CN101091807B - Monodisperse bioglass nanoparticles with nanopores and preparation method thereof - Google Patents

Monodisperse bioglass nanoparticles with nanopores and preparation method thereof Download PDF

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CN101091807B
CN101091807B CN2007100557142A CN200710055714A CN101091807B CN 101091807 B CN101091807 B CN 101091807B CN 2007100557142 A CN2007100557142 A CN 2007100557142A CN 200710055714 A CN200710055714 A CN 200710055714A CN 101091807 B CN101091807 B CN 101091807B
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obtains
surfactant
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CN101091807A (en
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陈学思
刘爱学
庄秀丽
魏俊超
李哲
景遐斌
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Changchun Institute of Applied Chemistry of CAS
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Abstract

本发明提供了具有纳米孔道的单分散生物玻璃纳米粒子及其制备方法，其成分构成及配比为：Si∶Ca∶P质量含量比为50-100∶1-50∶1-15。使用阳离子表面活性剂或者三嵌段非离子表面活性剂为模板剂，采用正硅酸乙酯为硅源，无机钙盐作为钙源，磷酸酯类或者磷酸盐作为磷源。首先在酸性条件下进行水解，然后在碱性条件下进行缩聚；最后通过高温碚烧的方法去除有机物质，进而得到具有纳米孔道的纳米粒子。该方法得到的粒子具有高度有序的纳米孔道，较高的比表面积和孔体积，并且具有较高的生物活性，在骨组织修复，齿科修复，组织工程修复，药物控制释放等方面具有极大的应用前景。The invention provides monodisperse biological glass nanoparticles with nanometer channels and a preparation method thereof. The composition and ratio of the ingredients are: Si:Ca:P mass content ratio is 50-100:1-50:1-15. Cationic surfactants or tri-block nonionic surfactants are used as templates, ethyl orthosilicate is used as silicon sources, inorganic calcium salts are used as calcium sources, and phosphates or phosphates are used as phosphorus sources. First, hydrolysis is carried out under acidic conditions, and then polycondensation is carried out under alkaline conditions; finally, organic substances are removed by high-temperature calcining, and then nanoparticles with nanopores are obtained. The particles obtained by this method have highly ordered nanopores, high specific surface area and pore volume, and high biological activity. Great application prospects.

Description

Single bio-vitric nanoparticle and preparation method thereof that disperses with nano pore
Technical field
The invention belongs to field of inorganic nano material, be specifically related to have single bio-vitric nanoparticle and preparation method thereof that disperses of nano pore.
Technical background
Since preparing M41S series mesopore molecular sieve first from Mobil company in 1992, the scientist has prepared the mesoporous material of various forms and size.Because having the duct of rule, this material arranges, higher specific surface area, thereby have the character of self uniqueness, and separating and absorption, catalysis, pick off, biochip, aspects such as nanometer organic composite material have represented wide application prospect.
In present bone tissue restoration field, have certain biocompatibility and bioactive material such as artificial Corallium Japonicum Kishinouye, hydroxyapatite, bio-vitric, inorganic material such as calcium phosphate have obtained extensive studies.Wherein bio-vitric is than other material, have very high activity, have higher bone formation performance than hydroxyapatite, and meanwhile, have higher biocompatibility and degradation property, obtained the authentication of FDA (FDA).
A lot of people studies show that, increase the specific surface area of bio-vitric, help improving the activity of bio-vitric.This is that bioglass material is more rapid with the exchange of particles of body fluid, helps the deposition of calcium on its surface owing to the raising along with specific surface area.Improving its specific surface area, two kinds of approach are arranged, is the material that preparation has loose structure on the one hand, on the other hand, can reduce the size of particle.The mesoporous bioglass that present stage obtains, size is more than micron, thereby specific surface area is little, and be unfavorable for preparing the nanometer organic composite material as inorganic material, therefore preparation has the nanometer regular pore canal, and the particle of particle size in nanometer range has very high using value for bone tissue restoration.
Summary of the invention
The present invention adopts sol-gel process to prepare to have single bio-vitric nanoparticle that disperses of nano pore, and it utilizes template to carry out self assembly.This single composition of bio-vitric nanoparticle that disperses with nano pore constitutes: Si: Ca: the P mass content is than being 50-100: 1-50: 1-15, and described nano pore diameter is 2-10nm, this bio-vitric nanoparticle particle diameter be 40nm-60nm.
According to the difference that adopts the phosphorus source, the single bio-vitric nano-particle that disperses with nano pore adopts different preparation methoies.When inorganic phosphorous sources is phosphate, employing method 1 described preparation method; When the organophosphor source is phosphoric acid ester, employing method 2 described preparation methoies.
Method 1
1) at first surfactant is joined in 25-50 ℃ the deionized water, stir, it is dissolved fully, obtain the clear solution of surfactant; The quality of surfactant and the volume ratio of deionized water (g/ml) are 4: 350-20: 350.Described surfactant is ionic surfactant or non-ionic surface active agent;
Described ionic surfactant is a long chain quaternary, is Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide or octadecyl trimethylammonium bromide;
Described non-ionic surface active agent is the non-ionic surface active agent of block or three blocks, with poly-oxireme (PEO) as hydrophilic block, poly-epoxy third (PPO) alkene or poly-person's epoxy butylene (PBO) are as hydrophobic block, and the non-ionic surface active agent molecular formula of three blocks is PEO nPPO mPEO n, n=10-140, m=5-100, perhaps molecular formula is PEO nPBO mPEO n, n=10-200, m=10-100, the non-ionic surface active agent molecular formula of two blocks is PEO nPBO m, n=10-100, m=5-60; Be F127 (PEO 99PPO 67PE0 99), F108 (PEO 128PPO 54PE0 128), P85 (PEO 26PPO 40PE0 26), P123 (PEO 20PPO 70PE0 20); PEO is the oxireme unit, and PPO is the propylene oxide unit.
2) in the clear solution that step 1) obtains, add positive silicate class and calcium source respectively, making Si concentration is 0.02-0.06mol/L, and the concentration that makes Ca is 0-0.06mol/L, and regulating PH with acid is 1-4, hydrolysis 2-8 hour, obtains sol solution;
Described positive silicate class is ethyl orthosilicate, methyl silicate or positive silicic acid propyl ester, and described calcium source is lime nitrate or calcium acetate.
3) with step 2) sol solution that obtains of step adds inorganic phosphorous sources, the concentration that makes phosphorus is between 0mol/l-0.02mol/l, and it is 9-11 that PH is regulated with ammonia in inorganic phosphorous sources dissolving back, carries out polycondensation reaction 12h, be warmed up to 60-100 ℃ then and kept 2-72 hour, obtain the white gels suspension; Described inorganic phosphorous sources is Ammonium biphosphate or diammonium phosphate.
4) the white gels suspension filtered that step 3) is obtained, drying obtains the white gels powder.
5) the white gels powder that step 4) is obtained, at 500 ℃-900 ℃, calcination 3-24 hour, remove template, then obtain having single bio-vitric nanoparticle that disperses of nano pore.
Method 2
1) at first surfactant is joined in 25-50 ℃ the deionized water, stir, it is dissolved fully, the quality of surfactant and the volume ratio of water (g/ml) are 4: 350-20: 350; Described surfactant is ionic surfactant or non-ionic surface active agent;
Described ionic surfactant is a long chain quaternary, preferred Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide or octadecyl trimethylammonium bromide;
Described non-ionic surface active agent is the non-ionic surface active agent of block or three blocks, with poly-oxireme (PEO) as hydrophilic block, poly-epoxy third (PPO) alkene or poly-person's epoxy butylene (PBO) are as hydrophobic block, and the non-ionic surface active agent molecular formula of three blocks is PEO nPPO mPEO n, n=10-140, m=5-100, perhaps molecular formula is PEO nPBO mPEO n, n=10-200, m=10-100, perhaps two block non-ionic surface active agent molecular formula are PEO nPBO m, n=10-100, m=5-60 is as F127 (PEO 99PPO 67PEO 99), F108 (PEO 128PPO 54PEO 128), P85 (PEO 26PPO 40PEO 26), P123 (PEO 20PPO 70PEO 20), PEO is the oxireme unit, PPO is the propylene oxide unit.
2) in the clear solution that step 1) obtains, add positive silicate class, making Si concentration is 0.02mol/L-0.06mol/L, it is 0mol/L-0.06mol/L that adding calcium source makes the concentration of Ca, adding the organophosphor source is organophosphorus compounds, and the concentration that makes phosphorus is regulated PH between 1 and 4 with acid then at 0mol/L-0.02mol/L, hydrolysis 2-8 hour, obtain sol solution;
Described positive silicate class is ethyl orthosilicate, methyl silicate or positive silicic acid propyl ester, and described calcium source is lime nitrate or calcium acetate, and the organophosphor source of described organophosphorus compounds is trimethyl phosphate or triethyl phosphate.
3 steps 2) sol solution that obtains of hydrolysis, regulating PH with alkali is 9-11, carries out polycondensation reaction 12h, is warmed up to 60-100 ℃ then and keeps 2-72 hour, obtains gel suspension.
4) gel suspension that the step 3) polycondensation is obtained filters, and drying obtains gel powder.
5) gel powder that step 4) is obtained, at 500 ℃-900 ℃, calcination 3-24 hour, remove surfactant and organic principle as template, obtain having single bio-vitric nanoparticle that disperses of nano pore.
Compared with prior art, reaction condition of the present invention is relatively gentleer, easy and simple to handle; The method of a kind of dimension reduction with mesoporous bioglass in the nanoscale is provided, obtained the mesoporous bioglass granule of grain size in 40nm-100nm, improved the specific surface area of bio-vitric greatly, thereby improved its activity in body fluid; Can be applied to medicine control and release, bone tissue restoration, organizational project etc.
Description of drawings
Fig. 1 is the transmission electron microscope photo of meso-porous nano bio-vitric.
Fig. 2 is the stereoscan photograph of meso-porous nano bio-vitric.
Fig. 3 is the X-ray diffractogram of accompanying drawing 3 mesoporous nano bio-vitrics.
Fig. 4 is BET specific surface area analysis figure.
The specific embodiment
Embodiment 1
1) at first the 6g cetyl trimethyl ammonium bromide is joined in 35 ℃ the 350ml deionized water, stir 30min, it is dissolved fully;
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 3.15gCa (NO 3) 24H 2O regulates PH=2 with nitric acid, hydrolysis 6 hours;
3) with step 2) solution that obtains of step adds 0.4g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 48 hours, obtains the white gels suspension;
4) step 3) is obtained the white gels suspension, filter, drying obtains gel powder;
5) gel powder that step 4) is obtained,, at 500 ℃, calcination 3-24 hour, remove template and organic principle, then obtain containing the nanometer biological glass particles of nano pore.
The granule that obtains is tested its electron scanning micrograph such as accompanying drawing 1, transmission microscopy photo such as accompanying drawing 2, XRD spectra such as accompanying drawing 3, BET specific surface area analysis such as accompanying drawing 4; XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 200m 2/ g.The scanning electron microscope proof is of a size of 60nm.
Embodiment 2
1) at first the 10g cetyl trimethyl ammonium bromide is joined in 35 ℃ the 350ml deionized water, stir 30min, it is dissolved fully;
2) 2)-5) step is identical with example 1.
The granule that obtains is tested, and XRD and transmission electron microscope show and have orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 260m 2/ g.The scanning electron microscope proof is of a size of 60nm.
Embodiment 3
1) earlier the 15g cetyl trimethyl ammonium bromide is joined in 35 ℃ the 350ml deionized water, stir 30min, it is dissolved fully;
2) 2)-5) step is identical with example 1;
The granule that obtains is tested, and XRD and transmission electron microscope show and have orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 280m 2/ g.The scanning electron microscope proof is of a size of 60nm.
Embodiment 4
1) the 20g cetyl trimethyl ammonium bromide is joined in 35 ℃ the 350ml deionized water, stir 30min, it is dissolved fully;
2) 2)-5) step is identical with example 1;
The granule that obtains is tested, and XRD and transmission electron microscope show and have orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 350m 2/ g.The scanning electron microscope proof is of a size of 70nm.
Embodiment 5
1) the 10g cetyl trimethyl ammonium bromide is joined in 35 ℃ the 350ml deionized water, stir 30min, it is dissolved fully;
2) in the clear solution that step 1) is obtained, add the positive silicic acid acetate esters of 2.6g and regulate PH=2, hydrolysis 6 hours with acid;
3) with step 2) sol solution that obtains is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 48 hours, obtains the white gels suspension;
4) step 3) is obtained the white gels suspension, filter, drying obtains gel powder;
5) gel powder that step 4) is obtained, at 500 ℃, calcination 3-24 hour, remove template and organic principle, then obtain containing the nanometer biological glass particles of nano pore.
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 820m 2/ g.The scanning electron microscope proof is of a size of 60nm.
Embodiment 6
1) with example 4 the 1st) step;
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) solution that obtains of step adds 0.2g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 48 hours, obtains the white gels suspension;
4) step 3) is obtained the white gels suspension, filter, drying obtains gel powder;
5) gel powder that step 4) is obtained, at 500 ℃, calcination 3-24 hour, remove template and organic principle, obtain having single bio-vitric nanoparticle that disperses of nano pore;
The single bio-vitric nanoparticle that disperses with nano pore that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 310m 2/ g, the scanning electron microscope proof is of a size of 80nm.
Embodiment 7
1) example 5 the 1st) step;
2) in the clear solution that step 1) is obtained, add 2.6g silicic acid acetate esters and 0.8gCa (NO 3) 24H 2O regulates PH=2 with hydrochloric acid, hydrolysis 6 hours;
3) with step 2) solution that obtains of step adds 0.1g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 48 hours, obtains the white gels suspension;
4) with example 5 step 4);
5) with example 5 step 5);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 460m 2/ g.The scanning electron microscope proof is of a size of 50nm.
Embodiment 8
1) with example 4 step 1);
2) with step with 1) in the clear solution that obtains, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2 with nitric acid, hydrolysis 6 hours.；
3) with step 2) solution that obtains of step adds 0.2g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 24 hours, obtains the white gels suspension.；
4) with example 6 step 4);
5) with example 6 step 5);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 280m 2/ g, scanning electron microscope proof size is about 70nm.
Embodiment 9
1) with example 4 step 1);
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) solution that obtains of step adds 0.2g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 100 ℃ then and keeps 72 hours, obtains the white gels suspension;
4) with example 6 step 4);
5) with example 6 step 5).
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 360m 2/ g.
Embodiment 10
1) with example 4 step 1);
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) solution that obtains of step adds 0.2g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 12h, is warmed up to 60 ℃ then and keeps 48 hours, obtains the white gels suspension;
4) with example 6 step 4);
5) with example 6 step 5);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 240m 2/ g.
Embodiment 11
1) with example 4 step 1);
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) solution that obtains of step adds 0.2g (NH 4) 2HPO 4, the dissolving back is adjusted to alkalescence with ammonia with PH, makes PH=10, carries out polycondensation reaction 48h and obtains the white gels suspension;
4) with example 6 step 4);
5) with example 6 step 5);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 220m 2/ g.
Embodiment 12
1) with example 4 the 1st) step;
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 3.15gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) sol solution that obtains, with ammonia PH is adjusted to alkalescence, make PH=10, hydrolysis 12 hours is warmed up to 100 ℃ then and kept 72 hours, obtains the white gels suspension;
4) with example 6 step 4);
5) with example 6 step 5).
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 323m 2/ g.
Embodiment 13
1) with example 4 the 1st) step;
2) in the clear solution that step 1) is obtained, add positive silicic acid acetate esters of 2.6g and 1.6gCa (NO 3) 24H 2O regulates PH=2, hydrolysis 6 hours with acid;
3) with step 2) sol solution that obtains is adjusted to alkalescence with ammonia with PH, makes PH=10, and hydrolysis 12 hours is warmed up to 100 ℃ then and kept 72 hours, obtains the white gels suspension;
4) with example 6 step 4);
5) with example 6 step 5).；
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, specific surface area 462m 2/ g.
Embodiment 14
1) earlier the 10g cetyl trimethyl ammonium bromide is joined in 35 ℃ the deionized water, stir 30min, it is dissolved fully, the quality of surfactant and the volume ratio of water are (g/ml)=4/350-20/350;
2) in the clear solution that step 1) is obtained, positive silicic acid acetate esters of 2.6g and 3.15gCa (NO 3) 24H 2O,, the 0.42g trimethyl phosphate, 0mol/1-0.02mol/l regulates between the PH=2 hydrolysis 2-8 hour then with acid;
3) with step 2) sol solution that obtains after finishing of hydrolysis is adjusted to alkalescence with alkali PH, and PH=1-11 carried out polycondensation reaction 2-72 hour, obtained the white gels suspension;
What 4) step 3) is obtained after polycondensation reaction is finished filters gel particle drying.Obtain the white gels powder.The white powder that obtains after the drying at 550 ℃ of calcination 3-24 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore;
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, N 2Absorption shows its specific surface area 336m 2/ g.
Embodiment 15
1) the 10g Dodecyl trimethyl ammonium chloride is joined in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 steps 2);
3) with example 13 step 3);
4) with example 13 step 4);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 2-3nm, N 2Absorption shows its specific surface area 273m 2/ g.
Embodiment 16
1) 10g octadecyl trimethylammonium bromide is joined in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 steps 2);
3) with example 13 step 3);
4) with example 13 step 4);
The granule that obtains is tested, and XRD shows and has orderly hexagonal mesoporous structure, aperture 3-4nm, N 2Absorption shows its specific surface area 396m 2/ g.
Embodiment 17
1) with 10g F127 (PEO 106PPO 70PEO 106) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying at 550 ℃ of calcination 3-24 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.
Embodiment 18
1) with 10g P123 (PEO 20PPO 70PEO 20) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying 550 ℃ of calcinations 5 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.
Embodiment 19
1) 10g F108 (PEO 132PPO 20PEO 132) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying 550 ℃ of calcinations 5 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.
Embodiment 20
1) with 10g F108 (PEO 132PPO 20PEO 132) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying 550 ℃ of calcinations 5 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.
Embodiment 21
1) with 10g P65 (PEO 20PPO 30PEO 20) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying 550 ℃ of calcinations 3 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.
Embodiment 22
1) 10g P85 (PEO 26PPO 39PEO 26) join in 35 ℃ the deionized water, stir 30min, it is dissolved fully;
2) with example 13 the 2nd);
3) with example 13 the 3rd);
4) after polycondensation reaction is finished, gel particle is filtered drying.Obtain the white gels powder.The white powder that obtains after the drying 550 ℃ of calcinations 3 hours, is removed template and organic principle, then obtains containing the nanometer biological glass particles of nano pore.

Claims (5)

1. have single bio-vitric nanoparticle that disperses of nano pore, it is characterized in that its composition constitutes and proportioning is: Si: Ca: the P mass content is than being 50-100: 1-50: 1-15;
The particle diameter of this bio-vitric nanoparticle is 40nm-60nm, and it has the nano pore diameter is 2-10nm.
2. the single bio-vitric nanometer particle process method of disperseing with nano pore described in claim 1 is characterized in that,
1) at first surfactant is joined in 25-50 ℃ the deionized water, stir, it is dissolved fully, obtain the clear solution of surfactant, the quality of surfactant and the volume ratio of deionized water (g/ml) they are 4: 350-20: 350, and described surfactant is ionic surfactant or non-ionic surface active agent; Described ionic surfactant is a long chain quaternary;
Described non-ionic surface active agent is the non-ionic surface active agent of block or three blocks, and as hydrophilic block, poly-epoxy third (PPO) alkene or poly-epoxy butylene (PBO) are as hydrophobic block with poly-oxireme (PEO); Described PEO is the oxireme unit, and PPO is the propylene oxide unit;
The non-ionic surface active agent molecular formula of described three blocks is PEO nPPO mPEO n, n=10-140, m=5-100, perhaps molecular formula is PEO nPBO mPEO n, n=10-200, m=10-100, the non-ionic surface active agent molecular formula of two blocks is PEO nPBO m, n=10-100, m=5-60;
2) in the clear solution that step 1) obtains, add positive silicate class and calcium source respectively, making Si concentration is 0.02-0.06mol/L, and the concentration that makes Ca is greater than 0mol/L and less than 0.06mol/L, and regulating PH with acid is 1-4, hydrolysis 2-8 hour, obtains sol solution;
Described positive silicate class is ethyl orthosilicate, methyl silicate or positive silicic acid propyl ester, and described calcium source is lime nitrate or calcium acetate;
3) with step 2) sol solution that obtains of step adds inorganic phosphorous sources, the concentration that makes phosphorus is greater than 0mol/L and less than 0.02mol/L, and it is 9-11 that PH is regulated with ammonia in inorganic phosphorous sources dissolving back, carries out polycondensation reaction 12h, be warmed up to 60-100 ℃ then and kept 2-72 hour, obtain the white gels suspension; Described inorganic phosphorous sources is Ammonium biphosphate or diammonium phosphate;
4) the white gels suspension filtered that step 3) is obtained, drying obtains the white gels powder;
5) the white gels powder that step 4) is obtained, at 500 ℃-900 ℃, calcination 3-24 hour, remove surfactant and organic component as template, then obtain having single bio-vitric nanoparticle that disperses of nano pore.
3. the single bio-vitric nanometer particle process method of disperseing with nano pore as claimed in claim 2, it is characterized in that described long chain quaternary is Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide or octadecyl trimethylammonium bromide.
4. the single bio-vitric nanometer particle process method of disperseing with nano pore as claimed in claim 1 is characterized in that,
1) at first surfactant is joined in 25-50 ℃ the deionized water, stir, it is dissolved fully, the quality of surfactant and the volume ratio of water (g/ml) are 4: 350-20: 350; Described surfactant is ionic surfactant or non-ionic surface active agent;
Described ionic surfactant is a long chain quaternary;
Described non-ionic surface active agent is the non-ionic surface active agent of block or three blocks, and as hydrophilic block, poly-epoxy third (PPO) alkene or poly-person's epoxy butylene (PBO) are as hydrophobic block with poly-oxireme (PEO);
The non-ionic surface active agent molecular formula of described three blocks is PEO nPPO mPEO n, n=10-140, m=5-100, perhaps molecular formula is PEO nPBO mPEO n, n=10-200, m=10-100, perhaps two block non-ionic surface active agent molecular formula are PEOnPBOm, n=10-100, m=5-60; PEO is the oxireme unit, and PPO is the propylene oxide unit;
2) in the clear solution that step 1) obtains, add positive silicate class, making Si concentration is 0.02mol/L-0.06mol/L, adding the calcium source makes the concentration of Ca greater than 0mol/L and less than 0.06mol/L, adding the organophosphor source is organophosphorus compounds, and the concentration that makes phosphorus is regulated PH between 1 and 4 with acid then greater than 0mol/L and less than 0.02mol/L, hydrolysis 2-8 hour, obtain sol solution;
Described positive silicate class is ethyl orthosilicate, methyl silicate or positive silicic acid propyl ester, and described calcium source is lime nitrate or calcium acetate, and the organophosphor source of described organophosphorus compounds is trimethyl phosphate or triethyl phosphate;
3) step 2) sol solution that obtains of hydrolysis, regulating PH with alkali is 9-11, carries out polycondensation reaction 12h, is warmed up to 60-100 ℃ then and keeps 2-72 hour, obtains gel suspension;
4) gel suspension that the step 3) polycondensation is obtained filters, and drying obtains gel powder;
5) gel powder that step 4) is obtained, at 500 ℃-900 ℃, calcination 3-24 hour, remove surfactant and organic principle as template, obtain having single bio-vitric nanoparticle that disperses of nano pore.
5. the single bio-vitric nanometer particle process method of disperseing with nano pore as claimed in claim 4, it is characterized in that, described long chain quaternary is Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide or octadecyl trimethylammonium bromide.
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