Biodegradable fluorescent mesoporous silica composite nanosphere and preparation method thereof

Abstract

The invention provides a biodegradable fluorescent mesoporous silicon dioxide composite nanosphere and a preparing method thereof. The biodegradable fluorescent mesoporous silicon dioxide composite nanosphere is prepared from p-toluenesulfonic acid hexadecyl trimethyl ammonium, triethanolamine, silicate ester, a HPO42- ionic solution, a Ca2+ ionic solution and a Eu3+ inonic solution, wherein p-toluenesulfonic acid hexadecyl trimethyl ammonium is a template, triethanolamine is a catalyst, and the mole ratio of the HPO42- ionic solution to the Ca2+ ionic solution is (2:3)-(5:8). According to the prepared Eu3+:HAp / MSN composite nanosphere, a spherical mesoporous material with the size of 60 nm-80nm is synthesized; by adopting an in-situ sol-gel method, biodegradable HAp is doped to a framework of MSN, and not only a large MSN specific surface area and an ordered pore structure are maintained, but also a biodegradation function of MSN is achieved; by doping Eu3+ ions in a HAp crystal lattice, fluorescent silicon dioxide with infrared emission is obtained. The preparing method of the biodegradable fluorescent mesoporous silicon dioxide composite nanosphere is simple in technology and mild in reaction condition.

Description

technical field

[0001] The invention relates to the field of fluorescent nanometers, in particular to a biodegradable fluorescent mesoporous silica composite nanosphere and a preparation method thereof. Background technique

[0002] Multifunctional nano-drug carriers can integrate disease diagnosis, treatment and drug tracking, and have attractive application prospects in the field of biomedicine, and are also one of the hot research topics in recent years. At present, porous silica nanomaterials are considered as an excellent drug carrier, because the material has a large pore size (greater than 2 nm), huge specific surface area and pore volume, which is conducive to the loading and storage of drugs; good biological Compatibility and hydrophilic properties, very suitable for biological applications. In addition, its surface is rich in silanol groups, which is easy to modify and modify its surface. However, the surface group of pure silica material is single (Si-OH), and i...

Examples

Embodiment 1

[0028] A preparation method of biodegradable fluorescent mesoporous silica composite nanospheres, comprising the following steps,

[0029] (1) Take 5×10 -4 mol~10×10 -4 mol cetyltrimethylammonium p-toluenesulfonate (CTAT) was added to the three-necked flask, and then 20-80 mL deionized water and 5×10 -4 mol~6.7×10 -3 mol triethanolamine (TEA), magnetically stirred at 70-90°C for 40-60 min to prepare template micelles in the reaction system;

[0030] (2) Add 5×10 -4 mol~1.6×10 -3 molHPO 4 2- Ionic solution, magnetic stirring at 70-90°C for 30-50 minutes. Then, under mechanical stirring at 600-1000 rpm, add 6×10 -3 mol~1.2×10 -2 mol silicate, after stirring for 3-10 min, quickly add 7.5×10 -4 mol~2.56×10 -3 mol Ca 2+ ionic solution and 5 x 10 -6 mol~5×10 -5 mol of Eu 3+ Ionic solution, 70-90 °C water bath, continue to stir for 4-6 h, cool to room temperature and centrifuge to obtain the precipitate, wash the precipitate with deionized water and absolute ethanol fo...

Embodiment 2

[0033] (1) Add 0.342 g of cetyltrimethylammonium p-toluenesulfonate (CTAT) into a 100 mL three-necked bottle, then add 50 mL of deionized water, and ultrasonically disperse for 5 min to obtain a transparent and uniform mixed solution. Add 0.2 g of triethanolamine (TEA) to the mixture, seal it, and magnetically stir it in a water bath at 80°C for 40 min to prepare template micelles in the reaction system;

[0034] (2) Then add 0.32 g Na to the step-up solution 2 HPO 4 •12H2 O, continue stirring for 30 min. Under mechanical stirring at a speed of 1000 rpm, 2.0 mL tetraethyl orthosilicate (TEOS) was added dropwise at a rate of 1 drop / s, and the addition was completed within 5 minutes, and the stirring was continued for 3 minutes. Then quickly add 0.15 g of anhydrous CaCl 2 and a volume of 50 μL of EuCl at a concentration of 0.5 mol / L 3 The solution was stirred in a water bath at 80 °C for 4 h, cooled to room temperature, and centrifuged at a speed of 5000 rpm to obtain a prec...

Embodiment 3

[0037] A preparation method of biodegradable fluorescent mesoporous silica composite nanospheres, comprising the following steps,

[0038] (1) Add 0.360 g of cetyltrimethylammonium p-toluenesulfonate (CTAT) into a three-neck flask, then add 80 mL of deionized water and 1.0 g of triethanolamine (TEA), and stir magnetically at 90°C for 60 min to prepare Obtain the template agent micelle in the reaction system;

[0039] (2) Add 0.50g Na to the template micelles in the reaction system prepared in step (1) 2 HPO 4 •12H 2 O, magnetic stirring at 70-90°C for 30-50 minutes. Then, under mechanical stirring at 1000 rpm, 3.0 mL of methyl orthosilicate was added dropwise at a rate of 2 drops / second, and after stirring for 3 to 10 min, 0.2 g of Ca(NO 3 ) 2 powder and a volume of 100 μL of EuCl at a concentration of 0.5 mol / L 3 The solution was continuously stirred in a water bath at 90°C for 5 h, cooled to room temperature and then centrifuged, the precipitate was washed twice with d...

technical field

[0001] The invention relates to the field of fluorescent nanometers, in particular to a biodegradable fluorescent mesoporous silica composite nanosphere and a preparation method thereof. Background technique

[0002] Multifunctional nano-drug carriers can integrate disease diagnosis, treatment and drug tracking, and have attractive application prospects in the field of biomedicine, and are also one of the hot research topics in recent years. At present, porous silica nanomaterials are considered as an excellent drug carrier, because the material has a large pore size (greater than 2 nm), huge specific surface area and pore volume, which is conducive to the loading and storage of drugs; good biological Compatibility and hydrophilic properties, very suitable for biological applications. In addition, its surface is rich in silanol groups, which is easy to modify and modify its surface. However, the surface group of pure silica material is single (Si-OH), and i...

Examples

Embodiment 1

[0028] A preparation method of biodegradable fluorescent mesoporous silica composite nanospheres, comprising the following steps,

[0029] (1) Take 5×10 -4 mol~10×10 -4 mol cetyltrimethylammonium p-toluenesulfonate (CTAT) was added to the three-necked flask, and then 20-80 mL deionized water and 5×10 -4 mol~6.7×10 -3 mol triethanolamine (TEA), magnetically stirred at 70-90°C for 40-60 min to prepare template micelles in the reaction system;

[0030] (2) Add 5×10 -4 mol~1.6×10 -3 molHPO 4 2- Ionic solution, magnetic stirring at 70-90°C for 30-50 minutes. Then, under mechanical stirring at 600-1000 rpm, add 6×10 -3 mol~1.2×10 -2 mol silicate, after stirring for 3-10 min, quickly add 7.5×10 -4 mol~2.56×10 -3 mol Ca 2+ ionic solution and 5 x 10 -6 mol~5×10 -5 mol of Eu 3+ Ionic solution, 70-90 °C water bath, continue to stir for 4-6 h, cool to room temperature and centrifuge to obtain the precipitate, wash the precipitate with deionized water and absolute ethanol fo...

Embodiment 2

[0033] (1) Add 0.342 g of cetyltrimethylammonium p-toluenesulfonate (CTAT) into a 100 mL three-necked bottle, then add 50 mL of deionized water, and ultrasonically disperse for 5 min to obtain a transparent and uniform mixed solution. Add 0.2 g of triethanolamine (TEA) to the mixture, seal it, and magnetically stir it in a water bath at 80°C for 40 min to prepare template micelles in the reaction system;

[0034] (2) Then add 0.32 g Na to the step-up solution 2 HPO 4 •12H2 O, continue stirring for 30 min. Under mechanical stirring at a speed of 1000 rpm, 2.0 mL tetraethyl orthosilicate (TEOS) was added dropwise at a rate of 1 drop / s, and the addition was completed within 5 minutes, and the stirring was continued for 3 minutes. Then quickly add 0.15 g of anhydrous CaCl 2 and a volume of 50 μL of EuCl at a concentration of 0.5 mol / L 3 The solution was stirred in a water bath at 80 °C for 4 h, cooled to room temperature, and centrifuged at a speed of 5000 rpm to obtain a prec...

Embodiment 3

[0037] A preparation method of biodegradable fluorescent mesoporous silica composite nanospheres, comprising the following steps,

[0038] (1) Add 0.360 g of cetyltrimethylammonium p-toluenesulfonate (CTAT) into a three-neck flask, then add 80 mL of deionized water and 1.0 g of triethanolamine (TEA), and stir magnetically at 90°C for 60 min to prepare Obtain the template agent micelle in the reaction system;

[0039] (2) Add 0.50g Na to the template micelles in the reaction system prepared in step (1) 2 HPO 4 •12H 2 O, magnetic stirring at 70-90°C for 30-50 minutes. Then, under mechanical stirring at 1000 rpm, 3.0 mL of methyl orthosilicate was added dropwise at a rate of 2 drops / second, and after stirring for 3 to 10 min, 0.2 g of Ca(NO 3 ) 2 powder and a volume of 100 μL of EuCl at a concentration of 0.5 mol / L 3 The solution was continuously stirred in a water bath at 90°C for 5 h, cooled to room temperature and then centrifuged, the precipitate was washed twice with d...

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