CN105950147A - Preparation method of strontium-containing hydroxylapatite fluorescent material - Google Patents

Abstract

The invention discloses a method for preparing a strontium-containing hydroxyapatite fluorescent material. The invention provides a strontium-containing hydroxyapatite with higher fluorescence intensity, higher fluorescence lifetime and good biocompatibility Preparation method of stone fluorescent material. In the experiment, a soluble rare earth europium nitrate solution was first prepared for doping, and then the (Ca ²⁺ +Sr ^{2+ )} /P molar ratio was 1.67, and a certain amount of strontium nitrate, calcium nitrate, and diammonium hydrogen phosphate were weighed to prepare To form a solution, measure a certain amount of strontium nitrate, calcium nitrate, and diammonium hydrogen phosphate solution, mix and mix evenly, take the diammonium hydrogen phosphate solution and slowly add it dropwise to the above mixed solution, mix evenly, and adjust the pH value with sodium hydroxide solution. The solution was aged at 80°C for 24 h, washed, filtered with suction, dried and ground to obtain strontium-containing hydroxyapatite fluorescent material.

Description

A kind of preparation method of strontium-containing hydroxyapatite fluorescent material

technical field

The invention relates to a preparation method of a fluorescent material, in particular to a preparation method of a strontium-containing hydroxyapatite fluorescent material.

Background technique

With the development of life sciences, people hope to obtain rich and detailed intuitive information about tissues, cells, etc., prompting the rapid development of various imaging technologies. Among them, bioluminescent imaging has always been the focus of attention due to its advantages of less destructive, high sensitivity, and good selectivity. However, the development of fluorescence imaging is restricted by the performance of fluorescent probes. Hydroxyapatite has excellent biocompatibility, osteoinductivity, non-immunogenicity, and degradability, and is widely used in tissue engineering, drug and gene delivery, and other biological fields. At the same time, hydroxyapatite is also a good ion-doped matrix material, which is often endowed with new physical and chemical properties by impurity ions. Hydroxyapatite has excellent biocompatibility and good biodegradability, but conventional rare earth ion-doped hydroxyapatite fluorescent probes are easily quenched by hydroxyl groups in the lattice, making it an ideal biological probe Materials should have good photochemical stability, particle size in the nanometer scale, and non-toxic effects on organisms.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing a strontium-containing hydroxyapatite fluorescent material with higher fluorescence intensity, higher fluorescence lifetime and good biocompatibility.

The technical scheme of the present invention is as follows: a method for preparing a strontium-containing hydroxyapatite fluorescent material is realized by the following steps:

Step 1: the preparation of europium nitrate:

Weigh a certain amount of europium oxide and dissolve it in concentrated nitric acid;

Place the solution obtained after dissolving in a water bath with a water bath temperature of 85°C to obtain europium nitrate crystals;

Dissolve europium nitrate crystals in deionized water to obtain europium nitrate aqueous solution, and set aside;

Step 2: Preparation of strontium-containing hydroxyapatite fluorescent material:

Dissolve strontium nitrate, calcium nitrate and diammonium hydrogen phosphate in deionized water respectively to obtain strontium nitrate aqueous solution, calcium nitrate aqueous solution and diammonium hydrogen phosphate aqueous solution;

Measure a certain amount of strontium nitrate aqueous solution and calcium nitrate aqueous solution and add it to the europium nitrate aqueous solution, and stir evenly to obtain a mixed solution;

Take diammonium hydrogen phosphate aqueous solution and sodium hydroxide aqueous solution and drop them into the mixed solution at a low speed, and keep stirring until the molar ratio of (strontium+calcium)/phosphorus in the reaction system is 1.67, adjust the pH range of the system to 10-14, continue Stir for 1 hour, seal, and leave to age at 80°C for 24 hours to obtain a suspension of strontium-containing hydroxyapatite fluorescent material;

Remove the supernatant by suction filtration to obtain the lower strontium-containing hydroxyapatite fluorescent material precipitate;

The obtained strontium-containing hydroxyapatite fluorescent material precipitate was washed and filtered with deionized water, placed in an oven at a temperature of 80° C. for 24 hours, and finally ground to obtain strontium-containing hydroxyapatite fluorescent material powder.

In the second step, the molar ratio of strontium to calcium ranges from 0.01 to 100 mol%.

In the second step, the molar ratio of europium to (calcium+strontium) is in the range of 0.01-10 mol%.

A strontium-containing hydroxyapatite fluorescent material is prepared by a method for preparing a strontium-containing hydroxyapatite fluorescent material.

Beneficial effect

The raw materials of the preparation method of the present invention are cheap and easy to obtain, the cost is low, and the synthesis process is simple and easy to realize. The technical scheme can be used to obtain strontium-containing hydroxyapatite fluorescent materials. Obviously, the fluorescence lifetime is higher.

Description of drawings

Figure 1 is an X-ray diffraction (XRD) diagram of a strontium-containing hydroxyapatite fluorescent material prepared by a method for preparing a strontium-containing hydroxyapatite fluorescent material of the present invention;

Fig. 2 is a fluorescence emission spectrum diagram of a strontium-containing hydroxyapatite fluorescent material prepared by a method for preparing a strontium-containing hydroxyapatite fluorescent material of the present invention (excitation wavelength is 394 nm);

Fig. 3 is a fluorescence decay curve of a strontium-containing hydroxyapatite fluorescent material prepared by a method for preparing a strontium-containing hydroxyapatite fluorescent material according to the present invention (the excitation wavelength is 394 nm, and the emission wavelength is 618 nm).

detailed description

Example 1

The first step: the preparation of europium nitrate:

First, weigh 0.05g of europium oxide and dissolve it with concentrated nitric acid; secondly, heat the dissolved solution in a water bath at 85°C until light pink europium nitrate crystals are precipitated; finally, prepare europium nitrate into 0.05mol/L europium nitrate aqueous solution 5m;

The second step: preparation of strontium-containing hydroxyapatite fluorescent material:

Prepare concentration respectively with deionized water and be 0.5mol/L calcium nitrate aqueous solution 70ml, concentration be that 0.5mol/L strontium nitrate aqueous solution 30ml and concentration be 0.6mol/L diammonium hydrogen phosphate aqueous solution 50ml; The aqueous solution and the europium nitrate aqueous solution are uniformly mixed to obtain a mixed solution, and are constantly stirred;

Slowly add diammonium hydrogen phosphate aqueous solution dropwise to the above mixed solution. When the molar mass ratio of (strontium+calcium)/phosphorus in the reaction system is 1.67, stop dripping diammonium hydrogen phosphate aqueous solution; 1 L of sodium hydroxide aqueous solution, and constantly stirring, to keep the pH value of the reaction system at 10 to 14, to obtain a suspension containing strontium-containing hydroxyapatite fluorescent material;

The suspension containing the strontium-containing hydroxyapatite fluorescent material was continuously stirred for 1 hour, and then the mouth of the beaker was sealed with a plastic wrap, and left to stand at 80° C. for 24 hours. The suspension containing the strontium-containing hydroxyapatite fluorescent material The suspension is stratified, the upper layer is clear liquid, and the lower layer is the precipitate of strontium-containing hydroxyapatite fluorescent material;

The supernatant liquid is filtered off by suction filtration to obtain the lower strontium-containing hydroxyapatite fluorescent material precipitate, and then the strontium-containing hydroxyapatite fluorescent material precipitate is washed with deionized water and filtered. Less than 10 times;

The strontium-containing hydroxyapatite fluorescent material precipitate is dried at 80° C. for 24 hours, and then ground to obtain strontium-containing hydroxyapatite fluorescent material powder.

After preparing a strontium-containing hydroxyapatite fluorescent material, the composition and structure of the material were characterized by X-ray diffraction pattern (XRD). The XRD pattern is shown in curve a in Figure 1; The luminescence performance of the material under light excitation was characterized. The emission spectrum is shown in curve a in Figure 2, and the luminous intensity is 241.4 a.u.; the fluorescence decay curve is shown in curve a in Figure 3, and the fluorescence lifetime is 1.031 ms.

Example 2

The first step: the preparation of europium nitrate:

First, weigh 0.05g of europium oxide and dissolve it with concentrated nitric acid; secondly, heat the dissolved solution in a water bath at 85°C until light pink europium nitrate crystals are precipitated; finally, prepare europium nitrate into 0.05mol/L europium nitrate aqueous solution 5ml;

The second step: preparation of strontium-containing hydroxyapatite fluorescent material:

Prepare respectively 30ml of 0.5mol/L calcium nitrate aqueous solution, 70ml of 0.5mol/L strontium nitrate aqueous solution and 50ml of 0.6mol/L diammonium hydrogen phosphate aqueous solution with deionized water;

The calcium nitrate aqueous solution, the strontium nitrate aqueous solution and the europium nitrate aqueous solution are uniformly mixed to obtain a mixed solution, and continuously stirred;

Slowly add diammonium hydrogen phosphate aqueous solution dropwise to the above mixed solution. When the molar mass ratio of (strontium+calcium)/phosphorus in the reaction system is 1.67, stop dripping diammonium hydrogen phosphate aqueous solution; L of sodium hydroxide aqueous solution, and constantly stirring, to keep the pH value of the reaction system at 10 to 14, to obtain a suspension containing strontium-containing hydroxyapatite fluorescent material;

The suspension containing the strontium-containing hydroxyapatite fluorescent material was continuously stirred for 1 hour, and then the mouth of the beaker was sealed with a plastic wrap, and left to stand at 80° C. for 24 hours. The suspension containing the strontium-containing hydroxyapatite fluorescent material The suspension is stratified, the upper layer is clear liquid, and the lower layer is the precipitate of strontium-containing hydroxyapatite fluorescent material;

The supernatant liquid is filtered off by suction filtration to obtain the lower strontium-containing hydroxyapatite fluorescent material precipitate, and then the strontium-containing hydroxyapatite fluorescent material precipitate is washed with deionized water and filtered. Less than 10 times;

The strontium-containing hydroxyapatite fluorescent material precipitate is dried at 80° C. for 24 hours, and then ground to obtain strontium-containing hydroxyapatite fluorescent material powder.

After preparing a strontium-containing hydroxyapatite fluorescent material, the composition and structure of the material were characterized by X-ray diffraction pattern (XRD). The XRD pattern is shown in curve b in Figure 1; The luminescence performance of the material under light excitation was characterized. The emission spectrum is shown in curve b in Figure 2, and the luminous intensity is 493.2 a.u.; the fluorescence decay curve is shown in curve b in Figure 3, and the fluorescence lifetime is 1.192 ms.

The content of the present invention is not limited to the examples listed, and any equivalent transformations to the technical solution of the present invention adopted by persons of ordinary skill in the art by reading the description of the present invention are covered by the claims of the present invention.

Claims (4)

1. A method for preparing strontium-containing hydroxyapatite fluorescent material, characterized in that: Achieved by the following steps: Step 1: the preparation of europium nitrate: Weigh a certain amount of europium oxide and dissolve it in concentrated nitric acid; Place the solution obtained after dissolving in a water bath with a water bath temperature of 85°C to obtain europium nitrate crystals; Dissolve europium nitrate crystals in deionized water to obtain europium nitrate aqueous solution, and set aside; Step 2: Preparation of strontium-containing hydroxyapatite fluorescent material: Dissolve strontium nitrate, calcium nitrate and diammonium hydrogen phosphate in deionized water respectively to obtain strontium nitrate aqueous solution, calcium nitrate aqueous solution and diammonium hydrogen phosphate aqueous solution; Measure a certain amount of strontium nitrate aqueous solution and calcium nitrate aqueous solution and add it to the europium nitrate aqueous solution, and stir evenly to obtain a mixed solution; Take diammonium hydrogen phosphate aqueous solution and sodium hydroxide aqueous solution and drop them into the mixed solution at a low speed, and keep stirring until the molar ratio of (strontium+calcium)/phosphorus in the reaction system is 1.67, adjust the pH range of the system to 10-14, continue Stir for 1 hour, seal, and leave to age at 80°C for 24 hours to obtain a suspension of strontium-containing hydroxyapatite fluorescent material; Remove the supernatant by suction filtration to obtain the lower strontium-containing hydroxyapatite fluorescent material precipitate; The obtained strontium-containing hydroxyapatite fluorescent material precipitate was washed and filtered with deionized water, placed in an oven at a temperature of 80° C. for 24 hours, and finally ground to obtain strontium-containing hydroxyapatite fluorescent material powder. 2. A method for preparing a strontium-containing hydroxyapatite fluorescent material according to claim 1, wherein in step 2, the molar ratio of strontium to calcium ranges from 0.01 to 100 mol%. 3 . The method for preparing a strontium-containing hydroxyapatite fluorescent material according to claim 1 , wherein in step 2, the molar ratio of europium to (calcium + strontium) is in the range of 0.01-10 mol%. 4. A strontium-containing hydroxyapatite fluorescent material prepared according to the preparation method of a strontium-containing hydroxyapatite fluorescent material according to claim 1.