2022-07-08 | 南京信息工程大学 | CuS/carbon black composite photothermal conversion material and preparation method thereof |
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| CN102219251B (en) * | 2011-03-30 | 2014-04-16 | 东华大学 | Copper sulfide superstructure and its application in improving near infrared thermal conversion efficiency |
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Inventor after: Li Xiaofeng Inventor after: Zhang Yingjie Inventor after: An Yan Inventor after: Tao Fujun Inventor after: Dong Lihua Inventor after: Yin Yansheng Inventor before: Zhang Yingjie Inventor before: Li Xiaofeng Inventor before: An Yan Inventor before: Tao Fujun Inventor before: Dong Lihua Inventor before: Yin Yansheng |
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