CN105748510A - Fluorine controlled-release calcium phosphate bioactive material and preparation method thereof - Google Patents
Fluorine controlled-release calcium phosphate bioactive material and preparation method thereof Download PDFInfo
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- CN105748510A CN105748510A CN201610127249.8A CN201610127249A CN105748510A CN 105748510 A CN105748510 A CN 105748510A CN 201610127249 A CN201610127249 A CN 201610127249A CN 105748510 A CN105748510 A CN 105748510A
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- fluorine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/16—Fluorine compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
Abstract
The present invention discloses a fluorine controlled-release calcium phosphate bioactive material and a preparation method thereof. Fluorinion loaded in apatite structure is used as a fluorine source, and beta-tricalcium phosphate (beta-TCP) and carbonate ions are used to substitute apatite as a carrier for fluoride release; a co-precipitation method is employed for the synthesis of a fluorine and carbonate ion co-doped apatite and beta-TCP biphasic bioactive materials; and by controlling the phase ratio of beta-TCP and apatite, and substitution of carbonate ions in apatite, the regulation of dissolution and absorption of apatite is achieved, thereby regulating the slow release of fluorinion in the apatite structure. The material not only has good biocompatibility and bioactivity, but also can maintain local effective fluorine concentration for a long time, and can be widely used in osteoporosis treatment and dental treatment; therefore, the material has significant economic benefits.
Description
Technical field
The present invention relates to a kind of fluorine slow-release bio material, be specifically related to a kind of controlled fluorine sustained release calcium phosphate bioactive material
And preparation method thereof.
Background technology
The micro elements needed by human that fluorine is well recognized as, is primarily present in the sclerous tissues such as bone, tooth.In field, oral cavity,
The fluor-apatite that fluorine release recrystallization is formed has the surface texture of densification, it is possible to decrease surface free energy, reduces the adhesion of bacterium；
Solubility is little in an acidic solution, can improve the capacity antacid of gum；And may also rely on dissolution trace F-Sterilization make
With (the energetic supersession required for direct bacteria growing inhibiting；The activity of suppression glycolytic ferment；The exocellular polysaccharide inhibiting bacterium closes
Become) can pre-anti-caries.In bone tissue field, fluorine ion has positive therapeutic action to osteoporosis.Fluorine can promote body
Inside and outside osteoblast activity, directly increases osteoblastic diffusivity and alkaline phosphatase activities, strengthens new bone tissue and is formed.
Research shows, fluorine is treated can promote osteoblastic propagation and differentiation, is reasonably resistant to the absorption of osteoclast.
Need to reach certain concentration requirement and long-lasting in view of internal F treatment, have fluorine therapeutic effect and fluorine will not be caused
Poisoning, until the completing of enamel recrystallization and osteanagenesis process.Therefore, using which kind of mode to introduce fluorine is that a key is asked
Topic.There is the fluorine-containing things such as the sodium fluoride of highly soluble, calcirm-fluoride and sodium monofluorophosphate and can not control the slowly release and not of fluorine
Ceramic body can be sintered into and be not suitable for being sustained embedded material directly as fluorine, and often be combined (such as compound resin, fibre with organic carrier
Dimension element, PLA, aluminosilicate polyacrylate, alginates, methyl amine, carboxymethyl chitosan etc.) prepare fluorine slow-release material, but this
A little carriers the most all also exist some problems, such as relatively low mechanical strength, the sensitivity of initial humidity, the filter of harmful constituent
Go out, cytotoxicity that may be present etc..Using bioactivity glass as releasing fluorine carrier, biological living can be adjusted by changing formula
Property glass degradation rate, but introduce fluorine can lose in a large number in bio-vitric melting process；The most directly use fluorine phosphorus
Lime stone can be because the reason such as solubility is low and sintering temperature is high so that the Oil repellent of release is too low does not reaches treatment requirement.Cause
This, select to have excellent mechanical performances and biology performance, controlled fluorine release concentration and fluorine release the carrier of speed become preparation can
The key of control fluorine slow releasing bioactivity material.
Calcium phosphate biological ceramic mainly includes apatite and tricalcium phosphate, and the apatite used as biomaterial is usually
Ca Yu P atomic ratio is the hydroxyapatite Ca of 1. 6710(PO4)6(OH)2(being called for short HA), tricalcium phosphate is Ca and P
Atomic ratio is the β-tricalcium phosphate β-Ca of 1. 53 (PO4)2(being called for short β-TCP).Calcium phosphate is mainly with the phosphorus ash of crystalline state
Stone constitutes the main body of human body hard tissue mutually.Therefore synthos pottery have with mineralization of skeleton species as composition, surface and
Bulk structure, has good biocompatibility with tissue, can form firm synostosis with natural bone.
HA crystal is hexagonal crystal system, there is a bigger passage along six square shafts, can accommodate more doping in structure
Ion, carbonate, fluorine, silicon, magnesium, sodium plasma all can enter HA structure and adulterate.Carbonate (CO3) it is that osteolith contains
Measuring most Doped ions, the existence of carbonate has and helps to meet human body natural's bone and should have certain stability again may be by just
The physiological requirements often absorbed.CO3 2-Replacement can make crystalline size diminish, degree of crystallinity reduce, distortion of lattice increase, specific surface area and
Active surface activity increases, thus improves dissolution velocity and solubility, promotes Ca in apatite2+Dissociation and biomineralization
Effect；And the small-sized crystals produced due to carbonate substitute and high-load lattice defect, significantly reduce sintering temperature.
There are some researches show, and HA compares, β-TCP is easier to dissolve in vivo, and its solubility is about high 10 ~ 20 times than HA.
Therefore, by the control of carbonate substitute in composition phase content and apatite, calcium phosphate ceramic degraded in vivo can be changed
Speed.
Therefore, in apatite structure, the fluorine ion of load is as fluorine source, with β-TCP and carbonate substitute apatite for releasing
Fluorine carrier, uses Co deposited synthesis fluorine and the composite mixed apatite of carbonate and β-TCP two-phase bioactive materials, passes through
In the thing Phase Proportion of control β-TCP and HA and HA, the replacement of carbonate regulates and controls dissolving and the absorption of apatite, thus regulates and controls phosphorus ash
The slow release of fluorine ion in stone structure.This material not only has good biocompatibility and biologically active, and can be long-acting
Maintain topically effective Funing tablet, can be widely used for each phase osteoporosis and the treatment of dentistry.
With β-TCP and carbonate substitute apatite for releasing fluorine carrier, prepare controlled fluorine sustained release by coprecipitation
There is not been reported both at home and abroad for calcium phosphate bioactive material.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, environmental protection, can improve biocompatibility and
Bioactive one controlled fluorine sustained release calcium phosphate bioactive material and preparation method thereof.
The present invention is achieved by the following technical programs: a kind of controlled fluorine sustained release calcium phosphate bioactive material, it is special
Levy and be: the thing of described controlled fluorine sustained release calcium phosphate bioactive material by the composite mixed apatite of fluorine and carbonate and β-
Tricalcium phosphate constitute, the mol ratio of its dispensing n [Ca]/n [P] is 1.5～1.7, the mol ratio of n [F]/n [Ca] be 0.05～
0.2, n [CO3]/n[PO4] mol ratio be 0.05～1.
In described controlled fluorine sustained release calcium phosphate bioactive material, the content of doped with fluorine ion is 0.01～2wt%, and adulterate carbon
The content of acid group is 2～10wt%.
The preparation method of above-mentioned controlled fluorine sustained release calcium phosphate bioactive material, it is characterised in that comprise the following steps:
Step one: preparation calcium source and phosphorus source solution, the ratio controlling n [Ca]/n [P] is 1.5～1.7, forms 0.5～2.5mol/l
Precursor solution, and at n [CO3]/n[PO4] be 0.05～1, n [F]/n [Ca] be to determine F ion in the range of 0.05～0.2
And CO3The value of ion, then adds a certain amount of fluorine source and carbonate source in phosphorus source solution uniform stirring, until solid
Fully dissolve；
Step 2: the mixed solution of aforementioned phosphorus source, fluorine source and carbonate source is added drop-wise to calcium source solution lentamente by constant flow pump
In, it being stirred vigorously while titration, keep the pH value of mixed liquor not less than 10 with alkali lye, reaction temperature is automatic by water-bath
Thermostatic control, after reaction completely, mixed liquor is put and is continued stirring 2～12h at room temperature；
Step 3: after the aged operation of mixed liquor after stirring, is washed till neutrality with distilled water washing, suction filtration, ethanol, then through dry
Ground 200～325 mesh sieves after dry, obtain the calcium phosphate bioactive powder of controlled fluorine sustained release；
Step 4: repressed for powder molding procedure being placed in tube-type atmosphere furnace and be heat-treated, protective atmosphere is CO2Gas
Body, flow is 0.5～1.5 L/min, and programming rate is 2～10 DEG C/min, and heat treatment temperature is 600～1000 DEG C, during insulation
Between be 1～4h, cooling rate is 1～5 DEG C/min.
Described calcium source is the one in calcium nitrate, calcium acetate, calcium chloride and calcium hydroxide；Described phosphorus source be phosphoric acid,
One in diammonium hydrogen phosphate, ammonium phosphate；Described fluorine source is ammonium fluoride or sodium fluoride；Described carbonate source is sodium acid carbonate
Or ammonium hydrogen carbonate；Described alkali lye is NaOH and ammoniacal liquor.
In described step 2, the speed of titration is 2～10 ml/min, and the reaction temperature of water-bath is 0～90 DEG C.
The step being aged operation in described step 3 is that mixed liquor is stood 12～48h, pours out supernatant liquor, residue is mixed
Close liquid and carry out distillation washing, until pH value is 7, finally carry out filtering to obtain filter cake with absolute ethyl alcohol.
Baking temperature in described step 3 is 60～100 DEG C, and drying time is 12～48h.
In described step 4, the step of compressing operation is: after powder granulation, is pressed in advance under the pressure of 20 MPa
A diameter of 10mm, the thick cylinder sample being about 5mm, then become block with the isostatic pressing of 250MPa.
The present invention using the fluorine ion of load in apatite structure, as fluorine source, with β-TCP and carbonate substitute apatite is
Release the composite mixed apatite of fluorine carrier, employing Co deposited synthesis fluorine and carbonate and β-TCP two-phase bioactive materials, logical
Cross the dissolving substituting regulation and control apatite and the absorption of carbonate in control β-TCP and the thing Phase Proportion of apatite and apatite,
Thus regulate and control the slow release of fluorine ion in apatite structure.This material not only has good biocompatibility and biology is lived
Property, and the energy topically effective Funing tablet of long-acting maintenance, can be widely used for each phase osteoporosis and the treatment of dentistry, have notable
Economic benefit.
Detailed description of the invention
By further illustrating the technological means and effect that the present invention taked by reaching predetermined goal of the invention, below in conjunction with
Preferred embodiment, the present invention is described in detail:
Embodiment 1
According to the Ca (NO that the mol ratio of n [Ca]/n [P] is 1.58 preparation 1 mol/L3)2•4H2O and 1 mol/L (NH4)2HPO4
Solution, by n [CO3]/ n [PO4]=0.5, the mol ratio of n [F]/n [Ca]=0.1 is respectively by appropriate NH4F and NaHCO3Add
Enter to (NH4)2HPO4Solution stirs, forms uniform settled solution.
By (NH4)2HPO4、NH4F and NaHCO3Mixed liquor added the most lentamente with the speed of 5ml/min by constant flow pump
Enter to Ca (NO3)2•4H2In O, being stirred vigorously while titration, the pH value keeping mixed liquor with ammoniacal liquor is 10, mixed after reaction completely
Close liquid and put continuation stirring 4h at room temperature.Mixed liquor is stood 24h, pours out supernatant liquor, residual mixed liquor is carried out distilled water
Wash, until pH value is 7, finally filter with absolute ethyl alcohol.Gained filter cake is placed in drying box in 60 DEG C of dry 48h.By institute
Obtain product to be ground in grinding alms bowl, then sieve by 325 mesh sieve and finally give controlled fluorine sustained release calcium phosphate bioactive
Material.
Pressed by powder shaping is placed in tube-type atmosphere furnace and carries out CO2Heat treatment under protective atmosphere, wet CO2Gas stream
Amount is 1 l/min.Programming rate is 2 DEG C/min, and heat treatment temperature is 800 DEG C, and temperature retention time is 2h, and cooling rate is 1
℃/min.After above-mentioned for 40mg fluorine slow-release material is placed in 15ml normal saline solution immersion 48h, fluorine is released concentration and is about 80 μ g/
L, calcium ion concentration reaches 30ppm, and fluorine sustained release and biology performance are good.
Embodiment 2
According to (the CH that the mol ratio of n [Ca]/n [P] is 1.6 preparation 0.5 mol/L3COO)2Ca•H2O and 0.5 mol/L (NH4)3PO4Solution, by n [CO3]/[PO4]=0.8, the stoicheiometry of n [F]/n [Ca]=0.12 is respectively by appropriate NaF and NaHCO3Add
Enter to (NH4)3PO4Solution stirs, forms uniform settled solution.
By (NH4)3PO4, NaF and NaHCO3Mixed liquor added the most lentamente with the speed of 8ml/min by constant flow pump
Enter to (CH3COO)2Ca•H2In O, being stirred vigorously while titration, the pH value keeping mixed liquor with NaOH is 12, has reacted
After complete, mixed liquor is put and is continued stirring 8h at room temperature.Mixed liquor is stood 24h, pours out supernatant liquor, residual mixed liquor is carried out
Distillation washing, until pH value is 7, finally filters with absolute ethyl alcohol.Gained filter cake is placed in drying box and is dried in 70 DEG C
48h.Products therefrom is ground in grinding alms bowl, then sieves by 325 mesh sieve and finally give controlled fluorine sustained release carbon phosphoric acid
Calcium bioactive materials.
Pressed by powder shaping is placed in tube-type atmosphere furnace and carries out CO2Heat treatment under protective atmosphere, wet CO2Gas flow
It is 1.5 l/min.Programming rate is 3 DEG C/min, and heat treatment temperature is 700 DEG C, and temperature retention time is 2h, and cooling rate is 1
℃/min.After above-mentioned for 40mg fluorine slow-release material is placed in 15ml normal saline solution immersion 48h, fluorine is released concentration and is about 100 μ g/
L, calcium ion concentration reaches 40ppm, and fluorine sustained release and biology performance are good.
Embodiment 3
According to the Ca (OH) that the mol ratio of n [Ca]/n [P] is 1.65 preparation 0.75 mol/L2With 0.75 mol/LH3PO4Solution,
By n [CO3]/n[PO4]=0.4, the stoicheiometry of n [F]/n [Ca]=0.06 is respectively by appropriate NH4F and NH4HCO3Join
H3PO4Solution stirs, forms uniform settled solution.
By H3PO4、NH4F and NH4HCO3Mixed solution added the most lentamente with the speed of 10ml/min by constant flow pump
Enter to Ca (OH)2In solution, being stirred vigorously while titration, the pH value keeping mixed liquor with ammoniacal liquor is 11, mixed after reaction completely
Close liquid and put continuation stirring 6h at room temperature.Mixed liquor is stood 24h, pours out supernatant liquor, residual mixed liquor is carried out distilled water
Wash, until pH value is 7, finally filter with absolute ethyl alcohol.Gained filter cake is placed in drying box in 80 DEG C of dry 24h.By institute
Obtain product to be ground in grinding alms bowl, then sieve by 250 mesh sieve and finally give controlled fluorine sustained release calcium phosphate bioactive
Material.
Pressed by powder shaping is placed in tube-type atmosphere furnace and carries out CO2Heat treatment under protective atmosphere, wet CO2Gas flow
It is 0.5 l/min.Programming rate is 4 DEG C/min, and heat treatment temperature is 900 DEG C, and temperature retention time is 2h, cooling rate is 3 DEG C/
min.After above-mentioned for 40mg fluorine slow-release material is placed in 15ml normal saline solution immersion 48h, fluorine is released concentration and is about 50 μ g/l, calcium
Ion concentration reaches 15ppm, and fluorine sustained release and biology performance are good.
Embodiment 4
According to the CaCl that the mol ratio of n [Ca]/n [P] is 1.62 preparation 1.5 mol/L2With 1.5 mol/L (NH4)2HPO4Molten
Liquid, by n [CO3]/ [PO4]=0.6, the stoicheiometry of n [F]/n [Ca]=0.08 is respectively by appropriate NaF and NH4HCO3Add
To (NH4)2HPO4Solution stirs, forms uniform settled solution.
By (NH4)2HPO4, NaF and NH4HCO3Mixed solution by constant flow pump with the speed of 4ml/min the most slowly
Join CaCl2In, it being stirred vigorously while titration, the pH value keeping mixed liquor with NaOH is 11, mixed after reaction completely
Close liquid and put continuation stirring 8h at room temperature.Mixed liquor is stood 24h, pours out supernatant liquor, residual mixed liquor is carried out distilled water
Wash, until pH value is 7, finally filter with absolute ethyl alcohol.Gained filter cake is placed in drying box in 90 DEG C of dry 12h.By institute
Obtain product to be ground in grinding alms bowl, then sieve by 200 mesh sieve and finally give controlled fluorine sustained release calcium phosphate bioactive
Material.
Pressed by powder shaping is placed in tube-type atmosphere furnace and carries out CO2Heat treatment under protective atmosphere, wet CO2Gas flow
For 0.5l/min.Programming rate is 5 DEG C/min, and heat treatment temperature is 600 DEG C, and temperature retention time is 2h, cooling rate is 4 DEG C/
min.After above-mentioned for 40mg fluorine slow-release material is placed in 15ml normal saline solution immersion 48h, fluorine is released concentration and is about 70 μ g/l, calcium
Ion concentration reaches 25ppm, and fluorine sustained release and biology performance are good.
Claims (8)
1. a controlled fluorine sustained release calcium phosphate bioactive material, it is characterised in that: the thing of described calcium phosphate bioactive material
The apatite composite mixed by fluorine and carbonate is constituted with β-TCP, in its dispensing the mol ratio of n [Ca]/n [P] be 1.5～
The mol ratio of 1.7, n [F]/n [Ca] is 0.05～0.2, n [CO3]/n[PO4] mol ratio be 0.05～1.
Controlled fluorine the most according to claim 1 sustained release calcium phosphate bioactive material, it is characterised in that: described controlled fluorine delays
Releasing the content of doped with fluorine ion in calcium phosphate bioactive material is 0.01～2wt%, doping carbonate content be 2～
10wt%。
The preparation method of controlled fluorine the most according to claim 1 sustained release calcium phosphate bioactive material, it is characterised in that bag
Include following steps:
Step one: preparation calcium source and phosphorus source solution, controlling n [Ca]/n [P] mol ratio is 1.5～1.7, formed 0.5～
The precursor solution of 2.5mol/l, and at n [CO3]/n[PO4] be 0.05～1, n [F]/n [Ca] be in the range of 0.05～0.2
Determine F ion and CO3The value of ion, then adds to a certain amount of fluorine source and carbonate source in phosphorus source solution and uniformly stirs
Mix, until solid fully dissolves；
Step 2: the mixed solution of aforementioned phosphorus source, fluorine source and carbonate source is added drop-wise to calcium source solution lentamente by constant flow pump
In, it being stirred vigorously while titration, keep the pH value of mixed liquor not less than 10 with alkali lye, reaction temperature is automatic by water-bath
Thermostatic control, after reaction completely, mixed liquor is put and is continued stirring 2～12h at room temperature；
Step 3: after the aged operation of mixed liquor after stirring, is washed till neutrality with distilled water washing, suction filtration, ethanol, then through dry
Ground 200～325 mesh sieves after dry, obtain the calcium phosphate bioactive powder of controlled fluorine sustained release；
Step 4: repressed for powder molding procedure being placed in tube-type atmosphere furnace and be heat-treated, protective atmosphere is CO2Gas,
Flow is 0.5～1.5 L/min, and programming rate is 2～10 DEG C/min, and heat treatment temperature is 600～1000 DEG C, temperature retention time
Being 1～4h, cooling rate is 1～5 DEG C/min.
Preparation method the most according to claim 3, it is characterised in that: described calcium source is calcium nitrate, calcium acetate, calcium chloride
With the one in calcium hydroxide；Described phosphorus source is the one in phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate；Described fluorine source is fluorine
Change ammonium or sodium fluoride；Described carbonate source is sodium acid carbonate or ammonium hydrogen carbonate, and described alkali lye is NaOH and ammoniacal liquor.
Preparation method the most according to claim 3, it is characterised in that: in described step 2, the speed of titration is 2～10
Ml/min, the reaction temperature of water-bath is 0～90 DEG C.
Preparation method the most according to claim 3, it is characterised in that: described step 3 is aged the step of operation for mixing
Close liquid and stand 12～48h, pour out supernatant liquor, residual mixed liquor is carried out distillation washing, until pH value is 7, finally with anhydrous
Ethanol carries out filtering to obtain filter cake.
Preparation method the most according to claim 3, it is characterised in that: the baking temperature in described step 3 is 60～100
DEG C,
Drying time is 12～48h.
Preparation method the most according to claim 3, it is characterised in that: the step of compressing operation in described step 4
For:
After powder granulation, under the pressure of 20MPa, it is pressed into a diameter of 10mm in advance, the cylinder sample of thickness about 5mm, then with
The isostatic pressing of 250MPa becomes block.
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Cited By (7)
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| CN109432514A (en) * | 2018-12-12 | 2019-03-08 | 西南大学 | Have degradable magnesium alloy bone nail and preparation method that squamous imitates bone nano-structured coating |
| CN109549762A (en) * | 2018-11-27 | 2019-04-02 | 微普安全科技（徐州）股份有限公司 | A kind of bioactive materials and its application |
| CN110241453A (en) * | 2019-04-25 | 2019-09-17 | 西南大学 | A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof |
| CN110433338A (en) * | 2019-08-13 | 2019-11-12 | 浙江理工大学 | A kind of preparation method of sclerous tissues' planting body coating material |
| CN111956863A (en) * | 2020-07-20 | 2020-11-20 | 广东省微生物研究所（广东省微生物分析检测中心） | Anion-cation co-doped nano calcium phosphate antibacterial material and preparation method thereof |
| CN112535763A (en) * | 2019-09-23 | 2021-03-23 | 天津工业大学 | Controllable fluorine slow-release hydroxyapatite porous microsphere carrier material and preparation method thereof |
| CN116196222A (en) * | 2023-02-28 | 2023-06-02 | 上海沐良医疗器械有限公司 | Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109549762A (en) * | 2018-11-27 | 2019-04-02 | 微普安全科技（徐州）股份有限公司 | A kind of bioactive materials and its application |
| CN109432514A (en) * | 2018-12-12 | 2019-03-08 | 西南大学 | Have degradable magnesium alloy bone nail and preparation method that squamous imitates bone nano-structured coating |
| CN110241453A (en) * | 2019-04-25 | 2019-09-17 | 西南大学 | A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof |
| CN110433338A (en) * | 2019-08-13 | 2019-11-12 | 浙江理工大学 | A kind of preparation method of sclerous tissues' planting body coating material |
| CN112535763A (en) * | 2019-09-23 | 2021-03-23 | 天津工业大学 | Controllable fluorine slow-release hydroxyapatite porous microsphere carrier material and preparation method thereof |
| CN111956863A (en) * | 2020-07-20 | 2020-11-20 | 广东省微生物研究所（广东省微生物分析检测中心） | Anion-cation co-doped nano calcium phosphate antibacterial material and preparation method thereof |
| CN116196222A (en) * | 2023-02-28 | 2023-06-02 | 上海沐良医疗器械有限公司 | Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance |
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|---|---|
| CN105748510B (en) | 2018-10-30 |
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