CN103525417A - Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles - Google Patents
Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles Download PDFInfo
- Publication number
- CN103525417A CN103525417A CN201310435997.9A CN201310435997A CN103525417A CN 103525417 A CN103525417 A CN 103525417A CN 201310435997 A CN201310435997 A CN 201310435997A CN 103525417 A CN103525417 A CN 103525417A
- Authority
- CN
- China
- Prior art keywords
- europium
- aqueous solution
- hap
- nano particles
- fluorescent nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles, which comprises the following steps of 1) preparing a mixed aqueous solution of calcium chloride and europium chloride, controlling the molar ratio of Eu to Ca and Eu together at 0.1-4%, preparing an aqueous solution of disodium hydrogen phosphate, quickly pouring the aqueous solution of disodium hydrogen phosphate into the mixed aqueous solution of calcium chloride and europium chloride at room temperature, uniformly stirring and mixing, after reaction, centrifuging to obtain precipitates, washing the precipitates with deionized water, and then dispersing into the deionized water again; 2) adding a stabilizer, and performing ultrasonic dispersion treatment by use of a high-energy ultrasonic probe to obtain a stable suspension; 3) performing hydrothermal treatment on the suspension by use of a high-pressure sterilization pot to obtain a stable suspension of europium-doped HAP fluorescent nanoparticles. The method provided by the invention has the beneficial effects that effective control on the size of rare earth europium-doped HAP fluorescent nanoparticles can be realized while the crystallinity and fluorescence are improved, and the stable suspension of the europium-doped HAP fluorescent nanoparticles is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of europium doped hydroxyapatite fluorescent nano particles.
Background technology
Inorganic salt in hydroxyapatite (HAP) chemical composition, crystalline structure and skeleton are quite similar, have good biocompatibility, in bone defect healing, are widely applied.In recent years, development along with nanotechnology, the special performance that HAP nano material has is embodied day by day, for example the high-specific surface area of HAP nanoparticle can improve ceramic fracture toughness property, HAP nanophase pottery can improve bone amalgamation, and HAP nanoparticle can be used as medicine or genophore.Especially, rear-earth-doped HAP nanoparticle has also received people's concern as the research of biology fluorescent probe in recent years, is expected to become a kind of novel inorganic fluorescence probe material, for cell marking.
The research of rear-earth-doped HAP is early before this for laser host material.Afterwards, people had carried out again rear-earth-doped HAP as the applied research of fluorescent probe, and the preparation method of rear-earth-doped HAP nanoparticle fluorescent probe has been carried out to correlative study.For example, adopt the precipitator method in water-ethanol medium, to synthesize rear-earth-doped phosphorite nanocrystalline at low temperature (37 ℃); By adding NH
3 +-CH
2cH
2-PO
4h
-improved precipitator method preparation technology, reduced size of particles, improved its stability, at 80 ℃ of needle-like Ln that obtained stable 4nm * 12nm in water medium
3+doping phosphorite nano particle; Adopt the precipitator method, directly add DNA and be adsorbed onto particle surface and play stabilization, prepared the stable europium with certain degree of crystallinity and terbium doped apatite fluorescent nanoparticle (50nm * 200-300nm rhabdolith); Adopt cats product to synthesize 20-40nm * 100-200nm, mesoporous bar-shaped Eu as template
3+doping HAP nanoparticle; By adding 2-amino-ethyl phosphonic acids, adopt the precipitator method to prepare the Eu that mean sizes is 30nm
3+doping phosphorite nano particle, has reduced size of particles.
For rear-earth-doped HAP fluorescent nano particles, fluorescence intensity becomes positive correlation with its degree of crystallinity.In order to improve its degree of crystallinity, the temperature that can improve reaction system by heating improves its degree of crystallinity, or calcining improves its degree of crystallinity at a certain temperature.The former can improve its degree of crystallinity to a certain extent, but the amplitude improving with respect to the latter is limited; Though and the latter can largely improve its degree of crystallinity, calcination processing can cause excessively growing up of crystal grain.That is to say, for rear-earth-doped HAP fluorescent nano particles, between size of particles and fluorescence intensity, exist conflicting relation.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned prior art, to propose a kind of preparation method of europium doped hydroxyapatite fluorescent nano particles, it improves the precipitator method, by adding biocompatible stablizer, in conjunction with ultrasonic dispersion technology, obtain stable europium doping HAP fluorescent nano particles suspension, and improve its degree of crystallinity and then improve its fluorescence by hydrothermal treatment consists.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of europium doped hydroxyapatite fluorescent nano particles, is characterized in that including following steps:
1) mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, and Eu/ (Ca+Eu) mol ratio is 0.1-4%, the configuration Sodium phosphate dibasic aqueous solution, controls PO
4 3-concentration is 0.02mol/L, according to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times;
2) add stablizer, high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 4-8 minute, obtains stable suspension;
3) with high-pressure sterilizing pot, suspension is carried out to hydrothermal treatment consists, obtain europium doped hydroxyapatite fluorescent nano particles stable suspension.
Press such scheme, 121 ℃ of the temperature of described hydrothermal treatment consists, the time is 0.5-1.5 hour.
Press such scheme, described stablizer is polysaccharose substance heparin sodium, and its concentration is at 0.2-0.6mg/mL.
Europium content in described europium doped hydroxyapatite fluorescent nano particles stable suspension is Eu/ (Ca+Eu) mol ratio at 0.1-4%() between, gained europium doped hydroxyapatite fluorescent nano particles is mainly 10-30nm almost spherical and 10-30nm * 20-100nm short cylinder nanoparticle under transmission electron microscope, the median size that dynamic light scattering detects is 73.6nm-119.4nm, zeta current potential is-32.9mV--49.5mV, 394nm excites down at 592nm, 618nm and 700nm and occurs obvious emission peak, launches strong red fluorescence under fluorescent microscope.
The main reaction mechanism of the present invention is: the present invention relates to chemical reaction and be shown below:
Ca
2++ Eu
3++ PO
4 3-→ Ca
10-xeu
x(PO
4)
6(OH)
2, x=0.1-4% wherein.By coprecipitation method, form the phosphatic rock throw out that contains europium, add after stablizer under the sound cavitation effect of ultrasonic generation, formed the stable europium Doping Phosphorus lime stone nanoparticle suspension of stablizer, by hydrothermal treatment consists, further promote crystallization to obtain the stable europium doped hydroxyapatite nanoparticle suspension of stablizer, wherein stablizer heparin sodium is adsorbed onto on hydroxyapatite nano particle surface by the electrostatic interaction between its electronegative sulfate and carboxylic group and the positively charged calcium ion of hydroxyapatite surface, plays stabilization.
The invention has the beneficial effects as follows: take the precipitator method as basis, add biocompatible stablizer, in conjunction with ultrasonic dispersion technology and hydro-thermal treatment method, form the preparation method that a kind of precipitator method-ultrasonic-hydro-thermal multiple technologies combine, can realize the effective control to rare-earth europium doping HAP fluorescent nano particles size, improve its degree of crystallinity and fluorescence simultaneously, by this inventive method, can obtain the stable suspension of europium doping HAP fluorescent nano particles.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the europium doping HAP fluorescent nano particles that obtains of embodiment 1-5, and wherein A:Eu content 0.1%, stabilizer concentration 0.6mg/mL; B:Eu content 2%, stabilizer concentration 0.6mg/mL; C:Eu content 4%, stabilizer concentration 0.6mg/mL; D:Eu content 2%, stabilizer concentration 0.2mg/mL; E:Eu content 2%, stabilizer concentration 0.4mg/mL;
Fig. 2 is the transmission electron microscope pattern picture of the europium doping HAP fluorescent nano particles that obtains of embodiment 1-5, and wherein A:Eu content 0.1%, stabilizer concentration 0.6mg/mL; B:Eu content 2%, stabilizer concentration 0.6mg/mL; C:Eu content 4%, stabilizer concentration 0.6mg/mL; D:Eu content 2%, stabilizer concentration 0.2mg/mL; E:Eu content 2%, stabilizer concentration 0.4mg/mL;
Fig. 3 is the fluorescence emission spectrum of the europium doping HAP fluorescent nano particles that obtains of embodiment 1-5 under 394nm excites, and wherein A:Eu content 0.1%, stabilizer concentration 0.6mg/mL; B:Eu content 2%, stabilizer concentration 0.6mg/mL; C:Eu content 4%, stabilizer concentration 0.6mg/mL; D:Eu content 2%, stabilizer concentration 0.2mg/mL; E:Eu content 2%, stabilizer concentration 0.4mg/mL;
Fig. 4 is the fluorescent microscope picture of the europium doping HAP fluorescent nano particles that obtains of embodiment 1-5, and wherein A:Eu content 0.1%, stabilizer concentration 0.6mg/mL; B:Eu content 2%, stabilizer concentration 0.6mg/mL; C:Eu content 4%, stabilizer concentration 0.6mg/mL; D:Eu content 2%, stabilizer concentration 0.2mg/mL; E:Eu content 2%, stabilizer concentration 0.4mg/mL.
Fig. 5 is the fluorescent microscope picture of embodiment 6 europium doping HAP fluorescent nanometer particle to mark cells.
Embodiment
Below by embodiment, the present invention will be further described in detail, but this explanation can not be construed as limiting the invention.Embodiment 1
First, the mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, wherein Eu/ (Ca+Eu) mol ratio is 0.1%.The configuration Sodium phosphate dibasic aqueous solution, PO
4 3-concentration is 0.02mol/L.According to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times.Then, add stablizer polysaccharose substance heparin sodium (concentration is 0.6mg/mL), high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 6 minutes, obtains stable suspension.Finally, with high-pressure sterilizing pot, at 121 ℃, carry out hydrothermal treatment consists 1 hour, obtain europium doping HAP fluorescent nano particles stable suspension.X ray diffracting spectrum (Figure 1A) proves that product crystalline phase is HAP.Transmission electron microscope observing (Fig. 2 A) shows that product is mainly 20-30nm almost spherical nanoparticle.It is 73.6nm that dynamic light scattering detects median size, and zeta current potential is-39.2mV.At 394nm, excite lower europium doping HAP fluorescent nano particles to occur faint emission peak (Fig. 3 A) at 700nm.Under fluorescent microscope, launch faint red fluorescence (Fig. 4 A).
Embodiment 2
First, the mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, wherein Eu/ (Ca+Eu) mol ratio is 2%.The configuration Sodium phosphate dibasic aqueous solution, PO
4 3-concentration is 0.02mol/L.According to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times.Then, add stablizer polysaccharose substance heparin sodium (concentration is 0.6mg/mL), high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 6 minutes, obtains stable suspension.Finally, with high-pressure sterilizing pot, at 121 ℃, carry out hydrothermal treatment consists 1 hour, obtain europium doping HAP fluorescent nano particles stable suspension.X ray diffracting spectrum (Figure 1B) proves that product crystalline phase is HAP.Transmission electron microscope observing (Fig. 2 B) shows that product is mainly 20-30nm almost spherical and 20-30nm * 60-80nm short cylinder nanoparticle.It is 81.5nm that dynamic light scattering detects median size, and zeta current potential is-45.6mV.At 394nm, excite lower europium doping HAP fluorescent nano particles to occur obvious emission peak (Fig. 3 B) at 592nm, 618nm and 700nm.Under fluorescent microscope, launch strong red fluorescence (Fig. 4 B).
Embodiment 3
First, the mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, wherein Eu/ (Ca+Eu) mol ratio is 4%.The configuration Sodium phosphate dibasic aqueous solution, PO
4 3-concentration is 0.02mol/L.According to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times.Then, add stablizer polysaccharose substance heparin sodium (concentration is 0.6mg/mL), high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 6 minutes, obtains stable suspension.Finally, with high-pressure sterilizing pot, at 121 ℃, carry out hydrothermal treatment consists 1 hour, obtain europium doping HAP fluorescent nano particles stable suspension.X ray diffracting spectrum (Fig. 1 C) proves that product crystalline phase is HAP.Transmission electron microscope observing (Fig. 2 C) shows that product is mainly 10-20nm * 50-100nm short cylinder nanoparticle.It is 85.1nm that dynamic light scattering detects median size, and zeta current potential is-46mV.At 394nm, excite lower europium doping HAP fluorescent nano particles to occur obvious emission peak (Fig. 3 C) at 592nm, 618nm and 700nm.Under fluorescent microscope, launch very strong red fluorescence (Fig. 4 C).
Embodiment 4
First, the mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, wherein Eu/ (Ca+Eu) mol ratio is 2%.The configuration Sodium phosphate dibasic aqueous solution, PO
4 3-concentration is 0.02mol/L.According to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times.Then, add stablizer polysaccharose substance heparin sodium (concentration is 0.2mg/mL), high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 6 minutes, obtains stable suspension.Finally, with high-pressure sterilizing pot, at 121 ℃, carry out hydrothermal treatment consists 1 hour, obtain europium doping HAP fluorescent nano particles stable suspension.X ray diffracting spectrum (Fig. 1 D) proves that product crystalline phase is HAP.Transmission electron microscope observing (Fig. 2 D) shows that product is mainly 10-15nm almost spherical and 10-30nm * 20-40nm short cylinder nanoparticle.It is 119.4nm that dynamic light scattering detects median size, and zeta current potential is-32.9mV.At 394nm, excite lower europium doping HAP fluorescent nano particles to occur obvious emission peak (Fig. 3 D) at 592nm, 618nm and 700nm.Under fluorescent microscope, launch strong red fluorescence (Fig. 4 D).
Embodiment 5
First, the mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, wherein Eu/ (Ca+Eu) mol ratio is 2%.The configuration Sodium phosphate dibasic aqueous solution, PO
4 3-concentration is 0.02mol/L.According to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times.Then, add stablizer polysaccharose substance heparin sodium (concentration is 0.4mg/mL), high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 6 minutes, obtains stable suspension.Finally, with high-pressure sterilizing pot, at 121 ℃, carry out hydrothermal treatment consists 1 hour, obtain europium doping HAP fluorescent nano particles stable suspension.X ray diffracting spectrum (Fig. 1 E) proves that product crystalline phase is HAP.Transmission electron microscope observing (Fig. 2 E) shows that product is the approximate short cylinder nanoparticle of 20nm * 80nm.It is 96.9nm that dynamic light scattering detects median size, and zeta current potential is-49.5mV.At 394nm, excite lower europium doping HAP fluorescent nano particles to occur obvious emission peak (Fig. 3 E) at 592nm, 618nm and 700nm.Under fluorescent microscope, launch strong red fluorescence (Fig. 4 E).
Application Example 6
Take Bel-7402 human liver cancer cell as model, carry out europium doping HAP fluorescent nano particles cell marking.Bel-7402 human liver cancer cell is inoculated in culture dish, and inoculum density is 40,000/ holes, at 37 ℃, 5%CO
2under atmosphere, first cultivate 24 hours.Then embodiment 2 gained europiums being adulterated, HAP fluorescent nano particles (Eu content 2%, stabilizer concentration 0.6mg/mL) dilute afterwards with nutrient solution and Bel-7402 human liver cancer cell is cultivated after 5 hours altogether, and PBS rinses cell 3 times, carries out fluorescence microscope.Under fluorescent microscope, can observe cell and present red fluorescence (as Fig. 5).
Claims (3)
1. a preparation method for europium doped hydroxyapatite fluorescent nano particles, is characterized in that including following steps:
1) mixed aqueous solution of configuration calcium chloride and Europium trichloride, controls Ca
2+and Eu
3+total concn be 0.0334mol/L, and Eu/ (Ca+Eu) mol ratio is 0.1-4%, the configuration Sodium phosphate dibasic aqueous solution, controls PO
4 3-concentration is 0.02mol/L, according to mol ratio (Ca+Eu)/P=1.67, under room temperature, the 100mL Sodium phosphate dibasic aqueous solution is poured into rapidly in the mixed aqueous solution of 100mL calcium chloride and Europium trichloride, be uniformly mixed, react after 15 minutes, the centrifugal thing that is precipitated, is re-dispersed in 200mL deionized water with after deionized water rinsing 3 times;
2) add stablizer, high-energy ultrasonic Probe Ultrasonic Searching dispersion treatment 4-8 minute, obtains stable suspension;
3) with high-pressure sterilizing pot, suspension is carried out to hydrothermal treatment consists, obtain europium doped hydroxyapatite fluorescent nano particles stable suspension.
2. press the preparation method of europium doped hydroxyapatite fluorescent nano particles claimed in claim 1,121 ℃ of the temperature of the hydrothermal treatment consists described in it is characterized in that, the time is 0.5-1.5 hour.
3. by the preparation method of the europium doped hydroxyapatite fluorescent nano particles described in claim 1 or 2, it is characterized in that described stablizer is polysaccharose substance heparin sodium, its concentration is at 0.2-0.6mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435997.9A CN103525417B (en) | 2013-09-23 | 2013-09-23 | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435997.9A CN103525417B (en) | 2013-09-23 | 2013-09-23 | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103525417A true CN103525417A (en) | 2014-01-22 |
| CN103525417B CN103525417B (en) | 2015-04-22 |
Family
ID=49927778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310435997.9A Active CN103525417B (en) | 2013-09-23 | 2013-09-23 | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103525417B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
| CN103822906A (en) * | 2014-02-19 | 2014-05-28 | 武汉理工大学 | Quantitative detection tracing method of intracellular HPA (hydroxyapatite) nano particles |
| CN105018086A (en) * | 2015-07-03 | 2015-11-04 | 武汉理工大学 | Rare-earth-doped calcium phosphate fluorescent nanoparticles, and preparation method and application thereof |
| CN105018079A (en) * | 2015-07-17 | 2015-11-04 | 辽宁大学 | Preparation method of rare earth element-doped 4ZnO.B2O3.H2O: RE<3+>-type zinc borate |
| CN105950147A (en) * | 2015-12-31 | 2016-09-21 | 陕西科技大学 | Preparation method of strontium-containing hydroxylapatite fluorescent material |
| CN105950146A (en) * | 2015-12-22 | 2016-09-21 | 陕西科技大学 | Preparation method of hydroxylapatite fluorescent material doped with rare earth samarium |
| CN106010505A (en) * | 2016-05-16 | 2016-10-12 | 华东理工大学 | Preparation method of hydroxyapatite nano-probe |
| RU2628610C1 (en) * | 2016-06-17 | 2017-08-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) | Method for production of nano-dimensional high-luminescent apatite with europium (eu) impurity |
| CN107083241A (en) * | 2017-06-19 | 2017-08-22 | 中南大学 | Water soluble hydroxy apatite fluorescent nano-particle and its preparation and activity and the method for inhibition for testing and analyzing PKA |
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
| CN108929686A (en) * | 2018-08-27 | 2018-12-04 | 中北大学 | Multicolor luminous europium, gadolinium codope hydroxyapatite/carbon dots preparation method |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
| CN111257291A (en) * | 2020-01-20 | 2020-06-09 | 武汉理工大学 | Quantitative detection method for phosphate ions and application thereof |
| CN111732087A (en) * | 2020-06-24 | 2020-10-02 | 三峡大学 | Europium-selenium double-doped hydroxyapatite and application thereof in preparing medicine for monitoring and treating osteosarcoma |
| CN111748337A (en) * | 2020-07-27 | 2020-10-09 | 吉林大学 | Preparation method of fluorescent marker applied to osteoporosis |
-
2013
- 2013-09-23 CN CN201310435997.9A patent/CN103525417B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 孙玉绣等: "Eu3+掺杂纳米羟基磷灰石生物荧光探针的制备、性能与表征", 《化学通报》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103822906A (en) * | 2014-02-19 | 2014-05-28 | 武汉理工大学 | Quantitative detection tracing method of intracellular HPA (hydroxyapatite) nano particles |
| CN103822906B (en) * | 2014-02-19 | 2016-03-09 | 武汉理工大学 | A kind ofly quantitatively detect the method for spike for HAP nano particle in cell |
| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
| CN105018086A (en) * | 2015-07-03 | 2015-11-04 | 武汉理工大学 | Rare-earth-doped calcium phosphate fluorescent nanoparticles, and preparation method and application thereof |
| CN105018079A (en) * | 2015-07-17 | 2015-11-04 | 辽宁大学 | Preparation method of rare earth element-doped 4ZnO.B2O3.H2O: RE<3+>-type zinc borate |
| CN105950146A (en) * | 2015-12-22 | 2016-09-21 | 陕西科技大学 | Preparation method of hydroxylapatite fluorescent material doped with rare earth samarium |
| CN105950147A (en) * | 2015-12-31 | 2016-09-21 | 陕西科技大学 | Preparation method of strontium-containing hydroxylapatite fluorescent material |
| CN106010505A (en) * | 2016-05-16 | 2016-10-12 | 华东理工大学 | Preparation method of hydroxyapatite nano-probe |
| RU2628610C1 (en) * | 2016-06-17 | 2017-08-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) | Method for production of nano-dimensional high-luminescent apatite with europium (eu) impurity |
| CN107083241A (en) * | 2017-06-19 | 2017-08-22 | 中南大学 | Water soluble hydroxy apatite fluorescent nano-particle and its preparation and activity and the method for inhibition for testing and analyzing PKA |
| CN107083241B (en) * | 2017-06-19 | 2019-08-23 | 中南大学 | The method of water soluble hydroxy apatite fluorescent nano-particle and its preparation and activity and inhibition for testing and analyzing PKA |
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
| CN108929686A (en) * | 2018-08-27 | 2018-12-04 | 中北大学 | Multicolor luminous europium, gadolinium codope hydroxyapatite/carbon dots preparation method |
| CN108929686B (en) * | 2018-08-27 | 2021-06-22 | 中北大学 | Preparation method of multicolor luminous europium and gadolinium codoped hydroxyapatite/carbon dots |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
| CN111257291A (en) * | 2020-01-20 | 2020-06-09 | 武汉理工大学 | Quantitative detection method for phosphate ions and application thereof |
| CN111257291B (en) * | 2020-01-20 | 2020-12-22 | 武汉理工大学 | Quantitative detection method for phosphate ions and application thereof |
| CN111732087A (en) * | 2020-06-24 | 2020-10-02 | 三峡大学 | Europium-selenium double-doped hydroxyapatite and application thereof in preparing medicine for monitoring and treating osteosarcoma |
| CN111748337A (en) * | 2020-07-27 | 2020-10-09 | 吉林大学 | Preparation method of fluorescent marker applied to osteoporosis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103525417B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103525417B (en) | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles | |
| Sadat-Shojai et al. | Hydrothermal processing of hydroxyapatite nanoparticles—A Taguchi experimental design approach | |
| Boanini et al. | Ionic substitutions in calcium phosphates synthesized at low temperature | |
| Joshy et al. | In vitro sustained release of amoxicillin from lanthanum hydroxyapatite nano rods | |
| CN104961114B (en) | Calcium and magnesium phosphate nano structural material and preparation method thereof | |
| Ramya et al. | Physicochemical and biological properties of iron and zinc ions co-doped nanocrystalline hydroxyapatite, synthesized by ultrasonication | |
| US20120134919A1 (en) | Ion substituted calcium phosphate particles | |
| CN108249414A (en) | A kind of rear-earth-doped hydroxyapatite nanoparticle and preparation method thereof | |
| CN103569985A (en) | Whitlockite and method for manufacturing the same | |
| Jiang et al. | Strontium-substituted, luminescent and mesoporous hydroxyapatite microspheres for sustained drug release | |
| CN108219788B (en) | Hydroxyapatite powder with up-conversion fluorescence and superparamagnetism and preparation method thereof | |
| CN104192817B (en) | Utilize the method for the high specific surface area and mesoporous hydroxyapatite nano particle of template synthesis | |
| Kheradmandfard et al. | In vitro study of a novel multi-substituted hydroxyapatite nanopowder synthesized by an ultra-fast, efficient and green microwave-assisted method | |
| Xing et al. | Ultrasound-assisted synthesis and characterization of heparin-coated Eu3+ doped hydroxyapatite luminescent nanoparticles | |
| CN108030956B (en) | Bioactive glass ceramic bracket for treating neoplastic bone defect and preparation method and application thereof | |
| WO2017080390A1 (en) | Sr- and mg-doped amorphous apatite material and crystalline apatite material | |
| CN107847640A (en) | The Biocomposite material of the graphene oxide of biomineralization and its purposes for bone tissue engineer | |
| CN101920947A (en) | Preparation method of slice-shaped B type carbonate phosphorite | |
| CN106999355A (en) | For the method for the amorphous calcium phosphate nano particle for applying citrate for obtaining fluoride-doped | |
| Jiang et al. | Phosphate-dependent morphological evolution of hydroxyapatite and implication for biomineralisation | |
| Li et al. | Comparative investigation on the crystal structure and cell behavior of rare-earth doped fluorescent apatite nanocrystals | |
| Yang et al. | Eu 3+/Tb 3+-doped whitlockite nanocrystals: Controllable synthesis, cell imaging, and the degradation process in the bone reconstruction | |
| Sundarabharathi et al. | In‐vitro biocompatibility, bioactivity and photoluminescence properties of Eu3+/Sr2+ dual‐doped nano‐hydroxyapatite for biomedical applications | |
| CN1693415B (en) | Hydroxy phosphorite of near infrared fluorescence quantum point mark and its preparation process and application | |
| CN105219391A (en) | A kind of preparation method of fluoro-europium-doped column hydroxide radical phosphorite nanocrystalline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |