CN104961115A - Hollow hydroxyapatite microsphere and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method for a hollow hydroxyapatite microsphere, and belongs to the field of biomedical materials. The spherical diameter of the hollow hydroxyapatite microsphere ranges from 1 micrometer to 2 micrometers approximately, the wall thickness ranges from 150 nanometers to 300 nanometers approximately, the particle surface is of a prick-shaped structure, the middle of the microsphere is of a hollow structure, and the crystal form is mainly composed of hydroxyapatite. The preparation method for the material comprises the following steps that 1, sericin serves as a template and is regulated and controlled to obtain a calcium carbonate microsphere; 2, the calcium carbonate microsphere obtained in the first step serves as a pioneer template and is added into a phosphate aqueous solution, and the hollow hydroxyapatite microsphere is prepared in an anion exchange reaction through a hydrothermal method under high temperature; 3, centrifugation, washing and drying are conducted to collect the spherical hollow hydroxyapatite microsphere. The preparation method is simple, good in repeatability and suitable for industrial production; the prepared hollow hydroxyapatite microsphere has the advantage that the specific surface area is large; hollow hydroxyapatite microsphere has wide application prospects in the biomedical fields such as gene therapy vectors and drug controlled release carriers.
Description
Technical field
The present invention relates to a kind of preparation method of hollow hydroxyapatite micro-sphere, belong to lithotroph field of medical materials.
Background technology
Hydroxyapatite has extensive and great application prospect in medical science, pharmacy, food, environmental science, catalyzer, the multiple field of sensor.The bone of hydroxyapatite as humans and animals, the main inorganic composition of tooth, have good biocompatibility, biological activity and biodegradability, do not have toxic side effect simultaneously to normal cell.Hollow hydroxyapatite is rapid in the researchdevelopment in the fields such as human body hard tissue reparation, medicament slow release and gene therapy as a kind of novel inorganic solid support material, become the important inorganic materials in biology, pharmacopedics and Materials science crossing domain, be subjected to the extensive concern of domestic and international investigator at present.The hollow ball shape structure that hollow spheres hydroxyapatite possesses and the large feature of specific surface area give its larger carrying drug ratio, encapsulation rate and stronger absorption property, and its research application of delaying in controlled release carrier and gene delivery etc. at biomedical materials field Chinese traditional medicine is received much concern.
Hydroxyapatite must possess as vehicle the feature that specific surface area is large, the amount of carrying is high, preparation method is simple, reproducible.In recent years, in order to meet application requiring different in every field, investigators have obtained the hydroapatite particles of spherical, needle-like, bar-shaped, different-shape, particle diameter and the surface charge such as sheet, threadiness, crystal whisker-shaped by various material preparation technology.Wherein, hollow spheres hydroxyapatite has the advantages such as specific surface area is large, the amount of carrying is high, compactedness is high, affinity is good and is subject to extensive concern.(the Colloids and Surfaces A:Physicochemical and Engineering Aspects such as Zeng FZ, 2014,441:737-743.) by ultrasonic wave added hydro-thermal condensing reflux method, utilize cetyl trimethylammonium bromide (CTAB) micella as template and add 1,3,5-Three methyl Benzene (TMB) solubilizing agent, the bar-shaped hydroxyapatite of porous nano is prepared in regulation and control, this hydroxyapatite nano rod is about 50 ~ 150 nm, wide about 10 ~ 40 nm, aperture is about 4 ~ 15 nm.(the Materials Letters such as Wang P, 2009,63 (13): 1207-1209.) polyacrylic acid (PAA) is utilized to be organic formwork, four water-calcium nitrate is added drop-wise in polyacrylic acid and carries out chelating, then according to Ca/P be 1.67 ratio Secondary ammonium phosphate is joined in four water-calcium nitrate and polyacrylic mixing solutions and reacts, finally obtain the spherical hydroxyapatite that mean diameter is 150 nm.(the Journal of Materials Chemistry such as Qi C, 2012,22 (42): 22642-22650.) utilize DNA for regulation and control template, prepare diameter by hydro-thermal reaction method and be about 2.5 ~ 4.5, mean pore size is 21.8 nm, and the Porous hollow hydroxyapatite micro-sphere that the nanometer sheet being 20 nm by mean thickness assembles.(the The Journal of Physical Chemistry C such as Jiang SD, 2012,116 (7): 4484-4492.) utilize a kind of water-soluble biological polymeric polyaspartic acid as regulation and control template, by hydro-thermal reaction method, in hydrothermal reaction kettle, 180 DEG C of hydro-thermal reactions are prepared diameter for 24 hours and are about 2.5 μm, the hollow hydroxyapatite micro-sphere assembled by nanometer rod.In addition, the report of the difform hydroxyapatite preparation methods such as much needle-like, threadiness, crystal whisker-shaped is also had.Calcium carbonate is also a kind of important inorganic materials in technical field of biological material, there is good biocompatibility and biodegradability, and possess pattern mutability, it is the desirable template preparing hydroxyapatite, Chinese patent (patent No. 201310349352.3) utilizes calcium carbonate as template, has prepared a kind of hydroxyapatite micro-sphere by microwave method.
Summary of the invention
The preparation method of the hollow hydroxyapatite that the object of the present invention is to provide a kind of preparation technology simple, reproducible, the calcium carbonate microspheres regulating and controlling to prepare using silk gum is as template, joined in aqueous phosphatic, by hydrothermal method, carry out ion-exchange through phosphate radical and carbonate and prepare hollow hydroxyapatite micro-sphere.
Hollow hydroxyapatite micro-sphere provided by the invention, is characterized in that: spherical diameter is about 1 ~ 2 μm, wall thickness about 150 ~ 300 nm, and particle surface is bayonet fittings, and middle in hollow structure, crystal formation is mainly hydroxyapatite.Concrete grammar of the present invention comprises the following steps:
Step (1): silk cocoon is placed in 0.5 ~ 1% sodium carbonate solution and boils and come unstuck and 3 days obtained 1 ~ 10 mg/ml silk gum solution of dialysing, configuration concentration is 1 ~ 2 mol/L calcium salt soln and carbonate solution;
Step (2): at ambient temperature, dropwise join in the 200 ml silk gum solution at the uniform velocity stirred respectively by 5 ~ 10 ml equal-volume calcium salt solns configured and carbonate solution, dropping terminates rear continuation and at the uniform velocity stirs 30 min simultaneously;
Step (3): centrifugal 3 min of 8000 rpm after reaction terminates, deionized water and dehydrated alcohol wash 3 ~ 4 times respectively, collect and obtain calcium carbonate microspheres at 60 DEG C of temperature after oven drying;
Step (4): utilize 1 ~ 2 mol/L alkaline solution to regulate the pH of the aqueous phosphatic of 0.1 ~ 1 mol/ L to be 10 ~ 11;
Step (5): joined by the calcium carbonate microspheres of step (3) gained in above-mentioned aqueous phosphatic and at the uniform velocity stir formation suspension liquid, the calcium carbonate microspheres wherein added and phosphatic mol ratio are 1:0.6 ~ 5;
Step (6): joined by the suspension liquid of gained in polytetrafluoroethyllining lining hydrothermal reaction kettle, is placed in baking oven and carries out hydro-thermal reaction by it;
Step (7): centrifugal 3 min of 8000 rpm after reaction terminates, deionized water and dehydrated alcohol wash 3 ~ 4 times respectively, collect and obtain hollow hydroxyapatite micro-sphere at 60 DEG C of temperature after oven drying.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, it is characterized in that the concentration of sodium carbonate used preferably 0.5% that comes unstuck described in step (1), silk gum concentration is 5 mg/ml preferably; Described calcium salt soln is the aqueous solution of calcium chloride or nitrocalcite, and described carbonate solution is the aqueous solution of sodium carbonate or volatile salt, and concentration is 2 mol/L all preferably.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the room temperature condition preferably 21 DEG C described in step (2), rate of addition preferably 20 droplets/minute.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the calcium salt soln described in step (2) and carbonate solution all preferably 5 ml.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the obtained calcium carbonate microspheres crystal formation described in step (3) is vaterite.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the alkaline solution described in step (4) is sodium hydroxide solution or ammonia soln, preferred sodium hydroxide solution.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the aqueous phosphatic described in step (4) is Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC or Secondary ammonium phosphate, preferably phosphoric acid disodium hydrogen.
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, is characterized in that the aqueous phosphatic concentration preferably 0.1 mol/ L described in step (4).
The preparation method of described a kind of hollow hydroxyapatite micro-sphere, it is characterized in that step (6) described hydrothermal temperature is 100 ~ 140 DEG C, preferably 120 DEG C, the reaction times is 1 ~ 4 h, preferably 2 h.
Hollow hydroxyapatite micro-sphere material of the present invention, its surface is porous bayonet fittings, and centre is hollow structure.Have that specific surface area is large, light specific gravity and the advantage such as biodegradation rate is very fast, gene or the field such as medicine controlled release carrier, Cranial defect packing material can be applied to.Raw materials of the present invention is cheaply easy to get, and cost is lower, and preparation method is simple, is suitable for batch production.
The invention has the beneficial effects as follows:
The present invention is by hydrothermal method, calcium carbonate microspheres is carried out hydro-thermal reaction and is converted into hollow hydroxyapatite micro-sphere, and the reaction times is a few hours, and mild condition, be swift in response, simple to operate, can effectively enhance productivity.
In experimentation of the present invention, by hydro-thermal reaction, calcium carbonate microspheres conversion is obtained hollow hydroxyapatite micro-sphere, original pattern and size can not only be kept, and its structure can also be made to become porous thorn-like hollow structure.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope picture of the embodiment of the present invention 1 products therefrom.
Fig. 2 is the XRD figure spectrum of the embodiment of the present invention 1 products therefrom.
Fig. 3 is the FTIR collection of illustrative plates of the embodiment of the present invention 1 products therefrom.
Fig. 4 is the field emission scanning electron microscope picture of the embodiment of the present invention 2 products therefrom.
Fig. 5 is the field emission scanning electron microscope picture of the embodiment of the present invention 3 products therefrom.
Embodiment
In order to make the easier to understand and technical scheme of the present invention, advantage clearly understands, below in conjunction with embodiment and accompanying drawing, is further elaborated to the present invention.Should be appreciated that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention, NM specific experiment method in the following example, experimental technique carries out routinely usually.
Embodiment 1
Silk cocoon is placed in 0.5% sodium carbonate solution (bath raio is 1:100) to boil and come unstuck 2 times, often all over 30 min, then come unstuck 30 min in deionized water, collect silk gum stoste and be placed in the dialysis tubing dialysis 3 days that molecular weight cut-off is 8000 ~ 14000, dry concentrated, utilize deionized water to dilute the silk gum solution obtaining 5 mg/ml.Configure the sodium carbonate solution of calcium chloride solution that concentration is 2 mol/L and 2 mol/L, under room temperature 21 DEG C of conditions, 5 ml calcium chloride solutions and 5 ml sodium carbonate solutions are dropwise joined in the silk gum solution of 200 ml at the uniform velocity stirred with 20 droplets/minute respectively simultaneously, dropping terminates rear continuation and at the uniform velocity stirs 12 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain calcium carbonate microspheres powder after baking oven 60 DEG C of dryings.0.2 g calcium carbonate microspheres is joined with the sodium hydroxide of 1mol/L regulate pH be 11 the Sodium phosphate dibasic aqueous solution (100 ml, 0.1 M) in, at the uniform velocity stir at ambient temperature and form suspension liquid, then be transferred in hydrothermal reaction kettle and be placed in baking oven 120 DEG C of hydro-thermal reaction 2 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain hollow hydroxyapatite micro-sphere after baking oven 60 DEG C of dryings.
Carry out field emission scanning electron microscope analysis, X-ray diffraction analysis, infrared analysis to gained hollow hydroxyapatite micro-sphere, result is respectively as Fig. 1,2,3.Gained hollow hydroxyapatite micro-sphere diameter is about 1 ~ 2 μm, wall thickness about 150 ~ 300 nm, and surface is porous flake or bayonet fittings, and centre is hollow structure, and crystal formation is mainly hydroxyapatite.
Embodiment 2
Silk cocoon is placed in 1% sodium carbonate solution (bath raio is 1:100) to boil and come unstuck 2 times, often all over 30 min, then come unstuck 30 min in deionized water, collect silk gum stoste and be placed in the dialysis tubing dialysis 3 days that molecular weight cut-off is 8000 ~ 14000, dry concentrated, utilize deionized water to dilute the silk gum solution obtaining 5 mg/ml.Configure the sodium carbonate solution of calcium chloride solution that concentration is 1 mol/L and 1 mol/L, under room temperature 21 DEG C of conditions, 10 ml calcium chloride solutions and 10 ml sodium carbonate solutions are dropwise joined in the silk gum solution of 200 ml at the uniform velocity stirred with 20 droplets/minute respectively simultaneously, dropping terminates rear continuation and at the uniform velocity stirs 6 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain calcium carbonate microspheres powder after baking oven 60 DEG C of dryings.0.1 g calcium carbonate microspheres is joined with the sodium hydroxide of 1mol/L regulate pH be 11 the Sodium phosphate dibasic aqueous solution (50 ml, 0.1M), at the uniform velocity stir at ambient temperature and form suspension liquid, then be transferred in hydrothermal reaction kettle and be placed in baking oven 100 DEG C of hydro-thermal reaction 4 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain hollow hydroxyapatite micro-sphere after baking oven 60 DEG C of dryings.
The field emission scanning electron microscope of embodiment 2 gained hollow hydroxyapatite micro-sphere as shown in Figure 4.The technical parameter that the hollow hydroxyapatite micro-sphere that hollow hydroxyapatite micro-sphere all has with embodiment 1 obtains that embodiment 2 obtains is identical.
Embodiment 3
Silk cocoon is placed in 0.5% sodium carbonate solution (bath raio is 1:100) to boil and come unstuck 2 times, often all over 30 min, then come unstuck 30 min in deionized water, collect silk gum stoste and be placed in the dialysis tubing dialysis 3 days that molecular weight cut-off is 8000 ~ 14000, dry concentrated, utilize deionized water to dilute the silk gum solution obtaining 3 mg/ml.Configure the sodium carbonate solution of calcium chloride solution that concentration is 2 mol/L and 2 mol/L, under room temperature 21 DEG C of conditions, 5 ml calcium chloride solutions and 5 ml sodium carbonate solutions are dropwise joined in the silk gum solution of 200 ml at the uniform velocity stirred with 20 droplets/minute respectively simultaneously, dropping terminates rear continuation and at the uniform velocity stirs 3 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain calcium carbonate microspheres powder after baking oven 60 DEG C of dryings.0.2 g calcium carbonate microspheres is joined with ammoniacal liquor regulate pH be 11 the Sodium phosphate dibasic aqueous solution (100ml, 0.1M), at the uniform velocity stir at ambient temperature and form suspension liquid, then be transferred in hydrothermal reaction kettle and be placed in baking oven 140 DEG C of hydro-thermal reaction 1 h, centrifugal (8000 rpm, 3 min), deionized water and dehydrated alcohol wash three times respectively, collect and obtain hollow hydroxyapatite micro-sphere after baking oven 60 DEG C of dryings.
The field emission scanning electron microscope of embodiment 3 gained hollow hydroxyapatite micro-sphere as shown in Figure 5.The technical parameter that the hollow hydroxyapatite micro-sphere that hollow hydroxyapatite micro-sphere all has with embodiment 1 obtains that embodiment 3 obtains is identical.
Claims (8)
1. a hollow hydroxyapatite micro-sphere, is characterized in that: described hollow hydroxyapatite micro-sphere diameter is about 1 ~ 2 μm, wall thickness about 150 ~ 300 nm, and particle surface is bayonet fittings, and middle in hollow structure, crystal formation is mainly hydroxyapatite.
2. a preparation method for hollow hydroxyapatite micro-sphere according to claim 1, is characterized in that: comprise the steps:
Step (1): silk cocoon is placed in 0.5 ~ 1% sodium carbonate solution and boils and come unstuck and 3 days obtained 1 ~ 10 mg/ml silk gum solution of dialysing, configuration concentration is 1 ~ 2 mol/L calcium salt soln and carbonate solution;
Step (2): at ambient temperature, dropwise join in the 200 ml silk gum solution at the uniform velocity stirred respectively by 5 ~ 10 ml equal-volume calcium salt solns configured and carbonate solution, dropping terminates rear continuation and at the uniform velocity stirs 30 min simultaneously;
Step (3): centrifugal 3 min of 8000 rpm after reaction terminates, deionized water and dehydrated alcohol wash 3 ~ 4 times respectively, collect and obtain calcium carbonate microspheres at 60 DEG C of temperature after oven drying;
Step (4): utilize 1 ~ 2 mol/L alkaline solution to regulate the pH of the aqueous phosphatic of 0.1 ~ 1 mol/ L to be 10 ~ 11;
Step (5): joined by the calcium carbonate microspheres of step (3) gained in above-mentioned aqueous phosphatic and at the uniform velocity stir formation suspension liquid, the calcium carbonate microspheres wherein added and phosphatic mol ratio are 1:0.6 ~ 5;
Step (6): joined by the suspension liquid of gained in polytetrafluoroethyllining lining hydrothermal reaction kettle, is placed in baking oven and carries out hydro-thermal reaction by it;
Step (7): centrifugal 3 min of 8000 rpm after reaction terminates, deionized water and dehydrated alcohol wash 3 ~ 4 times respectively, collect and obtain hollow hydroxyapatite micro-sphere at 60 DEG C of temperature after oven drying.
3. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, is characterized in that: the calcium salt soln described in step (1) is the aqueous solution of calcium chloride or nitrocalcite, and described carbonate solution is the aqueous solution of sodium carbonate or volatile salt.
4. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, it is characterized in that: the room temperature condition described in step (2) is 18 ~ 25 DEG C, rate of addition is 10 ~ 20 droplets/minute.
5. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, is characterized in that: the obtained calcium carbonate microspheres crystal formation described in step (3) is vaterite.
6. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, is characterized in that: the alkaline solution described in step (4) is sodium hydroxide solution or ammonia soln.
7. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, is characterized in that: the aqueous phosphatic described in step (4) is Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC or Secondary ammonium phosphate.
8. the preparation method of a kind of hollow hydroxyapatite micro-sphere according to claim 2, it is characterized in that: step (6) described hydrothermal temperature is 100 ~ 140 DEG C, the reaction times is 1 ~ 4 h.
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Inventor after: Kong Xiangdong Inventor after: Lai Wen Inventor after: Chen Cen Inventor after: Li Linshe Inventor after: Yao Juming Inventor after: Jiang Guohua Inventor before: Kong Xiangdong Inventor before: Lai Wen |
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Application publication date: 20151007 |