CN101856310A - Composition for treating dental caries and method for preparing fluorapatite by using same - Google Patents
Composition for treating dental caries and method for preparing fluorapatite by using same Download PDFInfo
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- CN101856310A CN101856310A CN201010213917A CN201010213917A CN101856310A CN 101856310 A CN101856310 A CN 101856310A CN 201010213917 A CN201010213917 A CN 201010213917A CN 201010213917 A CN201010213917 A CN 201010213917A CN 101856310 A CN101856310 A CN 101856310A
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- enamel
- apatite
- dental caries
- fluor
- ammonium fluoride
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Abstract
The invention discloses a composition for treating dental caries, and belongs to the field of biological materials for dental repair. Tetracalcium phosphate, ammonium fluoride and aqueous solution of phosphoric acid are blended to form sludge, the sludge is filled to surfaces of teeth with deep caries and small holes and is cured for 1 to 3 days under the condition of the physiological environment of human bodies to form fluorapatite, so that the coloboma of carious enamel and particularly the large coloboma of the enamel (the deep caries) are repaired. The synthetic fluorapatite and the enamel have the similar chemical components, so the repair materials can be combined with natural enamel directly. The synthetic fluorapatite has a stoichiometric apatite structure, has the high chemical stability (low dissolubility) under the condition of physiological body fluid of the human bodies and releases fluorine slowly under the condition of acidity (during the existence of bacteria), and thus the materials can repair the deep caries and have the effect of caries prevention.
Description
Technical field
The invention belongs to the technical field of biological material that dental prosthetic is used, be specifically related to a kind of medical material that is used for the bad enamel defect repair of dental caries.
Background technology
Dental caries (dental caries) is that a kind of hard tooth tissue that is caused by multiple factor compound action in the oral cavity carries out the sexually transmitted disease (STD) damage, is the main commonly encountered diseases in oral cavity, is characterized in the sickness rate height, and it is wide to distribute.World Health Organization (WHO) is listed as human three big keypoint control diseases with itself and cancerous protuberance and cardiovascular disease.According to national oral epidemiology survey data report, China resident dental caries prevalence is 50%, deciduous teeth caries prevalence rate 80%.Add up according to investigations, the dental caries sum of China is up to more than 2,000,000,000, and all not receiving treatment more than 90% in these dental caries.The recent survey data of the U.S. estimates, nearly 80% child and 90% adult once were subjected to the puzzlement of dental caries.Along with economic development, living condition's continuous improvement, very big change has also taken place in modern's dietary structure, and dietary intake is meticulous sticking soft and sugar content is too high, causes dental caries to take place easily.Dental caries has become popular the widest bacterial infection disease, and people's oral health in serious threat.Tissue of tooth is damaged to influence chewing of oral cavity, and functions such as language also have a strong impact on attractive in appearance when betiding labial teeth.
Microorganism in the oral cavity (as Streptococcus mutans) forms dental plaque at enamel surface, by produce acid, to enamel process such as acid etching, demineralization repeatedly, cause enamel to destroy, and then destroy dentin.Clinically often according to bad degree of dental caries be divided into shallow, in, dark dental caries three phases.Shallow dental caries, dental caries are bad only to be confined to enamel, does not have obvious cavity.Middle dental caries: dental caries are bad to have reached the dentin shallow-layer, and obvious cavity is arranged.Dark dental caries: dental caries are bad to have reached the dentin deep layer, shows as big and dark cavity, or goes into young and deep layer has comparatively widely and destroys.Dental caries can cause enamel/essential irreversible destruction, causes tooth body afunction, also can cause dental pulp and disease of periapical tissues of tooth.The purpose of dental caries treatment is to stop pathological process, the intrinsic form and the function that stop it to continue development and recover tooth.Bad for the dental caries that taken place; the clinicist still also uses the bad tissue of tooth of traumatic worn dental caries (comprising enamel or and essence) at present; and with dental prosthetic material (as resin; metal or ceramic material) filling reparation (See Figure); these methods can not be recovered the prototype structure of dental tissue, and existence may take place, and recurrent caries is gone bad and the potential problems of infringement tooth body biomechanical property.In the generation of enamel aspect blocking-up dental caries and in the bad treatment that gives atraumatic in early days of enamel caries, can stop the dental caries development and the more havoc that causes.Because tooth structure is special, though the remineralization ability is arranged, to the damaged nothing of substance self repair ability.Therefore, to forming substantive damaged tooth, plombage is an at present most widely used general and effect method preferably, adopts plombage, inlay or artificial crown repairing and treating according to scope/volume of tooth defect, can recover the form and the function of tooth body.Bad to the dental caries that taken place; even very small dental caries are bad; the clinicist still uses the bad tissue of tooth of traumatic worn dental caries (comprising enamel or and essence) at present; the nest hole of preparation suitable shape; with the dental prosthetic material such as the resin of biologically inert, or repair with dental metal such as silver amalgam or ceramic material filling.This reparation means short-term still can play the good result of recovering tissue of tooth profile and function, but because the contraction of material is aging, often has long term recurrent caries to take place, perhaps the obturator breaking releasing.Yet to still should not being equipped with in early days the enamel caries in hole, or some dental caries that can't obtain drag or maintenance decrease, and should not carry out filling with above-mentioned material.
People such as Heneh have at first found the existence of fluor-apatite in tooth.Fluor-apatite has identical crystal structure with hydroxyapatite, just F
-Replaced the OH position.The electronegativity of known fluorine is 4, is the chemical element of electronegativity maximum, therefore, and F in the fluor-apatite
-With the bond strength of Ca OH in the hydroxyapatite
-With the bond strength of Ca, this is the stable one of the main reasons of fluor-apatite.Change owing to form to go up, the performance of respective material is also changed to some extent, the biomaterial scientist pays much attention to this both at home and abroad, and carried out comparatively deep research, because F is littler than OH group, make fluor-apatite tightr than hydroxyapatite crystal structure, therefore corresponding fluor-apatite lattice paprmeter is littler than hydroxyapatite.Because structure is tightr, makes the dissolubility of fluor-apatite less.This characteristic is very significant in clinical practice, and fluor-apatite can be used as bone and tooth replacement material.The load-bearing lotus structure hard tissue substituting material of fluor-apatite as Nondegradable, particularly when the fluor-apatite pottery uses as dental material, the Trace Fluoride ion can stimulate the growth of bone, can resist the erosion of body fluid, mouthful liquid again to material, thereby shorten the time of knitting, demonstrate the superiority of fluor-apatite biomaterial.
Summary of the invention
The object of the present invention is to provide the bad enamel impairment renovation material of a kind of dental caries, can on the thronely generate (the damaged place of bad enamel of dental caries), thereby it is damaged to repair bad enamel of dental caries, the reparation of particularly damaged greatly (dark dental caries).
The invention provides the adamantine compositions of a kind of repair deficiency, for tetracalcium phosphate, ammonium fluoride and phosphate aqueous solution mix, wherein:
1, the mole proportioning of tetracalcium phosphate and phosphoric acid is 5: 2.
2, the ratio of tetracalcium phosphate and ammonium fluoride mol ratio is 1: 1.
3, the percent concentration of phosphoric acid solution is 40~70%.
The present invention also provides a kind of preparation method of fluor-apatite, it is characterized in that, tetracalcium phosphate and ammonium fluoride are mixed, add phosphate aqueous solution then, form cement slurry by being in harmonious proportion, then at 35~38 ℃, 100% damp condition solidifies down, finally generates fluor-apatite.
Another preparation method of fluor-apatite of the present invention, it is characterized in that, with tetracalcium phosphate and phosphate aqueous solution, form firming body by hydration reaction, this firming body is clayed into power, this powder and ammonium fluoride, water are reconciled into cement-like material, then at 35~38 ℃, 100% damp condition solidifies down, finally generates fluor-apatite.
The ratio of tetracalcium phosphate and ammonium fluoride mol ratio is 1: 1, adds 1~4 gram tetracalcium phosphate in every milliliter of phosphate aqueous solution.
The equation of fluor-apatite hydration reaction:
Tetracalcium phosphate+phosphoric acid+ammonium fluoride-----fluor-apatite
5Ca
4(PO
4)
2O+2H
3PO
4+4NH
4F-----2Ca
10(PO
4)
6F
2
The present invention tetracalcium phosphate (Ca
4(PO
4)
2O), phosphoric acid (H
3PO
4) cement-like material that forms of aqueous solution and ammonium fluoride is filled into the dental surface and the duck eye of dark dental caries, after solidifying 1~3 day under the Human Physiology environmental condition, generate fluor-apatite, thereby repair dark dental caries.
The firming body of the bad enamel impairment renovation material of dental caries of the present invention forms closely with former enamel and combines, and promptly fluor-apatite of Sheng Chenging and enamel defect surfaces form combination closely.
Advantage of the present invention is:
Because the fluor-apatite and the enamel of preparation have similar chemical composition, therefore, repair materials can form direct combination with Natural tooth Enamel.The powder of material and water mix the formation cement-like material, hydration reaction by material, the final fluor-apatite that generates, the material of cement shape has certain viscosity, can also some chemical reactions take place with enamel surface, so just can fill and repair dark dental caries at the controlled fluor-apatite of the direct composite structure of enamel defect surfaces.In addition, the fluor-apatite of the present invention's preparation has stoichiometric apatite structure, under human physiology body fluid condition, have very high chemical stability (dissolubility is very low), and under acid condition (antibacterial exist in) slow releasing fluoride ion, thereby have the usefulness of preventing decayed tooth.By to fluor-apatite controlledly synthesis in (the damaged hole of tooth) at the damaged place of enamel, be expected to realize the direct regeneration of fluor-apatite on the human enamel surface, this will be a kind of brand-new enamel recovery scenario, will have revolutionary meaning to oral cavity health and regenerative medicine treatment.
Description of drawings
Fig. 1 is the XRD figure of synthetic fluor-apatite;
Fig. 2 is the IR collection of illustrative plates of synthetic fluor-apatite;
Fig. 3 is the EDS figure of synthetic fluor-apatite;
Fig. 4 is the SEM photo of synthetic fluor-apatite;
Fig. 5 fluor-apatite is repaired the photo of depth of threat dental caries, and wherein (a) is not preprosthetic photo; (b) for being filled with the photo of repair materials;
Fig. 6 is that synthetic fluor-apatite is repaired the damaged SEM photo of bad enamel of dental caries, and arrow is fluor-apatite and adamantine interface.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is further described by embodiment.
Example 1
With 1.33 gram tetracalcium phosphates and 0.16 gram ammonium fluoride uniform mixing, in mixture, add 0.196 gram phosphoric acid and 4mL water again, with key uniform mixing in the mediation dish, reconcile into cement slurry, place it in 37 ℃, in 100% humidity environment 3 days, the material XRD that obtains, IR and EDS characterize its chemical constitution and composition, and its result as shown in Figure 1-Figure 3.From XRD figure spectrum as can be seen: the product of preparation is in 2 θ=26 °, 2 θ=32 °, and 2 θ=34 °, all there is its characteristic peak 2 θ=40 ° near 2 θ=47 °, 2 θ=50 °.The result shows: synthetic product is a fluor-apatite.From the IR collection of illustrative plates as can be seen: at 1070cm
-1And 950cm
-1The place is PO
4 3-Absworption peak.1432 and 1750.8cm
-1Two absworption peaks at place and from 2800cm
-1To 3472cm
-1Between absworption peak be the hydroxyl absworption peak of water.The vibration peak of the P-O-H key of apatite is at 877.7cm
1-The place occurs.The EDS collection of illustrative plates shows: synthetic product comprises calcium, phosphorus and fluorine element, and quantitatively atomic molar than result of calculation is: calcium phosphorus atoms mol ratio is 1.67, calcium fluorine atom mol ratio 2, and this illustrates that also the product of generation is a fluor-apatite.
Example 2
With 2.66 gram tetracalcium phosphates and 0.16 gram ammonium fluoride uniform mixing; in mixture, add 0.196 gram phosphoric acid and 4mL water again; with key uniform mixing in the mediation dish; reconcile into cement slurry; it is inserted the damaged place of bad enamel of dental caries; tooth is placed on 37 ℃, in 100% humidity environment 3 days, obtains laboratory sample.With the microstructure on SEM exosyndrome material surface, as shown in Figure 4.From this SEM photo as seen, fluor-apatite and enamel have formed combination closely, do not have obvious gaps on the interface, and this also can show: the repair materials fluor-apatite has similar composition with enamel, makes them be easy to combine.Synthetic fluor-apatite is the needle bar shape crystal, closely combines.Material is cut open from the material center together with tooth, observed material and the bonded interface conditions of enamel defect surfaces, as shown in Figure 6.
Example 3
With 13.3 gram tetracalcium phosphates and 1.6 gram ammonium fluoride uniform mixing; in mixture, add 1.96 gram phosphoric acid and 6mL water again; with key uniform mixing in the mediation dish; reconcile into cement slurry with key; it is inserted the damaged place of bad enamel of dental caries; tooth is placed on 35~38 ℃, in 100% humidity environment 3 days, obtains fluor-apatite.
Example 4
With 2.66 gram tetracalcium phosphates and 0.196 gram phosphoric acid and 4mL water uniform mixing, reconcile into cement slurry with key, place it in 37 ℃, in 100% humidity environment 3 days, obtain firming body, it is clayed into power, add 0.16 gram ammonium fluoride uniform mixing, add 4mL water uniform mixing again.Reconcile into cement slurry with key, place it in 35~38 ℃, in 100% humidity environment 3 days, obtain fluor-apatite.
Example 5
With 1.33 gram tetracalcium phosphates and 0.098 gram phosphoric acid and 2mL water uniform mixing, reconcile into cement slurry with key, place it in 37 ℃, in 100% humidity environment 3 days, obtain firming body, it is clayed into power, add 0.08 gram ammonium fluoride uniform mixing, add 2mL water uniform mixing again.Reconcile into cement slurry with key, it is inserted the damaged place of bad enamel of dental caries, tooth is placed on 35~38 ℃, in 100% humidity environment 3 days, obtain fluor-apatite.
The purpose of the embodiment of the invention is to help further to understand the present invention, but it will be appreciated by those skilled in the art that: without departing from the spirit and scope of the invention and the appended claims, various substitutions and modifications all are possible.Therefore, the present invention should not be limited to the disclosed content of embodiment, and the scope of protection of present invention is as the criterion with the scope that claims define.
Claims (10)
1. a compositions for the treatment of dental caries is characterized in that, is the mixing of tetracalcium phosphate, ammonium fluoride and phosphate aqueous solution.
2. compositions as claimed in claim 1 is characterized in that, the mole proportioning of tetracalcium phosphate and phosphoric acid is 5: 2.
3. compositions as claimed in claim 2 is characterized in that, the consumption of tetracalcium phosphate and ammonium fluoride such as is at the mole proportioning.
4. compositions as claimed in claim 3 is characterized in that, the percent concentration of phosphoric acid solution is 40~70%.
5. the preparation method of a fluor-apatite, it is characterized in that, tetracalcium phosphate and ammonium fluoride are mixed, add phosphate aqueous solution then, wherein, the mole proportioning of tetracalcium phosphate and phosphoric acid is 5: 2, mole proportionings such as the consumption of tetracalcium phosphate and ammonium fluoride is are behind mediation formation cement slurry, at 35~38 ℃, under 100% humidity environment, solidified 1-3 days.
6. method as claimed in claim 5 is characterized in that, the percent concentration of phosphoric acid solution is 40~70%.
7. the preparation method of a fluor-apatite, it is characterized in that, with tetracalcium phosphate and phosphate aqueous solution, form firming body by hydration reaction, subsequently this firming body is clayed into power, above-mentioned powder and ammonium fluoride, water are reconciled into cement-like material, at 35~38 ℃, under 100% humidity environment, solidified 1-3 days.
8. method as claimed in claim 7 is characterized in that the concentration of phosphate aqueous solution is 40~70%, adds 1~4 gram tetracalcium phosphate in every milliliter of phosphate aqueous solution, and the cement-like material after the mediation is at 35~38 ℃, and 100% damp condition solidified 1~3 day down.
9. method as claimed in claim 8 is characterized in that, tetracalcium phosphate and ammonium fluoride mol ratio are 1: 1.
10. the application of compositions in the bad enamel defect repair of dental caries medical material according to claim 1.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN201010213917A CN101856310A (en) | 2010-06-30 | 2010-06-30 | Composition for treating dental caries and method for preparing fluorapatite by using same |
US13/256,617 US9090471B2 (en) | 2010-06-22 | 2010-09-02 | Method for producing fluorapatite and its application |
PCT/CN2010/001336 WO2011160265A1 (en) | 2010-06-22 | 2010-09-02 | Preparation method and application of fluorapatite |
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CN201010213917A CN101856310A (en) | 2010-06-30 | 2010-06-30 | Composition for treating dental caries and method for preparing fluorapatite by using same |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2452462C1 (en) * | 2011-04-06 | 2012-06-10 | Сергей Владимирович Сирак | Combined medicated paste for deep caries |
CN102961259A (en) * | 2012-12-12 | 2013-03-13 | 郑荣荣 | Hard coating material used for dental restoration and preparation method thereof |
CN105254333A (en) * | 2015-09-30 | 2016-01-20 | 杨富巍 | Stone cultural relic reinforcement and protection method based on fluorapatite materials |
CN106806152A (en) * | 2017-01-22 | 2017-06-09 | 桂林碳谷科技有限公司 | A kind of biological preventing decayed tooth teeth repairing material and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59122411A (en) * | 1982-12-29 | 1984-07-14 | Tokuyama Soda Co Ltd | Dental cement composition |
JPH06321515A (en) * | 1993-05-18 | 1994-11-22 | Osaka Cement Co Ltd | High-strength hardenable material |
-
2010
- 2010-06-30 CN CN201010213917A patent/CN101856310A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59122411A (en) * | 1982-12-29 | 1984-07-14 | Tokuyama Soda Co Ltd | Dental cement composition |
JPH06321515A (en) * | 1993-05-18 | 1994-11-22 | Osaka Cement Co Ltd | High-strength hardenable material |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2452462C1 (en) * | 2011-04-06 | 2012-06-10 | Сергей Владимирович Сирак | Combined medicated paste for deep caries |
CN102961259A (en) * | 2012-12-12 | 2013-03-13 | 郑荣荣 | Hard coating material used for dental restoration and preparation method thereof |
CN105254333A (en) * | 2015-09-30 | 2016-01-20 | 杨富巍 | Stone cultural relic reinforcement and protection method based on fluorapatite materials |
CN106806152A (en) * | 2017-01-22 | 2017-06-09 | 桂林碳谷科技有限公司 | A kind of biological preventing decayed tooth teeth repairing material and preparation method thereof |
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Open date: 20101013 |