CN105950147A - Preparation method of strontium-containing hydroxylapatite fluorescent material - Google Patents
Preparation method of strontium-containing hydroxylapatite fluorescent material Download PDFInfo
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- CN105950147A CN105950147A CN201511013517.5A CN201511013517A CN105950147A CN 105950147 A CN105950147 A CN 105950147A CN 201511013517 A CN201511013517 A CN 201511013517A CN 105950147 A CN105950147 A CN 105950147A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
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Abstract
The invention discloses a preparation method of a strontium-containing hydroxylapatite fluorescent material and provides the preparation method of the strontium-containing hydroxylapatite fluorescent material which has high fluorescent intensity, long fluorescent service life and excellent biocompatibility. The preparation method includes the steps of: 1) preparing a soluble rare earth europium nitrate solution for doping; 2) according to the molar ratio (Ca<2+> + Sr<2+>)/P being 1.67, weighing strontium nitrate, calcium nitrate and diammonium hydrogen phosphate in certain amounts and respectively preparing solutions, and weighing the strontium nitrate solution, the calcium nitrate solution, and the diammonium hydrogen phosphate solution according to certain ratio and uniformly mixing the solutions; and 3) slowly adding the diammonium hydrogen phosphate solution dropwisely to the mixed solution, uniformly mixing the solutions, regulating the pH value with a sodium hydroxide solution, aging the solution at 80 DEG C for 24 h, and washing, suction-filtering, drying and grinding the aged solution to obtain the strontium-containing hydroxylapatite fluorescent material.
Description
Technical field
The present invention relates to the preparation method of a kind of fluorescent material, be specifically related to the preparation method of a kind of strontium containing hydroxyapatite fluorescent material.
Background technology
Along with the development of life sciences, it is desirable to obtain the abundant detailed visual information about tissue, cell etc., promote various imaging technique to develop rapidly.Wherein, bioluminescence imaging is little with its destructiveness, highly sensitive, good selective, focus the most of concern.And the development of fluorescence imaging receives the restriction of fluorescent probe performance.Hydroxyapatite has the performances such as the biocompatibility of excellence, osteoinductive, non-immunogenic, degradability, is widely used in organizational project, medicine and gene delivery and other biological field.Meanwhile, hydroxyapatite is also the matrix material of a kind of good ion doping, is often given new physicochemical property by foreign ion.Hydroxyapatite has the biodegradability that excellent biocompatibility is become reconciled, but the hydroxyl apatite fluorescent probe of conventional rare ion doping is easily caused quenching phenomenon, preferable bioprobe material to possess good photochemical stability, particle size at nanoscale, to requirements such as organism nonhazardous effects by the hydroxyl in lattice.
Summary of the invention
The invention aims to overcome the deficiencies in the prior art, it is provided that a kind of have a higher fluorescence intensity, higher fluorescence lifetime also has the preparation method of a kind of strontium containing hydroxyapatite fluorescent material of good biocompatibility.
Technical solution of the present invention is as follows: the preparation method of a kind of strontium containing hydroxyapatite fluorescent material, following steps realize:
Step one: the preparation of europium nitrate:
Weigh a certain amount of europium oxide, be dissolved in concentrated nitric acid；
After dissolving, gained solution is positioned over the water-bath that bath temperature is 85 DEG C, obtains europium nitrate crystal；
Take europium nitrate dissolution of crystals and obtain europium nitrate aqueous solution in deionized water, standby；
Step 2: the preparation of strontium containing hydroxyapatite fluorescent material:
Strontium nitrate, calcium nitrate, diammonium phosphate are dissolved separately in deionized water and i.e. obtain strontium nitrate aqueous solution, calcium nitrate aqueous solution and ammonium dibasic phosphate aqueous solution；
Measured amounts strontium nitrate aqueous solution, calcium nitrate aqueous solution join europium nitrate aqueous solution, stir, obtain mixed solution；
Take ammonium dibasic phosphate aqueous solution and sodium hydrate aqueous solution low speed drips in mixed solution, it is stirred continuously, until the mol ratio of (strontium+calcium)/phosphorus is 1.67 in reaction system, regulation system pH value range is 10-14, continue stirring 1h, seal, at 80 DEG C of still aging 24h, obtain strontium containing hydroxyapatite fluorescent material suspension；
The supernatant, Ji get lower floor strontium containing hydroxyapatite fluorescent material precipitate is removed by sucking filtration；
Gained strontium containing hydroxyapatite fluorescent material precipitate is filtered by deionized water wash, be placed in baking oven 24h that temperature is 80 DEG C, finally grind, obtain strontium containing hydroxyapatite fluorescent material powder body.
In step 2, strontium is 0.01-100 mol% with the molar ratio range of calcium.
In step 2, europium and (calcium+strontium) molar ratio range are 0.01-10 mol%.
A kind of strontium containing hydroxyapatite fluorescent material that the preparation method of a kind of strontium containing hydroxyapatite fluorescent material prepares.
Beneficial effect
Preparation method cheaper starting materials of the present invention is easy to get, low cost, and synthesis technique the most easily realizes, utilize this technical scheme can obtain strontium containing hydroxyapatite fluorescent material, comparing rare earth hydroxyapatite, its fluorescence radiation intensity is higher and color becomes apparent from, and fluorescence lifetime is higher.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the strontium containing hydroxyapatite fluorescent material that the preparation method of a kind of strontium containing hydroxyapatite fluorescent material of the present invention prepares；
Fig. 2 is the fluorescence emission spectrogram (excitation wavelength is 394 nm) of the strontium containing hydroxyapatite fluorescent material that the preparation method of a kind of strontium containing hydroxyapatite fluorescent material of the present invention prepares；
Fig. 3 is the fluorescence decay curve figure (excitation wavelength is 394 nm, a length of 618 nm of transmitted wave) of the strontium containing hydroxyapatite fluorescent material that the preparation method of a kind of strontium containing hydroxyapatite fluorescent material of the present invention prepares.
Detailed description of the invention
Embodiment
1
First step: the preparation of europium nitrate:
First, weigh 0.05g europium oxide, dissolve with concentrated nitric acid；Secondly, after dissolving, gained solution carries out 85 DEG C of heating in water bath, until separating out pale pink europium nitrate crystal；Finally, europium nitrate is configured to the europium nitrate aqueous solution 5m of 0.05mol/L；
Second step: the preparation of strontium containing hydroxyapatite fluorescent material:
Being 0.5mol/L calcium nitrate aqueous solution 70ml with deionized water compound concentration respectively, concentration is 0.5mol/L strontium nitrate aqueous solution 30ml and concentration is 0.6mol/L ammonium dibasic phosphate aqueous solution 50ml；Described calcium nitrate aqueous solution, strontium nitrate aqueous solution and europium nitrate aqueous solution are uniformly mixed, obtains mixed solution, and be stirred continuously；
Ammonium dibasic phosphate aqueous solution is slowly added dropwise into above-mentioned mixed solution, when the ratio of the molal weight of (strontium+calcium)/phosphorus is 1.67 in reaction system, stops dropping ammonium dibasic phosphate aqueous solution；Being slowly added dropwise the sodium hydrate aqueous solution that concentration is 2mol/L simultaneously, and be stirred continuously, the pH value keeping reaction system is 10 ~ 14, obtains the suspension containing strontium containing hydroxyapatite fluorescent material；
The continuously stirred suspension being somebody's turn to do containing strontium containing hydroxyapatite fluorescent material 1 hour, then beaker mouth is sealed with preservative film, at 80 DEG C still aging 24 hours, layering should be produced by suspension containing strontium containing hydroxyapatite fluorescent material, upper strata is clear liquid, and lower floor is the precipitate of strontium containing hydroxyapatite fluorescent material；
The method using sucking filtration filters off the supernatant, obtains the strontium containing hydroxyapatite fluorescent material precipitate of lower floor, is then washed with deionized and filters described strontium containing hydroxyapatite fluorescent material precipitate, and washing and filtering number of times is no less than 10 times；
Described strontium containing hydroxyapatite fluorescent material precipitate is dried 24 hours at 80 DEG C, is then ground, finally give strontium containing hydroxyapatite fluorescent material powder body.
After having prepared a kind of strontium containing hydroxyapatite fluorescent material, using X ray diffracting spectrum (XRD) to characterize composition and the structure of material, its XRD figure is composed as shown in curve a in Fig. 1；Using spectrofluorophotometer to characterize material luminescent properties under light excites, its emission spectrum is as shown in curve a in Fig. 2, and luminous intensity is 241.4a.u.；Fluorescence decay curve is as shown in curve a in Fig. 3, and fluorescence lifetime is 1.031 ms.
Embodiment
2
First step: the preparation of europium nitrate:
First, weigh 0.05g europium oxide, dissolve with concentrated nitric acid；Secondly, after dissolving, gained solution carries out 85 DEG C of heating in water bath, until separating out pale pink europium nitrate crystal；Finally, europium nitrate is configured to the europium nitrate aqueous solution 5ml of 0.05mol/L；
Second step: the preparation of strontium containing hydroxyapatite fluorescent material:
Being 0.5mol/L calcium nitrate aqueous solution 30ml with deionized water compound concentration respectively, concentration is 0.5mol/L strontium nitrate aqueous solution 70ml and concentration is 0.6mol/L ammonium dibasic phosphate aqueous solution 50ml；
Described calcium nitrate aqueous solution, strontium nitrate aqueous solution and europium nitrate aqueous solution are uniformly mixed, obtains mixed solution, and be stirred continuously；
Ammonium dibasic phosphate aqueous solution is slowly added dropwise into above-mentioned mixed solution, when the ratio of the molal weight of (strontium+calcium)/phosphorus is 1.67 in reaction system, stops dropping ammonium dibasic phosphate aqueous solution；Being slowly added dropwise the sodium hydrate aqueous solution that concentration is 2mol/L simultaneously, and be stirred continuously, the pH value keeping reaction system is 10～14, obtains the suspension containing strontium containing hydroxyapatite fluorescent material；
The continuously stirred suspension being somebody's turn to do containing strontium containing hydroxyapatite fluorescent material 1 hour, then beaker mouth is sealed with preservative film, at 80 DEG C still aging 24 hours, layering should be produced by suspension containing strontium containing hydroxyapatite fluorescent material, upper strata is clear liquid, and lower floor is the precipitate of strontium containing hydroxyapatite fluorescent material；
The method using sucking filtration filters off the supernatant, obtains the strontium containing hydroxyapatite fluorescent material precipitate of lower floor, is then washed with deionized and filters described strontium containing hydroxyapatite fluorescent material precipitate, and washing and filtering number of times is no less than 10 times；
Described strontium containing hydroxyapatite fluorescent material precipitate is dried 24 hours at 80 DEG C, is then ground, finally give strontium containing hydroxyapatite fluorescent material powder body.
After having prepared a kind of strontium containing hydroxyapatite fluorescent material, using X ray diffracting spectrum (XRD) to characterize composition and the structure of material, its XRD figure is composed as shown in curve b in Fig. 1；Using spectrofluorophotometer to characterize material luminescent properties under light excites, its emission spectrum is as shown in curve b in Fig. 2, and luminous intensity is 493.2a.u.；Fluorescence decay curve is as shown in curve b in Fig. 3, and fluorescence lifetime is 1.192 ms.
Present invention is not limited to cited by embodiment, and the conversion of any equivalence that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention, the claim being the present invention is contained.
Claims (4)
1. the preparation method of a strontium containing hydroxyapatite fluorescent material, it is characterised in that:
Realized by following steps:
Step one: the preparation of europium nitrate:
Weigh a certain amount of europium oxide, be dissolved in concentrated nitric acid；
After dissolving, gained solution is positioned over the water-bath that bath temperature is 85 DEG C, obtains europium nitrate crystal；
Take europium nitrate dissolution of crystals and obtain europium nitrate aqueous solution in deionized water, standby；
Step 2: the preparation of strontium containing hydroxyapatite fluorescent material:
Strontium nitrate, calcium nitrate, diammonium phosphate are dissolved separately in deionized water and i.e. obtain strontium nitrate aqueous solution, calcium nitrate aqueous solution and ammonium dibasic phosphate aqueous solution；
Measured amounts strontium nitrate aqueous solution, calcium nitrate aqueous solution join europium nitrate aqueous solution, stir, obtain mixed solution；
Take ammonium dibasic phosphate aqueous solution and sodium hydrate aqueous solution low speed drips in mixed solution, it is stirred continuously, until the mol ratio of (strontium+calcium)/phosphorus is 1.67 in reaction system, regulation system pH value range is 10-14, continue stirring 1h, seal, at 80 DEG C of still aging 24h, obtain strontium containing hydroxyapatite fluorescent material suspension；
The supernatant, Ji get lower floor strontium containing hydroxyapatite fluorescent material precipitate is removed by sucking filtration；
Gained strontium containing hydroxyapatite fluorescent material precipitate is filtered by deionized water wash, be placed in baking oven 24h that temperature is 80 DEG C, finally grind, obtain strontium containing hydroxyapatite fluorescent material powder body.
The preparation method of a kind of strontium containing hydroxyapatite fluorescent material the most according to claim 1, it is characterised in that: in step 2, strontium is 0.01-100 with the molar ratio range of calcium
mol%。
The preparation method of a kind of strontium containing hydroxyapatite fluorescent material the most according to claim 1, it is characterised in that: in step 2, europium and (calcium+strontium) molar ratio range are 0.01-10 mol%.
A kind of strontium containing hydroxyapatite fluorescent material that the preparation method of a kind of strontium containing hydroxyapatite fluorescent material the most according to claim 1 prepares.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966376A (en) * | 2017-03-24 | 2017-07-21 | 陕西科技大学 | A kind of preparation method of boron, samarium codope hydroxyapatite embedded photoluminescent material |
| CN106986319A (en) * | 2017-03-24 | 2017-07-28 | 陕西科技大学 | Terbium/strontium of green fluorescent label with high luminous intensity is co-doped with the preparation method of hydroxyapatite nano particle |
| CN108324949A (en) * | 2018-03-21 | 2018-07-27 | 华北理工大学 | A kind of hydroxyapatite-carbonitride compound particle and its in-situ composite |
| CN110205126A (en) * | 2019-07-18 | 2019-09-06 | 长春理工大学 | The fluorescent material and preparation method and application of fluorescent material, glucan package |
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| US20130303363A1 (en) * | 2012-03-01 | 2013-11-14 | E I Du Pont De Nemours And Company | Conversion of ethanol to a reaction product comprising 1-butanol using hydroxyapatite catalysts |
| CN103525417A (en) * | 2013-09-23 | 2014-01-22 | 武汉理工大学 | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles |
| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
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2015
- 2015-12-31 CN CN201511013517.5A patent/CN105950147A/en active Pending
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| US20130303363A1 (en) * | 2012-03-01 | 2013-11-14 | E I Du Pont De Nemours And Company | Conversion of ethanol to a reaction product comprising 1-butanol using hydroxyapatite catalysts |
| CN103525417A (en) * | 2013-09-23 | 2014-01-22 | 武汉理工大学 | Preparation method of europium-doped hydroxyapatite (HAP) fluorescent nanoparticles |
| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966376A (en) * | 2017-03-24 | 2017-07-21 | 陕西科技大学 | A kind of preparation method of boron, samarium codope hydroxyapatite embedded photoluminescent material |
| CN106986319A (en) * | 2017-03-24 | 2017-07-28 | 陕西科技大学 | Terbium/strontium of green fluorescent label with high luminous intensity is co-doped with the preparation method of hydroxyapatite nano particle |
| CN108324949A (en) * | 2018-03-21 | 2018-07-27 | 华北理工大学 | A kind of hydroxyapatite-carbonitride compound particle and its in-situ composite |
| CN110205126A (en) * | 2019-07-18 | 2019-09-06 | 长春理工大学 | The fluorescent material and preparation method and application of fluorescent material, glucan package |
| CN110205126B (en) * | 2019-07-18 | 2022-02-01 | 长春理工大学 | Fluorescent material, glucan-coated fluorescent material, and preparation method and application thereof |
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Application publication date: 20160921 |