CN104961165A - Surface-modified ruthenium oxide hydrate, preparation thereof and application of surface-modified ruthenium oxide hydrate - Google Patents
Surface-modified ruthenium oxide hydrate, preparation thereof and application of surface-modified ruthenium oxide hydrate Download PDFInfo
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- CN104961165A CN104961165A CN201510349235.6A CN201510349235A CN104961165A CN 104961165 A CN104961165 A CN 104961165A CN 201510349235 A CN201510349235 A CN 201510349235A CN 104961165 A CN104961165 A CN 104961165A
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- oxide hydrate
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Abstract
The invention provides surface-modified ruthenium oxide hydrate, preparation thereof and application of the surface-modified ruthenium oxide hydrate. A preparation method is characterized by comprising the following steps of (1) weighing ruthenium trichloride hydrate (RuCl3 x H2O), adding water in the ruthenium trichloride hydrate, stirring the ruthenium trichloride hydrate in the water so as to dissolve the ruthenium trichloride hydrate, transferring the ruthenium trichloride hydrate in a polytetrafluoroethylene liner hydrothermal reaction kettle to perform hydrothermal reaction, cooling down the ruthenium trichloride hydrate to room temperature, centrifugally separating and washing the ruthenium trichloride hydrate to obtain the ruthenium oxide hydrate and dispersing the ruthenium oxide hydrate in water; and (2) performing ultrasound on obtained dispersed liquid at room temperature for the first time, adding polymer in the dispersed liquid, performing ultrasound for the second time, allowing reaction of the dispersed liquid at room temperature and centrifuging and washing the dispersed liquid to obtain the surface-modified ruthenium oxide hydrate. The surface-modified ruthenium oxide hydrate can be uniformly dispersed in phosphate buffer, has high biocompatibility and excellent solar-thermal conversion performance, and can serve as a near-infrared photo-thermal therapy preparation for in-vitro and in-vivo thermal therapy on cancers.
Description
Technical field
The invention belongs to preparation and the Application Areas thereof of ruthenium oxide hydrate, specifically relate to a kind of preparation method of ruthenium oxide hydrate of polyvinylpyrrolidone surface modification and the application near infrared light heat cure cancer thereof.
Background technology
Photo-thermal therapy is under the irradiation of near infrared light (700-1100nm), is heat energy by photothermal reagent by transform light energy, and then the emerging technology of cancer treatment of one making cancer cells heat dead.Because this technological operation is easy, be easy to features such as controlling, equipment is simple, with low cost, be more and more subject to the favor of scientist in recent years.Luminous energy is effectively converted into heat energy by the effect one that photothermal reagent plays most critical in the art.
More near infrared optical-thermal conversion material is had to be used as the thermotherapy of photothermal reagent application and cancer at present, as precious metal (gold and palladium) material.This kind of material is because of the local surface plasma resonance effect of its surface uniqueness, very strong absorption is had near infrared region, thus good photo-thermal conversion efficiency is shown, but expensive, factor limits its large-scale practical application in this field such as light stability is poor of this kind of material.Therefore, exploitation seeks that some are cheap, bio-compatibility good, photo-thermal conversion efficiency is high and the optical-thermal conversion material that light stability is strong is significant.
The price of ruthenium wants cheap many for the precious metals such as above gold and palladium, and the title complex of existing ruthenium is in the news for antineoplastic research, but does not have been reported at present as the research of photothermal reagent.The present invention has synthesized ruthenium oxide hydrate (RuO by simple hydro-thermal reaction
2xH
2o), this material shows very strong near-infrared absorption in aqueous, and has very high photo-thermal conversion efficiency.Improve the bio-compatibility of material by the method for surface modification, external photo-thermal experiment also shows: this material is 1.0W/cm in power density
2808 nano wave lengths laser irradiation under can kill cancer cells fast and effectively.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ruthenium oxide hydrate of surface modification, and it is used for thermotherapy cancer as the photothermal reagent that a class is novel.The present invention has the features such as synthetic method is simple, reaction raw materials is single, operating process is easy, environmental friendliness, can large-scale production and application.
In order to achieve the above object, the invention provides a kind of ruthenium oxide hydrate of surface modification, it is characterized in that, obtaining by using polymkeric substance to carry out surface modification to ruthenium oxide hydrate.
Present invention also offers the preparation method of the ruthenium oxide hydrate of above-mentioned surface modification, it is characterized in that, comprise the following steps:
Step 1: take raw material ruthenium trichloride hydrate (RuCl
3xH
2o) add water stirring and dissolving, proceeds in polytetrafluoroethylliner liner hydrothermal reaction kettle and carry out hydro-thermal reaction, after being cooled to room temperature, and centrifugation, washing, obtains ruthenium oxide hydrate, is scattered in water;
Step 2: the dispersion liquid of gained is carried out first time in room temperature ultrasonic, add polymkeric substance, it is ultrasonic to carry out second time, and room temperature reaction, through centrifugal, obtains the ruthenium oxide hydrate of surface modification after washing.
Preferably, described hydro-thermal reaction is carried out in air dry oven.
Preferably, the temperature of reaction of described hydro-thermal reaction is 160-200 DEG C, and the reaction times is 6-24 hour.
Preferably, ultrasonic time described first time is 0.5-2.0 hour, and ultrasonic power is 300W, described second time ultrasonic time be 0.5-2.0 hour, ultrasonic power is 300W.
Preferably, the reaction times of described room temperature reaction is 2-48 hour.
Preferably, the polymkeric substance in described step 2 is polyvinylpyrrolidone.
Preferably, in the dispersion liquid in described step 2, the ratio of ruthenium oxide hydrate and water is 1g: 50-200mL.
Preferably, the ruthenium oxide hydrate in the dispersion liquid in described step 2 and the weight ratio of polymkeric substance are 1: 0.5-20.0.
The ruthenium oxide hydrate that present invention also offers above-mentioned surface modification is preparing the application in cancer cells in vitro thermotherapy preparation as near infrared light thermal conversion reagent.
The application of the ruthenium oxide hydrate of a kind of surface modification of the present invention, described final product is 1.0W/cm at power
2under the laser irradiation of 808 nano wave lengths of power, cancer cells can be killed fast and effectively, develop ruthenium oxide hydrate optical-thermal conversion material first and be used for the treatment of cancer.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention has the features such as synthesis is simple, bio-compatibility is good about the preparation of ruthenium oxide hydrate material; The ruthenium oxide hydrate of surface modification prepared by the present invention, can be dispersed in phosphoric acid buffer, have good bio-compatibility, and shows excellent photothermal deformation performance, can as near infrared light heat cure preparation, application and inside and outside thermotherapy cancer.
(2) the ruthenium oxide hydrate material that prepared by the present invention shows very strong near infrared absorption characteristic, has potential using value in fields such as probe, photoelectrocatalysis, photothermal deformation;
(3) the ruthenium oxide hydrate material prepared of the present invention is under the laser irradiation of 808 nano wave lengths, there is very high photo-thermal conversion efficiency, solution temperature can be made to raise 5-50 DEG C, fast, efficiently can kill cancer cells, be used for wide application prospect at cancer therapy reverse side.
Accompanying drawing explanation
Fig. 1 is the RuO prepared in the present invention
2xH
2the TEM picture of O material under low power (a) and high power (b);
Fig. 2 is the RuO prepared in the present invention
2xH
2the XRD figure of O material;
Fig. 3 is the RuO prepared in the present invention
2xH
2intensification under the uv-absorbing figure (a) of O material and near infrared excite and temperature lowering curve figure (b);
Fig. 4 is the RuO prepared in the present invention
2xH
2the cytotoxicity (a) of the relative MCF-7 of O material and the external photo-thermal of Trypan Blue melt cancer cells figure (b);
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A ruthenium oxide hydrate for surface modification, obtains by using polyvinylpyrrolidone to carry out surface modification to ruthenium oxide hydrate.
The preparation method of the ruthenium oxide hydrate of described surface modification is:
(1) RuCl of 0.19g is taken
3xH
2o, add water 50mL, after stirring at room temperature 0.5 hour is dissolved, proceed to and be placed in air dry oven in 60mL polytetrafluoroethylliner liner hydrothermal reaction kettle and carry out hydro-thermal reaction, temperature of reaction is 180 DEG C, reaction times is 24 hours, after being cooled to room temperature, centrifugation, washes three times by the solid of gained, centrifugation, obtains the ruthenium oxide hydrate nanometer particle that diameter is 2-5nm; Getting 0.1g ruthenium oxide hydrate nanometer uniform particle is scattered in the water of 20mL, and refrigerator cold-storage is for subsequent use;
The TEM figure of the ruthenium oxide hydrate nanometer particle of gained is as shown in (a) He (b) in Fig. 1.Carry out x-ray diffraction experiment after getting the lyophilize of ruthenium oxide hydrate nanometer particle, product crystalline phase and standard oxidation ruthenium data coincide (as shown in Figure 2).
(2) 2.0mL above-mentioned ruthenium oxide hydrate nanometer particle dispersion is pipetted, add 20mL water, be under the condition of 300W in room temperature ultrasonic 0.5 hour at ultrasonic power, add 0.2g PVP-K30, be under the condition of 300W after ultrasonic 40 minutes at ultrasonic power, room temperature reaction 12 hours, through centrifugal, wash with water after obtain the ruthenium oxide hydrate of PVP surface modification, be scattered in phosphate buffered saline buffer (PBS) for subsequent use.
The ruthenium oxide hydrate of the PVP surface modification of gained can be good at being dispersed in PBS, and has very strong near-infrared absorption performance (as Suo Shi (a) in Fig. 3).
Embodiment 2
The method identical with embodiment 1 is adopted to prepare the ruthenium oxide hydrate of PVP surface modification, being scattered in phosphate buffered saline buffer (PBS) and obtaining the PBS dispersion liquid that ruthenium oxide concentration is 1600ppm (1ppm=1mg/kg), is 1.0W/cm by power density
2808nm laser irradiation 5 minutes, water temperature directly increases 25.5 degrees Celsius (as Suo Shi (b) in Fig. 3).
Embodiment 3
By 2 × 10
4individual MCF-7 cell is cultivated and is obtained MCF-7 cell culture fluid in DMEM cell culture medium under 37 DEG C of conditions.The method identical with embodiment 1 is adopted to prepare the ruthenium oxide hydrate of PVP surface modification, be scattered in phosphate buffered saline buffer (PBS), each 10 microlitres of PBS dispersion liquid getting serial different ruthenium oxide solubility are added in 0.1mL MCF-7 cell culture fluid respectively hatches 24 hours under 37 DEG C of conditions, the toxicity (as Suo Shi (a) in Fig. 4) of mtt assay assessment ruthenium oxide hydrate, the bio-compatibility of material is good.
The PBS dispersion liquid being 16mg/mL by 10 microlitre ruthenium oxide hydrate concentration is added in 0.1mL MCF-7 cell culture fluid, and hatching under 37 DEG C of conditions after 2 hours by power density is 1.0W/cm
2808nm laser irradiation 10 minutes, can find out (as Suo Shi (b) in Fig. 4) through the inspection of trypan blue dye, the basic death completely of cancer cells.
Claims (10)
1. a ruthenium oxide hydrate for surface modification, is characterized in that, obtains by using polymkeric substance to carry out surface modification to ruthenium oxide hydrate.
2. the preparation method of the ruthenium oxide hydrate of surface modification according to claim 1, is characterized in that, comprise the following steps:
Step 1: take raw material ruthenium trichloride hydrate and to add water stirring and dissolving, proceed in polytetrafluoroethylliner liner hydrothermal reaction kettle and carry out hydro-thermal reaction, after being cooled to room temperature, centrifugation, washing, obtains ruthenium oxide hydrate, is scattered in water;
Step 2: the dispersion liquid of gained is carried out first time in room temperature ultrasonic, add polymkeric substance, it is ultrasonic to carry out second time, and room temperature reaction, through centrifugal, obtains the ruthenium oxide hydrate of surface modification after washing.
3. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, described hydro-thermal reaction is carried out in air dry oven.
4. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, the temperature of reaction of described hydro-thermal reaction is 160-200 DEG C, and the reaction times is 6-24 hour.
5. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, ultrasonic time described first time is 0.5-2.0 hour, and ultrasonic power is 300W, described second time ultrasonic time be 0.5-2.0 hour, ultrasonic power is 300W.
6. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, the reaction times of described room temperature reaction is 2-48 hour.
7. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, the polymkeric substance in described step 2 is polyvinylpyrrolidone.
8. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, in the dispersion liquid in described step 2, the ratio of ruthenium oxide hydrate and water is 1g: 50-200mL.
9. the preparation method of the ruthenium oxide hydrate of surface modification as claimed in claim 2, it is characterized in that, the ruthenium oxide hydrate in the dispersion liquid in described step 2 and the weight ratio of polymkeric substance are 1: 0.5-20.
10. the ruthenium oxide hydrate of the surface modification described in claim 1 is preparing the application in cancer cells in vitro thermotherapy preparation as near infrared light thermal conversion reagent.
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| CN108622947A (en) * | 2017-03-24 | 2018-10-09 | 北京化工大学 | A kind of nanometer titanium dioxide ruthenium liquid dispersion and preparation method thereof |
| CN109771645A (en) * | 2019-03-07 | 2019-05-21 | 广西师范大学 | A kind of preparation and its application of the compound ovalbumin nano material of ruthenic oxide |
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Cited By (4)
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| CN109771645A (en) * | 2019-03-07 | 2019-05-21 | 广西师范大学 | A kind of preparation and its application of the compound ovalbumin nano material of ruthenic oxide |
| CN109771645B (en) * | 2019-03-07 | 2021-08-24 | 广西师范大学 | Preparation and application of ruthenium dioxide composite ovalbumin nano material |
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Application publication date: 20151007 |