CN110251733A - High active unformed calcium phosphate/calcium citrate composite granule of biomineralization and preparation method thereof - Google Patents
High active unformed calcium phosphate/calcium citrate composite granule of biomineralization and preparation method thereof Download PDFInfo
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- CN110251733A CN110251733A CN201910644520.9A CN201910644520A CN110251733A CN 110251733 A CN110251733 A CN 110251733A CN 201910644520 A CN201910644520 A CN 201910644520A CN 110251733 A CN110251733 A CN 110251733A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention belongs to medical bone renovating material fields, and in particular to a kind of high active unformed calcium phosphate/calcium citrate composite granule of biomineralization and preparation method thereof.The composite granule is compound by calcium citrate and unformed calcium phosphate, be by soluble calcium salt, citrate, phosphate solution be raw material, to control in a manner of dropwise addition, reaction temperature, pH value, alcohol water environment etc. obtained by precipitation process, the quality accounting of unformed calcium phosphate can be adjusted in 40% ~ 88% range.Unformed calcium phosphate/calcium citrate the composite granule obtained overcomes the unstability of unformed calcium phosphate, can be stabilized in water phase, and has high biomineralization activity.Since the composite granule can provide long-acting calcium ion and osteolith nucleation site during bone defect healing, the performance of calcium phosphate bone repair materials is optimized, is a kind of excellent bone renovating material.
Description
Technical field
The invention belongs to biomaterial for medical purpose fields, and in particular to the high active unformed calcium phosphate/lemon of biomineralization
Sour calcium composite granule and preparation method thereof.
Background technique
Unformed calcium phosphate because than the calcium phosphate of crystalline state have more excellent bioactivity and biodegradability, and by
In terms of being widely used in the bio-medicals such as biological coating and bone cement, while researcher also increasingly pays close attention to unformed calcium phosphate
Preparation.Unformed calcium phosphate is to be present in a kind of intermediate for preparing hydroxyapatite, is easily changed into crystalline state during the preparation process
Hydroxyapatite.Since the condition for preparing unformed calcium phosphate in water phase is extremely harsh, it usually needs use certain stabilization
Agent converts unformed calcium phosphate to crystalline state, this is resulted in the product of preparation, and there are some auxiliary to stablize unformed calcium phosphate
By-product, and these by-products reduce the bioactivity of unformed calcium phosphate.Such as Joseph M. Antonucci et al.
(Polymeric amorphous calcium phosphate compositions, Joseph M. Antonucci, et
Al.US5508342A P) is used2O7 4-、Mg2+、CO3 2-As stabilizer, it is added in unstable unformed calcium phosphate, in this way
The unformed calcium-phosphate product being prepared all contains other a degree of subsidiary ions, influences unformed calcium phosphate itself
Performance advantage.Dosuk D. Lee et al. (Synthesis of reactive amorphous calcium phosphates,
Dosuk D. Lee, et al. US5676976A) provide it is a kind of convert standard inert amorphous state calcium phosphate precipitation to it is high anti-
The new method of answering property non-crystalline solids, but test reaction temperature condition needs carried out under 4 ~ 5 °C, and with filter paper filtering and
Vacuum pressure is about 10-2Support, it is clear with about 4 liters of distilled water by adding water into filter tunnel after forming one thin cake shape
Wash material.Then washed material is collected with spatula, is immersed in the liquid nitrogen in 200 milliliters of containers.Once sediment shape
At hard Freezing block, container is transferred to vacuum chamber 24 hours (10-3Bristol), until obtaining fine powder and dry powder.In preparation nothing
It is formed during calcium phosphate there are the severity of temperature condition, increases technology difficulty, and the powder obtained does not emphasize powder
Stability, a kind of armorphous calcium phosphate is only prepared.So needing to solve problem above at present, easy system is used
The unformed calcium phosphate that Preparation Method is stabilized at room temperature.
Calcium citrate is a kind of nontoxicity, the good organic calcium salt of biological degradability, and calcium citrate is Bone Defect Repari process
The calcium ion at middle offer initial stage, for having great advantage in terms of bio-medical.Chinese patent application 200710179395
.6, containing the human body hard tissue filling renovation material of calcium citrate, one kind is provided with calcium citrate novel doctor as main component
Treat use human body hard tissue filling renovation material, with good biocompatibility, preferable biological degradability, preferable plasticity,
Certain mechanical strength, good material bioactivity and bone-forming effect repairs medical need to adapt to human body hard tissue filling
It wants.Ultra-fine calcium citrate made from Chinese patent CN108218694A has higher due to there is higher specific surface area
Activity is easier to be absorbed by organism, as calcium supplement or the bone renovating material calcium ion effect that then ultra-fine calcium citrate provides
It is more significant.This can also illustrate a series of advantages of calcium citrate, the especially unformed phosphoric acid good with same bioactivity simultaneously
After calcium is compound, it can more reinforce the bioactivity on bone renovating material.
A kind of high active unformed calcium phosphate/calcium citrate composite granule of biomineralization provided by the invention, this is compound
In system, it is that the chelating based on calcium citrate is captured that calcium citrate, which can inhibit unformed calcium phosphate to convert to hydroxyapatite,
The calcium ion that unformed calcium phosphate is converted to hydroxyapatite ensure that unformed phosphoric acid so that its calcium-phosphorus ratio no longer improves
Calcium is stabilized, while the process also inhibits the crystallization of calcium citrate.In the compound system, the both conducts of the calcium citrate of complexing
A kind of stabilizer of unformed calcium phosphate, but have good biocompatibility and degradability, with unformed calcium phosphate it is compound after
Composite granule 9 days are aged in water phase still with the presence of unformed state, be provided simultaneously with excellent biomineralization activity, curing
There is good application prospect with bone renovating material field.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high active unformed calcium phosphate/citric acids of biomineralization
Calcium composite granule and preparation method thereof, and this composite granule is to be stable in the presence of in water phase at room temperature, and composite granule has
Excellent biomineralization activity.
The step of the method for the present invention, is as follows:
(1) calcium chloride, citrate dihydrate trisodium and phosphoric acid hydrogen are weighed 40% ~ 88% by unformed calcium phosphate quality accounting range
Diammonium, is dissolved in deionized water respectively, and 100 ~ 600 ml concentration of preparation are the mol/L of 0.1 mol/L ~ 0.6 calcium chloride solution (solution
A), the sodium citrate solution (solution B) that 30 ~ 200 ml concentration are the mol/L of 0.05 mol/L ~ 0.2 is prepared, prepares 50 ~ 300
Ml concentration is the ammonium dihydrogen phosphate (solution C) of the mol/L of 0.1 mol/L ~ 0.3；By three sodium solution of citrate dihydrate and phosphorus
Sour two ammonium salt solution of hydrogen is uniformly mixed and obtains the mixed solution D of 80 ~ 500ml；
(2) the high active unformed calcium phosphate of biomineralization/calcium citrate composite granule preparation method described in step (1),
Middle calcium chloride can be replaced with calcium nitrate, and sodium citrate can use citric acid or ammonium citrate substitution, and diammonium hydrogen phosphate can be with
It is substituted with disodium hydrogen phosphate or phosphoric acid；
(3) according to three kinds of solution of the preparation in step (1), C is first added drop-wise to solution A, and after dripping C, it is molten that B is then added dropwise
Liquid；
(4) step (3) is also possible to mixed solution D to be added drop-wise in solution A；
(5) it during the dropwise addition of step (3) or (4), is added dropwise while stirring, rate of addition is 7~10 ml/L, stirring rate
For 5~60 r/min, addition alcohol water ratio is the 100 ml:50 ml ethanol waters of ml:100 ml ~ 200, with 10% ~ 25%(wt)
Ammonium hydroxide or 10% ~ 25%(wt) sodium hydroxide solution control entire reaction solution pH value be 8 ~ 12, maintain 20 °C ~ 80 °C
At a temperature of react 20 ~ 40 min arrive sediment；
(6) the precipitating digestion time obtained 3 ~ 9 days changes a deionized water daily, uses 60% ~ 90% ethanol water during ageing
After solution centrifuge washing 2-3 times, vacuum drying obtains composite granule under 20-60 °C.
The present invention have the advantages that it is following and the utility model has the advantages that
Present technology provides a kind of can to prepare stable unformed calcium phosphate in water phase.The preparation method technique letter of the material
It is single, it is easy to get, compound lemon acid calcium is only needed to can be obtained by unformed composite granule, unformed phosphorus is prepared before overcoming
The harsh conditions of sour calcium.The unformed composite granule being prepared simultaneously is with good stability, after precipitating ageing 9 days, according to
It is old there is no crystalline state.And and calcium citrate with biological advantages it is compound after, reduce other useless by-products, hair
The advantages of calcium citrate provides calcium ion during Bone Defect Repari is waved, so that this composite granule has more bioactivity, in bone
Repair application aspect advantageously.
Detailed description of the invention:
Fig. 1 is the SEM photograph of the composite granule prepared in the embodiment of the present invention 2；
Fig. 2 is the XRD spectra of the composite granule prepared in the embodiment of the present invention 3；
Fig. 3 is the XRD spectra of the composite granule prepared in the embodiment of the present invention 5.
Specific embodiment:
The present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
It is molten to weigh the calcium chloride that quality is 2.3305 g using electronic balance for the unformed calcium phosphate for being 88% according to quality accounting
In the deionized water of 105 ml, compound concentration is the solution A of 0.2 mol/L；Weigh the sodium citrate that quality is 1.1764 g
It is dissolved in the deionized water of 40 ml, is formulated as the B solution that concentration is 0.1 mol/L；Weigh the phosphoric acid hydrogen that quality is 1.3206 g
Diammonium is dissolved in the deionized water of 100 ml, and compound concentration is the C solution of 0.1 mol/L；C solution and B solution are uniformly mixed
(solution D) afterwards, preparation alcohol water ratio is 100 ml:100 ml ethanol waters, after mixing two kinds of acid solutions, at 30 °C
It is lower that solution A is stirred with the speed of 55 rad/min with magnetic stirrer, add D molten with 10 ml/min into solution A while stirring
Liquid, reaction stop after stirring 30 min, and after ageing 3 days, the ethanol water centrifuge washing that concentration is 70% is added using centrifuge
After 3 times, gained composite granule after being dried in vacuo under 60 °C；
Embodiment 2
It is molten to weigh the calcium chloride that quality is 4.9941 g using electronic balance for the unformed calcium phosphate for being 40% according to quality accounting
In the deionized water of 225 ml, compound concentration is the solution A of 0.2 mol/L；It is molten to weigh the sodium citrate that quality is 5.882 g
In the deionized water of 200 ml, it is formulated as the B solution that concentration is 0.1 mol/L；Weigh the phosphoric acid hydrogen that quality is 1.3206 g
Diammonium is dissolved in the deionized water of 100 ml, and compound concentration is the C solution of 0.1 mol/L；Preparation alcohol water ratio is 100 ml:100
The ethanol water of ml, after mixing (solution D) two kinds of acid solutions, with magnetic stirrer with 55 rad/ under 30 °C
The speed of min stirs solution D, adds solution A into solution D while stirring with 10 ml/min, with the ammonium hydroxide control pH of 15%(wt)=
10, while prepared ethanol water is added, stop after 40 min of reaction stirring, after ageing 3 days, is added using centrifuge dense
After degree is ethanol water centrifuge washing 3 times of 70%, gained composite granule after being dried in vacuo under 50 °C；Gained after vacuum drying
Composite granule SEM it is as shown in Figure 1.
Embodiment 3
It weighs the calcium chloride that quality is 3.3294 g using electronic balance to be dissolved in the deionized water of 150 ml, compound concentration is
The solution A of 0.2 mol/L；It weighs the sodium citrate that quality is 2.941 g to be dissolved in the deionized water of 100 ml, is formulated as concentration
For the B solution of 0.1 mol/L；It weighs the diammonium hydrogen phosphate that quality is 1.3206 g to be dissolved in the deionized water of 100 ml, prepare
Concentration is the C solution of 0.1 mol/L；Alcohol water is prepared than the ethanol water for 150 ml:150 ml, uses magnetic force under 30 °C
Blender stirs solution A with the speed of 55 rad/min, C solution is added drop-wise in solution A with the speed of 9 ml/min, with 15%
(wt) ammonium hydroxide controls pH=10, while prepared ethanol water is added, and stops after 35 min of reaction stirring, is aged 3 days
Afterwards, after the use of centrifuge addition concentration being ethanol water centrifuge washing 3 times of 70%, gained is compound after being dried in vacuo under 50 °C
Powder；The XRD of gained composite granule is as shown in Figure 2 after vacuum drying.
Embodiment 4
It weighs the calcium chloride that quality is 3.3294 g using electronic balance to be dissolved in the deionized water of 150 ml, compound concentration is
The solution A of 0.2 mol/L；It weighs the sodium citrate that quality is 2.941 g to be dissolved in the deionized water of 100 ml, is formulated as concentration
For the B solution of 0.1 mol/L；It weighs the diammonium hydrogen phosphate that quality is 1.3206 g to be dissolved in the deionized water of 100 ml, prepare
Concentration is the C solution of 0.1 mol/L；Alcohol water is prepared than the ethanol water for 150 ml:150 ml；Magnetic force is used at 35 °C
Blender stirs solution A with 60 r/min, C solution and B solution after mixing (solution D) with 7 ml/min to be added drop-wise to A molten
In liquid, the pH of solution is transferred to 10 with the ammonium hydroxide of 15%(wt), the ethanol water prepared is added, stops after 30 min of reaction stirring
Only, it after being aged 3 days, after the use of centrifuge addition concentration being ethanol water centrifuge washing 3 times of 70%, is dried in vacuo under 55 °C
Gained composite granule afterwards.
Embodiment 5
It weighs the calcium chloride that quality is 3.3294 g using electronic balance to be dissolved in the deionized water of 150 ml, compound concentration is
The solution A of 0.2 mol/L；It weighs the sodium citrate that quality is 2.941 g to be dissolved in the deionized water of 100 ml, is formulated as concentration
For the B solution of 0.1 mol/L；It weighs the diammonium hydrogen phosphate that quality is 1.3206 g to be dissolved in the deionized water of 100 ml, prepare
Concentration is the C solution of 0.1 mol/L；Prepare ethyl alcohol: deionized water=200 ml:150 ml ethanol water；At 30 °C
It is lower that solution A is stirred with the speed of 60 r/min using magnetic agitation, C solution and B solution after mixing (solution D) with 7
The speed of ml/min is added drop-wise in solution A, and the pH of solution is transferred to 10 with the ammonium hydroxide of 10%(wt), it is water-soluble that the ethyl alcohol prepared is added
Liquid, reaction stop after stirring 40min, and after ageing 9 days, the ethanol water centrifuge washing 3 that concentration is 75% is added using centrifuge
After secondary, gained composite granule after being dried in vacuo under 55 °C.The XRD of gained composite granule is as shown in Figure 3 after vacuum drying.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (7)
1. high active unformed calcium phosphate/calcium citrate composite granule of biomineralization and preparation method thereof, it is characterised in that: should
Composite granule is by calcium citrate and calcium phosphate two-phase is compound constitutes, and two-phase is unformed state.
2. the active unformed calcium phosphate/calcium citrate composite granule of high biomineralization according to claim 1, feature
Be: for unformed calcium phosphate quality accounting range 40% ~ 88%, other are calcium citrate in the composite granule.
3. the active unformed calcium phosphate/calcium citrate composite granule of high biomineralization according to claim 1, feature
Be: the composite granule can be stabilized in water phase with unformed shape.
4. the active unformed calcium phosphate of high biomineralization/calcium citrate composite granule preparation side according to claim 1
Method, which comprises the following steps:
(1) calcium chloride, citrate dihydrate trisodium and diammonium hydrogen phosphate are weighed, is dissolved in deionized water respectively, prepares 100 ~ 600 ml
Concentration is the calcium chloride solution (solution A) of the mol/L of 0.1 mol/L ~ 0.6, and 30 ~ 200 ml concentration of preparation are 0.05 mol/L
The sodium citrate solution (B solution) of ~ 0.2 mol/L prepares the phosphorus that 50 ~ 300 ml concentration are the mol/L of 0.1 mol/L ~ 0.3
Acid dihydride ammonium salt solution (C solution)；Both three sodium solution of citrate dihydrate (solution A) and ammonium dibasic phosphate solution (C solution) is mixed
It closes and uniformly obtains the mixed solution D of 80 ~ 500ml；
(2) C solution of 50 ~ 300 ml is first added drop-wise to the solution A of 100 ~ 600 ml, after dripping C solution, is then added dropwise 30
The B solution of ~ 200 ml；
(3) step (2) is also possible in the solution A for the solution D of 80 ~ 500ml being added drop-wise to 100 ~ 600 ml；
(4) it during the dropwise addition of step (2) or (3), is added dropwise while stirring with the stirring rate of 5~60 r/min, speed is added dropwise
Degree is 7~10 ml/min, while the ethanol water that alcohol water ratio is 100 ml:50 of ml:100 ml ~ 200 ml is added, and is used
10% ~ 25%(wt) ammonium hydroxide or 10% ~ 25%(wt) the sodium hydroxide solution pH value that controls entire reaction solution is 8 ~ 12, maintain 20
°C ~ 50 °C at a temperature of react 20 ~ 40 min arrive sediment；
(5) precipitating obtained is aged 3-9 days, changes a deionized water during ageing daily, the ethyl alcohol for the use of concentration being 60% ~ 90%
Vacuum drying obtains product under aqueous solution centrifuge washing 2-5 times, 20-60 °C.
5. the high active unformed calcium phosphate/calcium citrate composite powder of biomineralization according to step in claim 4 (1)
Preparation, wherein calcium chloride can be substituted with calcium nitrate, and sodium citrate can be substituted with citric acid or ammonium citrate, phosphorus
Sour hydrogen diammonium can be substituted with disodium hydrogen phosphate or phosphoric acid.
6. the active unformed calcium phosphate/calcium citrate composite granule of high biomineralization according to claim 4, preferably
, both three sodium solution of citrate dihydrate (solution A) and ammonium dibasic phosphate solution (C solution) are uniformly mixed and obtain 80 ~ 500ml
Mixed solution D be added drop-wise in the solution A of 100 ~ 600 ml.
7. the active unformed calcium phosphate/calcium citrate composite granule of high biomineralization according to claim 1, can be used as
Bone renovating material.
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Cited By (5)
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| CN112107732A (en) * | 2020-09-18 | 2020-12-22 | 成都理工大学 | Anti-scouring high-mineralization-activity composite bone cement and preparation method thereof |
| CN112107735A (en) * | 2020-09-18 | 2020-12-22 | 成都理工大学 | Injectable degradable high-mineralization-activity composite bone cement and preparation method thereof |
| CN113018512A (en) * | 2021-04-07 | 2021-06-25 | 成都理工大学 | Porous polyurethane bone repair material prepared by gas foaming method and application thereof |
| CN113209386A (en) * | 2021-04-21 | 2021-08-06 | 成都理工大学 | Preparation method of polyurethane bone scaffold with body temperature shape memory effect |
| CN113289069A (en) * | 2021-04-28 | 2021-08-24 | 成都理工大学 | Polyurethane composite porous bone scaffold with high biological activity and preparation method thereof |
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| CN113018512A (en) * | 2021-04-07 | 2021-06-25 | 成都理工大学 | Porous polyurethane bone repair material prepared by gas foaming method and application thereof |
| CN113209386A (en) * | 2021-04-21 | 2021-08-06 | 成都理工大学 | Preparation method of polyurethane bone scaffold with body temperature shape memory effect |
| CN113289069A (en) * | 2021-04-28 | 2021-08-24 | 成都理工大学 | Polyurethane composite porous bone scaffold with high biological activity and preparation method thereof |
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Application publication date: 20190920 |
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