CN101255335A - Preparation of Tb surface finished hydroxyl apatite fluorescent nano-particle - Google Patents
Preparation of Tb surface finished hydroxyl apatite fluorescent nano-particle Download PDFInfo
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- CN101255335A CN101255335A CNA2008100604006A CN200810060400A CN101255335A CN 101255335 A CN101255335 A CN 101255335A CN A2008100604006 A CNA2008100604006 A CN A2008100604006A CN 200810060400 A CN200810060400 A CN 200810060400A CN 101255335 A CN101255335 A CN 101255335A
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Abstract
A preparation of Tb surface modified hydroxylapatite fluorescent nano particle, which uses cetyl trimethyl ammonium bromide as additive, adds calcium salt solution into mixed solution of phosphate radical and cetyl trimethyl ammonium bromide drop by drop, adds aqueous ammonia drop by drop to regulate pH value of the solution, precipitates hydroxylapatite particles from the solution to form suspending liquid of hydroxylapatite, regulates pH value with alcaine, adds Tb<SUP>3+</SUP> drop by drop into suspending liquid to substitute surface portion Ca<SUP>2+</SUP> of hydroxylapatite nano particle with Tb<SUP>3+</SUP>, obtains rice shaped particles by filtering, abstersion, vacuum drying and collecting, which has a long diameter of 40-60mm, and short diameter of 15-20 mm. The inventive preparation is simple in process, easy to get raw materials. The product is characterized by evident fluorescent feature, miniature, good biodegradability, which can be used as stable biological probe material.
Description
Technical field
The present invention relates to a kind of bioprobe and carry out hydroxyl apatite fluorescent nano-particle of finishing and preparation method thereof with Tb.Belong to biotechnology and materials science field.
Background technology
Want the interior various variations that taken place of Real Time Observation organism, just usually need to use bioprobe.The bioprobe material that is widely used at present mainly can be divided into following two classes: the first kind, also be that a most widely used class is exactly the organic molecule with fluorescent characteristic simultaneously, Yang YK, Ko SK, Shin I, Tae J, Synthesis of a highly metal-selectiverhodamine-based probe and its use for the in vivo monitoring of mercury.NATUREPROTOCOLS, 2007,2:1740-1745; Tanaka K, Miura T, Umezawa N, Urano Y, Kikuchi K, HiguchiT, Nagano T, Rational design of fluorescein-based fluorescence probes.Mechanism-based design of a maximum fluorescence probe for singlet oxygen, JOURNALOF THE AMERICAN CHEMICAL SOCIETY, 2001,123 (11): 2530-2536, though these organic fluorescence probe susceptibilitys are higher, but a significant disadvantage is also arranged simultaneously, that is exactly photobleaching (photobleaching), ZondervanR, Kulzer F, Kol ' chenko M A, Orrit M, Photobleaching of rhodamine 6G in poly (vinylalcohol) at the ensemble and single-molecule levels, THE JOURNAL OF PHYSICALCHEMISTRY A, 2004,108 (10): 1657-1665 Talhavini M, Atvars TDZ.Dye-polymerinteractions controlling the kinetics of fluorescein photobleaching reactions inpoly (vinyl alcohol), JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A:CHEMISTRY, 1998,114 (1): 65-73, under light source activation, the fluorescence radiation intensity of these fluorescent probes can descend rapidly, so the organic fluorescence probe can not be applied to carry out long-time continuous observation and maybe needs to carry out in the experiment of detection by quantitative.
Second class bioprobe material---the semiconductor-quantum-point material, Gao X, Cui Y, Levenson RM, Chung LWK, NieS, in vivo cancer targeting and imaging with semiconductor quantum dots, NATUREBIOTECHNOLOGY, 2004,22 (8): 969-976, then overcome this shortcoming as CdSe-CdS, CdSe-ZnS, InAs, InP etc., have metastable fluorescence radiation intensity.But the problem of the biological safety that is caused by the toxicity of cadmium salt and indium salt makes this class fluorescence probe material application in vivo also be restricted.
Result of study shows, the nano inorganic luminescent material might become the new bioprobe of a class by the alternative semiconductors quantum dot, PatraCR, Bhattacharya R, Patra S, Basu S, Mukherjee P, Mukhopadhyay D, Inorganic phosphatenanorods are a novel fluorescent label in cell biology, JOURNAL OF NANOBIOTECHNOLOGY, 2006,4:11, the biological fluorescent labeling material in the ideal should have good bio-compatibility, biological activity and light stability, particle size is preferably nanoscale, and to the organism toxicological harmless.
(Hydroxyapatite is called for short HAP to hydroxyapatite, and molecular formula is Ca
10(PO
4)
6(OH)
2) be the main inorganic moiety of human body and animal body endoskeleton and tooth, have good bio-compatibility and biological activity, aspect plastic surgery and dentistry, HAP has obtained widespread use as the surrogate of skeleton and tooth.Sautier JM, Nefussi JR, ForestN.Ultrastructural study of bone formation on synthetic hydroxyapatite in osteoblastcultures, CELLS AND MATERIALS, 1991,1 (33): 209-217, can know by inference by the nanometer dissolution mode, in vivo in the environment, the nano-HAP particle can stable existence on kinetics, Tang R, Wang L, Orme CA, Bush PJ, Nancollas GH, Dissolution at the nanoscale:self-preservation of biominerals, ANGEWANDTE CHEMIE INTERNATIONAL EDITION, 2004,43 (20): 2697-2701.
Therefore nano-hydroapatite particles should be well suited for being used as bioprobe.But this there is no tangible fluorescent emission hydroxyapatite under excited by visible light, need it carries out finishing with ion pair that can be luminous.Also do not have at present the preparation method simple, to fluorescence under the basic toxicological harmless effect of organism, the excited by visible light obviously and the nanometer hydroxyapatite associated materials that can enter cell interior easily be in the news.
Summary of the invention
In order to overcome the shortcoming of existing bioprobe material, it is simple that the present invention proposes a kind of preparation method, has the preparation method of the compatible and stable hydroxyl apatite fluorescent nano-particle of good biological.
Total technical conceive of the present invention is: with Tb hydroxyapatite is carried out finishing, obtain the hydroxyl apatite fluorescent nano-particle after Tb modifies.A kind of new bioprobe material-Tb doped hydroxyapatite fluorescent nano particle is provided, and the preparation method of Tb doped hydroxyapatite fluorescent nano particle.
The present invention carries out surface modification method with Tb to hydroxyapatite: with cetyl trimethylammonium bromide (CTAB) is additive, calcium salt soln is dropwise added in the solution that contains phosphate radical and CTAB, while dropping ammonia solution regulator solution pH value, hydroapatite particles is separated out from solution, form the hydroxyapatite milk-white coloured suspension, with the pH value of hydrochloric acid conditioning solution, in solution, drip Tb again
3+Solution makes the portion C a on surface of hydroxyapatite nanoparticle
2+By Tb
3+Replace, after filtration, the washing, collect after the vacuum-drying, obtain Tb doped hydroxyapatite fluorescent nano particle.
Tb doped hydroxyapatite fluorescent nano particle provided by the invention, it is characterized in that: particle is grain of rice shape, the particle major diameter is about 40-60nm, minor axis is about 15-20nm, have obvious photoluminescent property, a plurality of excitation spectrum peak is arranged, the maximum excitation peak position is in 272nm, also have excitation peak to exist at visible light wave range (488nm), fluorescent grain emission maximum spectrum peak position is in 544nm.
The present invention carries out finishing with Tb hydroxyl apatite fluorescent nano-particle preparation method's concrete steps are as follows:
A) preparation contains the mixing solutions of phosphate radical and cetyl trimethylammonium bromide, with concentration is that the CTAB of 0.85～0.95mM and phosphate solution that concentration is 5.5～6.5mM stir, with the pH value that ammoniacal liquor is regulated mixing solutions, the pH value that makes solution is 9～10.
The Ca/P mol ratio is 1.65～1.69 amount when b) finishing by reaction, to mixed solution and dripping concentration is the 0.5M calcium salt soln, rate of addition is 1 droplet/second, ammoniacal liquor with 0.1M is regulated, make the pH value of reaction system remain between 9～10, stir, sustained reaction 1～3 hour obtains the hydroxyapatite colloidal sols milk-white coloured suspension;
C) in hydroxyapatite colloidal sols, with 1M HCl system pH is adjusted to 6.0～7.0, Tb in the system when finishing by reaction: (Ca+Tb)=1: 100～4: 100 amount, dripping concentration is the terbium salts solution of 4.0～6.0mM, rate of addition is 1 droplet/second;
D) reaction went out precipitation with the filtering with microporous membrane of 0.22 μ m after 22～24 hours, repeatedly replace thorough washing precipitation with deionized water and ethanol after, place 30 ℃ of vacuum drying oven dried overnight, can obtain the hydroxyl apatite fluorescent nano-particle after the Tb modification.
Phosphoric acid salt of the present invention can be: a second month in a season of Secondary ammonium phosphate, potassium primary phosphate, primary ammonium phosphate, Sodium phosphate dibasic, tertiary sodium phosphate, Tripotassium phosphate, be preferably Sodium phosphate dibasic.
Calcium salt of the present invention can be: nitrocalcite, calcium chloride.Be preferably calcium chloride.
Terbium salt of the present invention can be: Terbium trinitrate, terbium chloride.Be preferably Terbium trinitrate.
The concentration range of cetyl trimethylammonium bromide of the present invention is 0.85～0.95mM, is preferably 0.90mM.
The phosphate concentration scope is 5.5～6.5mM in the reaction system of the present invention, is preferably 6.0mM.
The Ca/P mol ratio was when the present invention dripped calcium salt soln reaction end: 1.65～1.69, be preferably 1.67.
After the present invention drips calcium salt, pH value of solution is adjusted between 9～10, is preferably 9.5 with ammoniacal liquor.
The reaction times that the present invention drips behind the calcium salt is 1～3 hour, is preferably 2 hours.
The present invention drips before the terbium salt, with hydrochloric acid pH value of solution is adjusted between 6.0～7.0, is preferably 6.5.
Tb of the present invention: (Ca+Tb) be: 1: 100～4: 100, be preferably 2: 100.
The reaction times that the present invention drips after the terbium salt is 22～24 hours, is preferably 23 hours.
The ammonia concn that reaction system of the present invention is regulated the pH value is 0.1M.
The concentration of hydrochloric acid that hydroxyapatite colloidal sols suspension liquid system pH of the present invention is regulated is 1M.
PH value of the present invention adopts accurate pH test paper to measure.
The nano hydroxylapatite doped fluorescent nano particle of Tb of the present invention, particle is grain of rice shape, its major diameter is about 40-60nm, minor axis is about 15-20nm, have obvious photoluminescent property, a plurality of excitation spectrum peak is arranged, its maximum excitation peak position is in 272nm, (488nm) also has excitation peak at visible light wave range, and emission maximum spectrum peak position is in 544nm.
The nano hydroxylapatite doped particle of Tb of the present invention, fluorescence obviously and can enter cell interior easily under excited by visible light, as the bioprobe material, to have good bio-compatibility, biological activity and light stability, particle size be nanoscale, to the basic toxicological harmless effect of organism, preparation technology is simple, starting material obtain easily, has obvious fluorescent characteristics, size is little, can be excited by visible light wave range again, has broad application prospects at bioengineering field.
Description of drawings
The transmission electron microscope picture of the hydroxyl apatite fluorescent nano-particle after accompanying drawing 1Tb modifies
The X-ray diffractogram of the hydroxyl apatite fluorescent nano-particle after accompanying drawing 2Tb modifies
When accompanying drawing 3 excitation wavelengths are 272nm, the fluorescent emission spectrogram of the hydroxyapatite nanoparticle after Tb modifies
Accompanying drawing 4 figure (a) be emission wavelength when 544nm, the fluorescent exciting spectrogram of the hydroxyapatite nanoparticle after Tb modifies.
Figure (b) is the details enlarged view of figure (a) in the 300-500nm zone.
Embodiment
Embodiment 1
A kind of hydroxyl apatite fluorescent nano-particle that carries out finishing with Tb, its preparation process is followed successively by:
1. with 1.8mmol Na
2HPO
412H
2O and 0.27mmol cetyl trimethylammonium bromide (CTAB) are dissolved in the 294mL deionized water, and be even with magnetic stirrer, and stirring velocity is 200 rev/mins;
2. above-mentioned the first step solution stirring is after 10 minutes, measures mixing solutions pH value with accurate pH test paper, is 9.5 with the ammoniacal liquor regulator solution pH of 0.1M;
3. slowly dripping concentration in the above-mentioned second step solution is the calcium chloride solution 6ml of 0.5M, rate of addition is 1 droplet/second, in the process of dropping calcium chloride solution, is the ammoniacal liquor regulator solution pH value at any time of 0.1M with concentration, make it maintain 9.5 all the time, obtain hydroxyapatite colloidal sols;
4. above-mentioned the 3rd step colloidal sol after one hour, transfers to pH=6.5 with 1M HCl with system through magnetic agitation, measures mixing solutions pH value with accurate pH test paper.
5. in above-mentioned the 4th step colloidal sol, slowly drip 12.2mL 5.0mMTb (NO
3)
3Solution, rate of addition are 1 droplet/second.
6. above-mentioned the 5th step colloidal sol is through magnetic agitation after 23 hours, leaches precipitation, usefulness washed with de-ionized water three times with the millipore filtration of 0.22 μ m;
7. precipitation is placed 30 ℃ of vacuum drying ovens dry 12 hours, and made the hydroxyapatite nanoparticle that Tb modifies.
8. with transmission electron microscope (JEM-200CX, JEOL Japan) pattern of the hydroxyapatite nanoparticle that Tb is modified has carried out analyzing (seeing accompanying drawing 1), the result shows that the nano particle major diameter is about 40-60nm, minor axis is about 15-20nm, with X-ray diffractometer (D/MAX-RA, Rigaku Japan) analyzed the phase composite (seeing accompanying drawing 2) of nano particle, shown that this nano particle has still kept hydroxyapatite structure.Use day island proper Tianjin RF-5301pc type spectrophotofluorometer that the photoluminescent property of nano particle has been carried out analyzing (seeing accompanying drawing 3 and accompanying drawing 4), the result shows that this particle has obvious photoluminescent property, a plurality of excitation spectrum peak is arranged, its maximum excitation peak position also has excitation peak to exist in 272nm at visible light wave range (488nm).This fluorescent grain emission maximum spectrum peak position is in 544nm.
Embodiment 2
With reference to the preparation process of embodiment 1, the phosphoric acid salt that different is in the mixing solutions adopts Secondary ammonium phosphate; Calcium salt adopts nitrocalcite, and terbium salt adopts terbium chloride; The concentration of cetyl trimethylammonium bromide is 0.85mM; The concentration of phosphate radical is 5.5mM; The Ca/P mol ratio was 1.65 when reaction finished; Be 9 with ammoniacal liquor regulator solution pH after dripping calcium salt; Drip the calcium salt afterreaction 1 hour, and with 1MHCl system was transferred to pH=6.0 then; After dripping terbium salt, Tb: (Ca+Tb) mol ratio is: 1: 100; After dripping terbium salt, the reaction times is 22 hours, and the hydroxyapatite nanoparticle major diameter that this moment, resulting Tb modified is about 40-50nm, and minor axis is about 15-17nm, and outer all the other character of particle-removing pattern size are all consistent with products obtained therefrom among the embodiment 1.
Embodiment 3
With reference to the preparation process of embodiment 1, the phosphoric acid salt that different is in the mixing solutions adopts dipotassium hydrogen phosphate; Calcium salt adopts nitrocalcite; The concentration of cetyl trimethylammonium bromide is 0.95mM; The concentration of phosphate radical is 6.5mM; The Ca/P mol ratio was 1.69 when reaction finished; Be 10 with ammoniacal liquor regulator solution pH after dripping calcium salt; Drip the calcium salt afterreaction 2 hours, and with 1MHCl system was transferred to pH=7.0 then; After dripping terbium salt, Tb: (Ca+Tb) mol ratio is: 4: 100; After dripping terbium salt, the reaction times is 24 hours, and the hydroxyapatite nanoparticle major diameter that this moment, resulting Tb modified is about 50-60nm, and minor axis is about 17-20nm, and outer all the other character of particle-removing pattern size are all consistent with products obtained therefrom among the embodiment 1.
Claims (10)
1, a kind of preparation method who carries out the hydroxyl apatite fluorescent nano-particle of finishing with Tb, it is characterized in that: be additive with the cetyl trimethylammonium bromide, calcium salt soln is dropwise added in the mixing solutions that contains phosphate radical and cetyl trimethylammonium bromide, dropping ammonia solution regulator solution pH value, hydroapatite particles is separated out from solution, form the hydroxyapatite milk-white coloured suspension, the pH value with hydrochloric acid conditioning solution drips Tb again in solution
3+Solution makes the portion C a on surface of hydroxyapatite nanoparticle
2+By Tb
3+Replace, after filtration, collect after the washing, vacuum-drying, obtain Tb doped hydroxyapatite fluorescent nano particle.
2, preparation method according to claim 1 obtains Tb doped hydroxyapatite fluorescent nano particle, it is characterized in that this particle is grain of rice shape, its major diameter is 40-60nm, minor axis is 15-20nm, have obvious photoluminescent property, a plurality of excitation spectrum peak is arranged, the maximum excitation peak position is in 272nm, at visible light wave range excitation peak is arranged also, emission maximum spectrum peak position is in 544nm.
3, preparation method according to claim 1 is characterized in that concrete steps are as follows:
A) preparation contains the mixing solutions of phosphate radical and cetyl trimethylammonium bromide, with concentration is that the cetyl trimethylammonium bromide of 0.85～0.95mM and phosphate solution that concentration is 5.5～6.5mM stir, with the pH value that concentration is regulated mixing solutions for 0.1M ammoniacal liquor, the pH value that makes solution is 9～10;
The Ca/P mol ratio is 1.65～1.69 amount when b) finishing by reaction, to mixed solution and dripping concentration is the 0.5M calcium salt soln, rate of addition is 1 droplet/second, ammoniacal liquor with 0.1M is regulated, make the pH value of reaction system remain between 9～10, stir, sustained reaction 1～3 hour obtains the hydroxyapatite colloidal sols milk-white coloured suspension;
C) in hydroxyapatite colloidal sols, with 1M HCl system pH is adjusted to 6.0～7.0,, Tb in the system when finishing by reaction: (Ca+Tb)=1: 100～4: 100 amount, dripping concentration is the terbium salts solution of 4.0～6.0mM, rate of addition is 1 droplet/second;
D) reaction went out precipitation with the filtering with microporous membrane of 0.22 μ m after 22～24 hours, repeatedly replace thorough washing precipitation with deionized water and ethanol after, place 30 ℃ of vacuum drying oven dried overnight, can obtain the hydroxyl apatite fluorescent nano-particle after the Tb modification.
4,, it is characterized in that described phosphoric acid salt comprises Secondary ammonium phosphate, potassium primary phosphate, primary ammonium phosphate, Sodium phosphate dibasic, tertiary sodium phosphate or Tripotassium phosphate according to claim 1 or 3 described preparation methods.
5,, it is characterized in that described calcium salt is: nitrocalcite, calcium chloride according to claim 1 or 3 described preparation methods.
6,, it is characterized in that described terbium salt is: Terbium trinitrate, terbium chloride according to claim 1 or 3 described preparation methods.
7, according to claim 1 or 3 described preparation methods, after it is characterized in that dripping calcium salt, solution is regulated pH 9.5 with ammoniacal liquor.
8, according to claim 1 or 3 described preparation methods, it is characterized in that dripping terbium salt before, with hydrochloric acid pH value of solution is regulated 6.5.
9, according to claim 1 or 3 described preparation methods, the Ca/P mol ratio is 1.67 when it is characterized in that the reaction of described dropping calcium salt soln finishes.
10, according to claim 1 or 3 described preparation methods, Tb when the terbium salts solution that it is characterized in that described dropping should finish: (Ca+Tb)=2: 100.
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| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
| 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 |
| CN108344738A (en) * | 2018-01-22 | 2018-07-31 | 翰飞骏德（北京）医疗科技有限公司 | Imaging method and its device for hydroxyapatite |
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| CN103788946A (en) * | 2014-03-05 | 2014-05-14 | 山东大学 | Method for preparing europium-doped hydroxyapatite nanorod |
| 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 |
| CN109072070A (en) * | 2016-03-28 | 2018-12-21 | 株式会社小原石英 | Luminous nano granule, using its detection method of cell, the treatment method of animal, medical device, cell method for visualizing and mitigate the method for cellular damage |
| CN116083081A (en) * | 2016-03-28 | 2023-05-09 | 株式会社小原 | Luminescent nanoparticle, method for detecting cell using same, method for treating animal, medical device, method for visualizing cell, and method for reducing cell damage |
| CN108344738A (en) * | 2018-01-22 | 2018-07-31 | 翰飞骏德（北京）医疗科技有限公司 | Imaging method and its device for hydroxyapatite |
| CN113415792A (en) * | 2021-07-19 | 2021-09-21 | 陈基施展 | Preparation method of fluorescent terbium-doped hydroxyapatite nanorod water-based lyotropic liquid crystal |
| CN114166810A (en) * | 2021-12-03 | 2022-03-11 | 南华大学 | Luminescent calcium-deficient hydroxyapatite composite material for detecting uranyl ions in water and preparation method thereof |
| CN114166810B (en) * | 2021-12-03 | 2022-11-22 | 南华大学 | Luminescent calcium-deficient hydroxyapatite composite material for detecting uranyl ions in water and preparation method thereof |
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