CN108079295B - Preparation method and application of boron-doped black zirconium dioxide nanoparticles - Google Patents
Preparation method and application of boron-doped black zirconium dioxide nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method and application of boron-doped black zirconium dioxide nanoparticles, wherein the preparation method comprises the steps of taking nano zirconium dioxide and sodium borohydride as raw materials, and modifying the raw materials through 3-aminopropyltriethoxysilane and hyaluronic acid to obtain the black zirconium dioxide nanoparticles, and the black zirconium dioxide nanoparticles can enter tumor cells to realize photo-thermal and photodynamic treatment effects. The raw materials required by the preparation method are cheap and easy to obtain, the preparation method is simple, the obtained product has good biocompatibility and water solubility, has strong absorption in ultraviolet, visible light and near infrared regions and good photothermal conversion efficiency, and can generate active oxygen under the illumination condition so as to be used for photothermal and photodynamic therapy. The boron-doped black zirconium dioxide nanoparticles prepared by the invention have wide application prospects in the aspects of photo-thermal and photodynamic treatment.
Description
Technical Field
The invention relates to preparation and application of nanoparticles, in particular to a preparation method and application of boron-doped black zirconium dioxide nanoparticles.
Background
Zirconium dioxide, which is a major oxide of zirconium, has been widely used in the fields of structural ceramics, sensors, solar cells, heat insulating materials, catalysts, etc. for the past few decades due to its excellent physical and chemical properties. However, the wider band gap determines that the zirconium dioxide can only absorb ultraviolet light which accounts for less than 5% of natural light, so that the improvement of the photocatalytic activity by doping and enhancing the light absorption performance of the zirconium dioxide is particularly important.
Photothermal therapy (PTT) is a therapeutic method for converting light energy into heat energy by a Photothermal conversion agent, thereby ablating tumor tissue. Photodynamic therapy (PDT) is a novel cancer treatment method in which Photodynamic agents generate active oxygen under irradiation of light, thereby killing tumor cells. Compared with the traditional operation treatment, chemotherapy and radiotherapy, the photothermal photodynamic therapy has the advantages of small wound, low toxicity and the like. The traditional photo-thermal photodynamic reagent mainly comprises gold nano materials, carbon nano materials and the like, and the nano materials have high cost, complex preparation, poor biocompatibility and no tumor targeting property, so that the application of the nano materials in the field of light treatment is greatly limited. Therefore, the development of new phototherapeutic materials is becoming a hotspot in current tumor therapy.
Disclosure of Invention
The invention aims to provide a preparation method and application of novel boron-doped black zirconium dioxide nanoparticles with photo-thermal and photodynamic treatment functions.
The technical scheme for realizing the purpose of the invention is as follows:
a preparation method of boron-doped black zirconium dioxide nanoparticles comprises the following steps:
(1) weighing a certain amount of nano zirconium dioxide and sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 2-6 h in a 500-700 ℃ tube furnace;
(3) washing the fired solid with distilled water and absolute ethyl alcohol respectively, centrifuging by using a centrifuge, and drying to obtain a black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, and simultaneously adding a certain amount of 3-aminopropyltriethoxysilane and hyaluronic acid and stirring for a period of time;
(5) dialyzing the stirred solution;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
The mass ratio of the nano zirconium dioxide to the sodium borohydride in the step (1) is 1: 0.2.
Washing with distilled water and absolute ethyl alcohol for 3 times respectively in the step (3), and centrifuging at 5000 r/min.
The 3-aminopropyltriethoxysilane added in the step (4) is 200 muL, and the mass ratio of the hyaluronic acid to the nano zirconium dioxide is 1: 1.
And (5) dialyzing by adopting a dialysis bag with the molecular weight cutoff of 10000 Da.
The invention also aims to apply the prepared boron-doped black zirconium dioxide nanoparticles to photo-thermal and photodynamic tumor treatment.
The boron-doped black zirconium dioxide nanoparticles prepared by the method are prepared into aqueous solutions with the concentrations of 25 mug/mL, 50 mug/mL and 125 mug/mL, and lasers (1W cm, 1 nm, 808 nm and 1064 nm) are respectively used-2) And (4) irradiating, and recording the temperature of the solution by an infrared thermal imaging instrument. The nanoparticle aqueous solutions with three concentrations have a photo-thermal effect and show concentration dependence. When the concentration reaches 125 mug/mL, the temperature of the solution can be raised to more than 50 ℃ under the laser irradiation of three wavelengths, and experiments prove that the prepared boron-doped black zirconium dioxide nanoparticles can be applied to photo-thermal and photodynamic tumor treatment.
The active Oxygen detection Kit (Reactive Oxygen specifices Assay Kit) is a Kit for detecting active Oxygen by using a fluorescent probe DCFH-DA. DCFH-DA has no fluorescence, can freely pass through cell membranes, and can be hydrolyzed by intracellular esterase to generate DCFH after entering cells. DCFH, however, does not permeate the cell membrane, thus allowing the probe to be easily loaded into the cell. Intracellular reactive oxygen species can oxidize non-fluorescent DCFH to produce fluorescent DCF. Adding 125 mug/mL of nanoparticles into the tumor cells for incubation for a period of time, and then adding DCFH-DA for incubation. After incubation is finished, 1064 nm laser is used for irradiating for 5 min, a fluorescence inverted microscope is used for observing cells, and the fluorescent intensity in the cells after illumination is far higher than that before illumination, so that the fact that a large amount of active oxygen is generated in the nanoparticles in the cells after 1064 nm laser irradiation is proved.
The boron-doped black zirconium dioxide nanoparticles prepared by the invention show photo-thermal and photodynamic treatment effects under the irradiation of near-infrared light with different wavelengths, have good photo-stability and have the potential of being applied to photo-thermal and photodynamic treatment of tumors.
The invention has the advantages that: the raw materials needed for preparation are cheap and easy to obtain; the prepared black zirconium dioxide nanoparticles have good photo-thermal stability, water solubility and biocompatibility; the near-infrared absorption is good, and the photo-thermal conversion efficiency is good; has good photodynamic effect; has the potential of being applied to photo-thermal and photodynamic tumor treatment.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1:
a preparation method of boron-doped black zirconium dioxide nanoparticles comprises the following steps:
(1) weighing 1g of nano zirconium dioxide and 0.2 g of sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 2 hours in a 650 ℃ tubular furnace;
(3) washing the fired solid with distilled water for 3 times, washing with ethanol for 3 times, centrifuging at 5000 r/min, and vacuum drying for 12h to obtain black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, adding 200 mu L of 3-aminopropyltriethoxysilane, adding 1g of hyaluronic acid, and stirring for 24 hours;
(5) dialyzing the stirred solution for 3 days by adopting a dialysis bag with the molecular weight cutoff of 10000 Da;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
Example 2:
a preparation method of boron-doped black zirconium dioxide nanoparticles comprises the following steps:
(1) weighing 1g of nano zirconium dioxide and 0.2 g of sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 4 hours in a 650 ℃ tubular furnace;
(3) washing the fired solid with distilled water for 3 times, washing with ethanol for 3 times, centrifuging at 5000 r/min, and vacuum drying for 12h to obtain black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, adding 200 mu L of 3-aminopropyltriethoxysilane, adding 1g of hyaluronic acid, and stirring for 24 hours;
(5) dialyzing the stirred solution for 3 days by adopting a dialysis bag with the molecular weight cutoff of 10000 Da;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
Example 3:
(1) weighing 1g of nano zirconium dioxide and 0.2 g of sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 6 hours in a 650 ℃ tube furnace;
(3) washing the fired solid with distilled water for 3 times, washing with ethanol for 3 times, centrifuging at 5000 r/min, and vacuum drying for 12h to obtain black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, adding 200 mu L of 3-aminopropyltriethoxysilane, adding 1g of hyaluronic acid, and stirring for 24 hours;
(5) dialyzing the stirred solution for 3 days by adopting a dialysis bag with the molecular weight cutoff of 10000 Da;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
Example 4:
(1) weighing 1g of nano zirconium dioxide and 0.2 g of sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 2 hours in a 500 ℃ tubular furnace;
(3) washing the fired solid with distilled water for 3 times, washing with ethanol for 3 times, centrifuging at 5000 r/min, and vacuum drying for 12h to obtain black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, adding 200 mu L of 3-aminopropyltriethoxysilane, adding 1g of hyaluronic acid, and stirring for 24 hours;
(5) dialyzing the stirred solution for 3 days by adopting a dialysis bag with the molecular weight cutoff of 10000 Da;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
Example 5:
(1) weighing 1g of nano zirconium dioxide and 0.2 g of sodium borohydride, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 2 hours in a 700 ℃ tube furnace;
(3) washing the fired solid with distilled water for 3 times, washing with ethanol for 3 times, centrifuging at 5000 r/min, and vacuum drying for 12h to obtain black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, adding 200 mu L of 3-aminopropyltriethoxysilane, adding 1g of hyaluronic acid, and stirring for 24 hours;
(5) dialyzing the stirred solution for 3 days by adopting a dialysis bag with the molecular weight cutoff of 10000 Da;
(6) and (4) freeze-drying the dialyzed solution to obtain the final product, namely the black zirconium dioxide nano-particle.
The black zirconium dioxide nano-particles prepared by the final products of the examples 1, 2, 3, 4 and 5 can be well dispersed in the aqueous solution and stably exist.
Claims (5)
1. A preparation method of boron-doped black zirconium dioxide nanoparticles with photo-thermal and photodynamic therapy functions is characterized by comprising the following steps:
(1) weighing nano zirconium dioxide and sodium borohydride according to the mass ratio of 1:0.2, and uniformly grinding for later use;
(2) putting the uniformly ground nano zirconium dioxide and sodium borohydride into an alumina crucible, and firing for 2-6 h in a 500-700 ℃ tube furnace;
(3) washing the fired solid with distilled water and absolute ethyl alcohol respectively, centrifuging by using a centrifuge, and drying to obtain a black solid;
(4) ultrasonically dispersing the obtained black solid in absolute ethyl alcohol, and simultaneously adding a certain amount of 3-aminopropyltriethoxysilane and hyaluronic acid and stirring for a period of time;
(5) dialyzing the stirred solution;
(6) and (3) freeze-drying the dialyzed solution to obtain the final product of the boron-doped black zirconium dioxide nano-particle with photo-thermal and photodynamic treatment functions.
2. The method for preparing boron-doped black zirconium dioxide nanoparticles with photothermal and photodynamic therapy functions as claimed in claim 1, wherein: washing with distilled water and absolute ethyl alcohol for 3 times respectively in the step (3), and centrifuging at 5000 r/min.
3. The method for preparing boron-doped black zirconium dioxide nanoparticles with photothermal and photodynamic therapy functions as claimed in claim 1, wherein: the 3-aminopropyltriethoxysilane added in the step (4) is 200 muL, and the mass ratio of the hyaluronic acid to the nano sodium zirconium dioxide is 1: 1.
4. The method for preparing boron-doped black zirconium dioxide nanoparticles with photothermal and photodynamic therapy functions as claimed in claim 1, wherein: and (5) dialyzing by adopting a dialysis bag with the molecular weight cutoff of 10000 Da.
5. A boron-doped black zirconium dioxide nanoparticle with photothermal and photodynamic therapeutic effects, prepared by the preparation method of any one of claims 1 to 4.
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| CN103103523A (en) * | 2013-03-01 | 2013-05-15 | 江苏大学 | Method for preparing laser thermal composite induction nanoparticle reinforcement laminated film |
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| CN106177952B (en) * | 2016-08-26 | 2019-12-27 | 广西师范大学 | Preparation method and application of molybdenum oxide nanoparticles with targeted photothermal and photodynamic therapy functions |
| CN106367065B (en) * | 2016-08-26 | 2018-09-25 | 广西师范大学 | The preparation method and its usage of copper, nitrogen-doped carbon quantum dot with dual light treatment effect and fluorescence imaging |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102743752A (en) * | 2012-05-25 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Composite nano-particles used in inorganic photodynamic therapy, and preparation method thereof |
| CN103103523A (en) * | 2013-03-01 | 2013-05-15 | 江苏大学 | Method for preparing laser thermal composite induction nanoparticle reinforcement laminated film |
| CN104888216A (en) * | 2015-02-12 | 2015-09-09 | 中国医科大学附属第一医院 | Zirconium dioxide composite nanometer material with microwave sensitization, chemotherapy dry release and CT imaging functions and preparation method and application thereof |
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| CN108126200A (en) * | 2017-12-30 | 2018-06-08 | 广西师范大学 | A kind of preparation method and applications of hyaluronic acid decorated ruthenium nanometer optothermal material |
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