CN106430137A - Preparation method of spherical nano hydroxyapatite particles - Google Patents
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses a preparation method of spherical nano hydroxyapatite particles. The preparation method comprises the following steps: (1) measuring a CQDs (carbon quantum dots) solution in a conical flask, regulating the pH value of the solution up to 10, and uniformly stirring at room temperature; (2) dropwisely adding a CaCl2 solution, and uniformly stirring; (3) dropwisely adding a Na2HPO4.12H2O solution, and standing at room temperature; (4) performing centrifugal separation on the prepared product, discarding the supernate, washing the underlayer product with distilled water and anhydrous ethanol respectively, then taking out the product, and drying in a drying oven to obtain khaki powder; and (5) calcining the powder in a muffle furnace, thereby removing carbon quantum dots to obtain white powder, namely HAP (hydroxyapatite) nanoparticles. According to the invention, the spherical hydroxyapatite nanoparticles are prepared at room temperature by using the carbon quantum dots as effective nucleation inducer through a chemical precipitation method. The hydroxyapatite prepared by the invention is quasi-spherical, and has the advantages of favorable dispersity, particle uniformity and high crystallinity. Besides, the preparation method has the advantages of simplicity, mild and controllable conditions and low cost.
Description
Technical field
The invention belongs to biology medical material technical field, it is related to a kind of new spherical nano hydroxyapatite granule
Preparation method.
Background technology
Hydroxyapatite (hydroxyapatite, HAP), as synthos most stable of under physiological condition, is that vertebra moves
The host inorganic mineralogical composition of thing skeleton and tooth.Because having good biocompatibility and biological activity, it is widely used in
Organizational project, the reparation of bone and replacement and dental materialss etc., having been found to mesoporous HAP can promote new bone by bone conduction mechanism
Generation and do not cause any toxicity, inflammation and rejection.Further, since the chemical composition of uniqueness and crystal structure, HAP pair
Biomolecule illustrates high-affinity, such as DNA and RNA, is therefore also widely used in protein, medicine, gene, somatomedin
Control release carrier.For example, as pharmaceutical carrier, nano-scale particle can pass through cell membrane faster, protects medicine
From enzymatic degradation, the release performance of regulating medicine, targeting can also be improved by ligand molecule surface modification or functionalization and arrive
Reach specific sick cell or tissue.
In recent years, with the fast development that nano-HAP is studied, research worker the characteristic of HAP is had deeper into
Solution, the physical and chemical performance having been found to HAP depends primarily on its pattern, particle diameter and degree of crystallinity.At present, both at home and abroad for different-shape
The research of hydroxyapatite and preparation method is more.In the existing document retrieving, Yang etc. adopts hydro-thermal method in citric acid
HAP microsphere [Yang H, Hao L J, Zhao N R, the et al.Hierarchical porous of hollow is synthesized under auxiliary
hydroxyapatite microsphere as drug delivery carrier.Crystengcomm,2013,15(29),
5760-5763], but obtained microsphere be by size in 400nm about nanometer rods or nanometer sheet gather as construction unit
Conjunction forms, and building-up process is higher to equipment requirements through High Temperature High Pressure.Lin etc. is not using any surfactant, template
Support and structure directing agent on the premise of, prepared using simple low-temperature hydrothermal process and had that uniformly to contain carbonatoapatite micro-
Ball [Lin K L, Chang J, Zhu Y J, et al.A facile one-step surfactant-free and low-
temperature hydrothermal method to prepare uniform 3D structured carbonated
Apatite flowers.Cryst Growth Des, 2009,9 (1), 177-181], these are by a large amount of thickness containing carbonatoapatite
Degree is about 75nm, wide 200-1000nm, and the nano-plates up to 5 μm for the length are polymerized, and the degree of crystallinity of product is relatively low.Lv Yupeng etc.
(CN1903706A) with four water-calcium nitrate (Ca (NO3)2·4H2) and diammonium phosphate ((NH O4)2HPO4) it is raw material, using chemistry
The sedimentation method are obtained hydroxyapatite slip, are then diluted addition ammonium hydrogen carbonate, carry out spraying treatment after stirring, in conjunction with
Subsequent heat treatment, has obtained the hollow hydroxyapatite micro-sphere being made up of nanocrystal, prepared hydroxyapatite micro-sphere
Epigranular, surface area is big, and hollow rate is high, but degree of crystallinity is relatively low, and particle diameter is larger.However, up to the present, there is regular shape
It is little that the spherical nano hydroxyapatite of looks is reported.Particularly with carbon quantum dot as core, hydroxyapatite coats to it
Also there is no relevant report to spherical granule.
Carbon quantum dot (CQDs), as the new zero-dimension nano material with carbon element being just found in recent years, its particle diameter is less than 10nm,
Have that stability is high, good biocompatibility and have the characteristics such as very strong controllable luminescence generated by light.Contain on the surface of carbon quantum dot
There is substantial amounts of-OH and-COOH, be that subsequent process adsorbs other predecessors or nanoparticle provides good chemical environment.
Content of the invention
It is an object of the invention to provide a kind of preparation method of spherical nano hydroxyapatite granule, using CQDs as center
Core, induction HAP is deposited on its surface, thus avoiding the random growth of HAP to obtain the spherical HAP nano-particle of regular pattern.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of spherical nano hydroxyapatite granule, comprises the steps:
(1) measure the CQDs solution that 20ml concentration is 0.0625~1.00mmol/L to conical flask, adjust pH value of solution liter
To 10,10~30min is stirred at room temperature;
(2) it is added dropwise over the CaCl that 1ml concentration is 40~100mmol/L2Solution, uniform stirring 20~40min;
(3) it is added dropwise over the Na that 1ml concentration is 24~60mmol/L2HPO4·12H2O solution, controls Ca/P mol ratio
1.7, stand 90~100h at room temperature;
(4) the product centrifugation being obtained, discards the supernatant, lower floor's product washes 3 with distilled water and dehydrated alcohol respectively
~5 times, the product after washing takes out, and is dried to obtain khaki powder in an oven;
(5) powder is put into Muffle furnace by room temperature to 500~600 DEG C, calcine 4~6h at such a temperature, except carbon elimination
Quantum dot obtains white powder and is HAP nano-particle.
In the present invention, using sucrose as carbon source, carbon quantum dot is prepared using hydro-thermal method, comprises the following steps that:Measure 5.0ml
Concentration is the sucrose solution of 0.01mol/L, the dilute H of 1.0ml2SO4Solution, 44.0ml distilled water three are placed in same conical flask,
It is allowed to mix homogeneously under magnetic agitation, then solution is transferred in politef autoclave, react 8h in 140 DEG C,
Naturally cool to room temperature, obtain CQDs solution.
Using the method for the present invention, using carbon quantum dot as effective nucleation derivant, using chemical precipitation method, in room temperature
Under obtained spherical hydroxyapatite nanoparticle.Hydroxyapatite prepared by the present invention is in torispherical, has good
Dispersibility, uniformly, degree of crystallinity is high for granule.Additionally, preparation method is simple, mild condition is controlled, and cost is relatively low.
Brief description
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of gained spherical nano hydroxyapatite and hydroxyl under optimum condition of the present invention
The standard diagram of apatite;
Fig. 2 is the Fourier transform infrared spectroscopy figure (FTIR) of hydroxyapatite after calcining under optimum condition of the present invention;
Fig. 3 is the impact of different carbon quantum dot concentrations on product patterns, a:0, b:0.0625mmol/L, c:0.250mmol/
L, d:1.00mmol/L;
Fig. 4 is CaCl2The impact to product morphology for the addition, a:40mmol/L, b:60mmol, c:80mmol/L, d:
100mmol/L.
Specific embodiment
Below in conjunction with the accompanying drawings technical scheme is further described, but is not limited thereto, every to this
Inventive technique scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should cover
In protection scope of the present invention.
The invention provides a kind of preparation method of spherical nano hydroxyapatite granule, first, the weak solution of sucrose exists
Carbon quantum dot is prepared, as effective nucleation derivant, wherein sulphuric acid is as carburization agent under hydrothermal treatment consists;Then spend from
Sub- water is diluted, and Deca sodium hydrate aqueous solution adjusts solution ph, is raw material using anhydrous calcium chloride and disodium hydrogen phosphate,
Ca2+One " egg-shell " structure is formed on the surface of carbon quantum dot by electrostatic attraction absorption;After adding phosphorus source, PO4 3-With Ca2+
Reaction, in the Surface Creation synthos of carbon quantum dot, through Ostwald ripening, is finally translated into more stable HAP
Thus obtaining spherical HAP nano-particle.Comprise the following steps that:
First, the preparation of CQDs
The preparation of solution:Weigh 0.343g sucrose to be dissolved in 100ml distilled water, be configured to the sucrose solution of 0.01mol/L;
Pipet measures the dense H of 0.10ml2SO4With distilled water diluting to 10ml, mix homogeneously.
The preparation of carbon quantum dot:Measure the above-mentioned sucrose solution of 5.0ml, the dilute H of 1.0ml2SO4Solution, 44.0ml distilled water three
It is placed in same conical flask, is allowed to mix homogeneously under magnetic stirring, then solution is transferred to politef reaction under high pressure
In kettle, react 8h in 140 DEG C, naturally cool to room temperature, obtain CQDs solution.
2nd, the preparation of nano-HAP
Solution is prepared:Weigh the anhydrous CaCl of 0.053g2It is dissolved in 6ml distilled water, the calcium chloride being configured to 80mmol/L is molten
Liquid;Equally weigh 0.103g Na2HPO4·12H2O is dissolved in 6ml distilled water, and Ca/P mol ratio 1.7 is configured to 48mmol/L's
Disodium phosphate soln;Weigh 0.200g NaOH to be dissolved in 5ml distilled water, be configured to the sodium hydroxide solution of 1mol/L;Measure
Dilute in CQDs solution 20ml to the 60ml distilled water of above-mentioned preparation, be uniformly mixed, obtaining concentration is 0.25mmol/L's
Carbon quantum dot solution.
The preparation of nano-HAP granule:Measure the CQDs solution 20ml after above-mentioned dilution to conical flask, dropwise add in stirring
The NaOH aqueous solution regulation pH value of solution entering 1mol/L rises to 10,20min is stirred at room temperature, is subsequently added dropwise over 1ml CaCl2Solution,
Uniform stirring 30min, is then added dropwise over 1ml Na2HPO4·12H2O solution, stands 96h at room temperature.Prepared product exists
Centrifugation under 9000r/min, discards the supernatant, and lower floor's product washes 3 times, after washing with distilled water and dehydrated alcohol respectively
Product takes out, and is dried to obtain khaki powder at 100 DEG C in an oven.By powder put into Muffle furnace by room temperature (2 DEG C/
Min) to 550 DEG C, calcine 5h at such a temperature, remove carbon quantum dot to obtain white powder is HAP nano-particle.
Fig. 1 is the standard diagram with HAP for the XRD spectrum of sample manufactured in the present embodiment.The standard diagram of comparison HAP
(JCPDS 09-0432) understands, in the XRD spectrum of post-calcination sample b, each diffraction maximum can be corresponded with it, does not have other miscellaneous
The appearance of mass peak, illustrates to define HAP rather than other synthos in prepared sample, HAP is hexagonal crystal system, belongs to
P63/ m space group.Positioned at 2 θ=26.73 °, 31.80 °, 33.57 °, 34.12 °, 39.86 °, 46.81 °, 48.16 ° and 49.54 °
The strong diffraction maximum at place is spreading out of HAP (002), (211), (300), (202), (310), (222), (213) and (004) crystal face respectively
Penetrate peak.Additionally, never can see that each diffraction maximum is wider in the XRD spectrum of calcining sample a, peak intensity is weaker;After calcining, can
Overlapping phenomenon is not substantially had with the diffraction maximum finding out sample b, becomes more sharp, peak intensity is remarkably reinforced, and degree of crystallinity is improved.
From figure 2 it can be seen that 3569cm-1And 633cm-1The absworption peak at place is respectively OH-Stretching vibration peak and bending
Vibration peak.Tetrahedral structure PO4 3-Characteristic absorption peak be located at 473cm-1、565cm-1、602cm-1、962cm-1、1032cm-1With
1089cm-1Place.473cm-1Corresponding PO4 3-γ2Vibration absorption peak, 565cm-1、602cm-1Corresponding PO4 3-γ4Absorption of vibrations
Peak, 962cm-1Corresponding PO4 3-γ1Vibration absorption peak, 1032cm-1And 1089cm-1Corresponding PO4 3-γ3Vibration absorption peak.Separately
Outward, 873cm-1And 1437cm-1And 1483cm-1The absworption peak at place is CO3 2-Absworption peak, these peaks appearance explanation CO3 2-Take
For the PO in HAP lattice4 3-It may be possible to absorb aerial CO2Caused.3448cm-1And 1629cm-1The absworption peak at place is corresponding
H2The stretching vibration of O and bending absworption peak, are because when grinding tabletting, tabletting absorbs what the moisture of in the air caused, because
It is that this peak there is also in the blank experiment of KBr.
From figure 3, it can be seen that can see granule when carbon quantum dot concentration is for 0.25mmol/L uniformly, dispersion is relatively
Good, no obvious agglomeration.With the decline of carbon quantum dot concentration, synthesize the pattern significant change of HAP.Prepared in (a)
Sample is in block, does not have regular morphology, and this is due to not having the presence of carbon quantum dot can not by lead to amorphous calcium phosphate salt
Control fast-growth causes.When carbon quantum dot concentration increases to 1.00mmol/L by 0.0625mmol/L, synthesized sample
Grain is in torispherical, and uniformly (about 40nm), this phenomenon at least illustrates that synthos have been intervened in the presence of carbon quantum dot to granule
Growth.When carbon quantum dot concentration is 0.25mmol/L, on this basis, increased or decrease the concentration of carbon quantum dot, final product
Granule is substantially reunited, but the size of granule does not change substantially.When reduce carbon quantum dot concentration by
During 0.0625mmol/L to 0, by significantly reuniting in bulk, this is the carboxylic being existed due to carbon quantum dot surface to the pattern of product
Base and the limited Ca being adsorbed by electrostatic attraction of hydroxyl2+Reach balance, no longer adsorbed the Ca of positively charged2+, remaining in solution
A large amount of Ca2+Presented in free state, as addition phosphorus source, PO in system4 3-Except with absorption on carbon quantum dot surface
Ca2+Generate unbodied synthos and be deposited on its surface, simultaneously also can be with Ca remaining in solution2+Reaction is unordered to be generated no
The synthos of setting, the product finally giving is except spherical HAP nano-particle, the also HAP of irregular pattern.Work as increase
When the concentration of carbon quantum dot is to 1.00mmol/L, this is because the Ca adding2+Deficiency, leads to carbon quantum dot by sharing Ca2+Phase
Mutually attract, thus leading to reunite between granule.As can be seen here, when carbon quantum dot concentration is 0.25mmol/L, obtained
Sample optimal, granule uniformly, is no substantially reunited.
Fig. 4 is CaCl during 0.25mmol/L for carbon quantum dot concentration2The impact to HAP pattern for the addition.By SEM photograph
As can be seen that working as CaCl2Addition when being 80mmol/L, obtained HAP product grain uniformly, about 40nm, no substantially
Agglomeration.This is due to adding CaCl in system2Amount be closer to carbon quantum dot surface carboxyl groups and hydroxyl institute adsorbable
Ca2+Amount, the Ca of free state in solution2+Less, the amorphous calcium phosphate salt of generation is substantially all the table being deposited on carbon quantum dot
Face.With CaCl in solution2The increase of addition, except graininess HAP in product, also a small amount of block HAP occurs, and this is
Due to Ca in solution2+Excessive, with the CaCl adding2Amount fix, when it is affected, carbon quantum dot is too for research carbon quantum dot concentration
Few reason is consistent.As CaCl in system2Addition when 80mmol/L drops to 40mmol/L it can be seen that granule occur group
Poly-, particle diameter is not changed in substantially, and this excessively causes granule that group occurs with probing into carbon quantum dot when carbon quantum dot concentration affects on it
Poly- reason is consistent.
Claims (10)
1. a kind of preparation method of spherical nano hydroxyapatite granule is it is characterised in that described preparation method step is as follows:
(1) measure the CQDs solution that 20ml concentration is 0.0625~1.00mmol/L to conical flask, adjust pH value of solution and rise to 10,
It is stirred at room temperature;
(2) it is added dropwise over the CaCl that 1ml concentration is 40~100mmol/L2Solution, uniform stirring;
(3) it is added dropwise over the Na that 1ml concentration is 24~60mmol/L2HPO4·12H2O solution, stands at room temperature;
(4) the product centrifugation being obtained, discards the supernatant, lower floor's product washes 3~5 with distilled water and dehydrated alcohol respectively
Secondary, the product after washing takes out, and is dried to obtain khaki powder in an oven;
(5) powder is put into calcining in Muffle furnace, remove carbon quantum dot and obtain white powder as HAP nano-particle.
2. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(1), in, mixing time is 10~30min.
3. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(1), in, the concentration of CQDs solution is 0.25mmol/L.
4. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described CQDs
The preparation method of solution is as follows:Measuring 5.0ml concentration is the sucrose solution of 0.01mol/L, the dilute H of 1.0ml2SO4Solution, 44.0ml
Distilled water three is placed in same conical flask, is allowed to mix homogeneously under magnetic stirring, then solution is transferred to polytetrafluoroethyl-ne
In alkene autoclave, react 8h in 140 DEG C, naturally cool to room temperature, obtain CQDs solution.
5. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(2), in, mixing time is 20~40min.
6. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(2) in, CaCl2The concentration of solution is 80mmol/L.
7. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(3), in, control Ca/P mol ratio 1.7.
8. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(3) in, Na2HPO4·12H2The concentration of O solution is 48mmol/L.
9. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(3), in, time of repose is 90~100h.
10. the preparation method of spherical nano hydroxyapatite granule according to claim 1 is it is characterised in that described step
(4) in, calcining heat is 500~600 DEG C, and the time is 4~6h.
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Cited By (5)
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CN108584898A (en) * | 2018-07-05 | 2018-09-28 | 华南理工大学 | A method of preparing small size nanometer hydroxyapatite by template of carbon dots |
CN110078037A (en) * | 2019-05-23 | 2019-08-02 | 哈尔滨理工大学 | A kind of synthetic method with spherical morphology hydroxyapatite nanoparticle |
CN110755625A (en) * | 2019-10-10 | 2020-02-07 | 广东药科大学 | Targeting type drug carrier based on nano-hydroxyapatite and construction method of nano-drug delivery system |
CN113521011A (en) * | 2021-07-31 | 2021-10-22 | 黑龙江八一农垦大学 | Nano gene medicine transfer carrier |
CN114275751A (en) * | 2022-02-16 | 2022-04-05 | 湖南大学 | Preparation method of hexagonal macroporous hydroxyapatite, product and application thereof |
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CN108584898A (en) * | 2018-07-05 | 2018-09-28 | 华南理工大学 | A method of preparing small size nanometer hydroxyapatite by template of carbon dots |
CN110078037A (en) * | 2019-05-23 | 2019-08-02 | 哈尔滨理工大学 | A kind of synthetic method with spherical morphology hydroxyapatite nanoparticle |
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CN110755625A (en) * | 2019-10-10 | 2020-02-07 | 广东药科大学 | Targeting type drug carrier based on nano-hydroxyapatite and construction method of nano-drug delivery system |
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CN114275751A (en) * | 2022-02-16 | 2022-04-05 | 湖南大学 | Preparation method of hexagonal macroporous hydroxyapatite, product and application thereof |
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