CN101843560A - Combination for repairing dental enamel and method for preparing fluorapatite by using the same - Google Patents

Combination for repairing dental enamel and method for preparing fluorapatite by using the same Download PDF

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Publication number
CN101843560A
CN101843560A CN201010205839A CN201010205839A CN101843560A CN 101843560 A CN101843560 A CN 101843560A CN 201010205839 A CN201010205839 A CN 201010205839A CN 201010205839 A CN201010205839 A CN 201010205839A CN 101843560 A CN101843560 A CN 101843560A
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China
Prior art keywords
enamel
sodium fluoride
dental
apatite
phosphate
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CN201010205839A
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Chinese (zh)
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魏世成
魏杰
刘晓晨
王成洁
张翼飞
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Peking University
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Peking University
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Priority to CN201010205839A priority Critical patent/CN101843560A/en
Priority to PCT/CN2010/001336 priority patent/WO2011160265A1/en
Priority to US13/256,617 priority patent/US9090471B2/en
Publication of CN101843560A publication Critical patent/CN101843560A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a combination for repairing damaged dental enamel, belonging to the field of dental repairing biomaterials. The method comprises steps that tetracalcium phosphate, calcium hydrophosphate and sodium fluoride are mixed, water is added for blending to form cement-like substances, the cement-like substances are filled in carious cavities of carious teeth with damaged enamel, the cement-like substances are cured for 1-3 days under a human body physiological environment to generate fluorapatite, and thereby the carious damaged enamel, especially large damaged enamel (deep caries) can be repaired. Since the synthesized fluorapatite has chemical components similar to the chemical components of the dental enamel, repairing materials can be directly combined with natural dental enamel. The synthesized fluorapatite has a stoichiometric phosphorite structure, the chemical stability under the condition of human physiological body liquid is very high (i.e. the dissolubility is low), fluorions are slowly released under the acidic condition (the existence of bacteria), and thereby the anticarious efficacy is obtained.

Description

The compositions of repairing dental enamel and prepare the method for fluor-apatite with said composition
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, aging often has recurrent caries to take place, perhaps the obturator breaking releasing long term.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, and just F-has replaced the OH position.The electronegativity of known fluorine is 4, is the chemical element of electronegativity maximum, therefore, the bond strength of the bond strength of F-and Ca OH-and Ca in the hydroxyapatite in the fluor-apatite, 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, saliva 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 generate (the damaged place of bad enamel of dental caries) in position, 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, be tetracalcium phosphate, calcium hydrogen phosphate, sodium fluoride and water, wherein:
1, the consumption of tetracalcium phosphate and calcium hydrogen phosphate such as is at the mole proportioning.
2, the mol ratio of tetracalcium phosphate and sodium fluoride is 1: 1.
3, the ratio of tetracalcium phosphate+calcium hydrogen phosphate+sodium fluoride mixed-powder and water is 1~4 (g/mL).
The present invention also provides a kind of preparation method of fluor-apatite, it is characterized in that, tetracalcium phosphate, calcium hydrogen phosphate and sodium fluoride is mixed, and add entry, is in harmonious proportion and forms cement-like material, at 35~38 ℃, under 100% humidity environment, solidifies 1-3 days.
The equation of fluor-apatite hydration reaction:
Tetracalcium phosphate+calcium hydrogen phosphate+sodium fluoride------fluor-apatite
2Ca 4(PO 4) 2O+2CaHPO 4+2NaF-----Ca10(PO 4) 6F 2
With particle diameter is that tetracalcium phosphate and the particle diameter of 1~20 μ m is 1~20 μ m calcium hydrogen phosphate, by star ball mill uniform mixing, mixes with sodium fluoride again, adds entry then.The cement-like material that forms is filled in the damaged cavity of bad enamel of dental caries, after solidifying 1~3 day under the Human Physiology environmental condition, generates fluor-apatite, thereby repair the bad enamel tissue defect that causes of dental caries.
With reference to figure 5; the present invention's (tetracalcium phosphate+calcium hydrogen phosphate+sodium fluoride) mixed-powder and water are in harmonious proportion; form cement-like material as the bad enamel impairment renovation material of dental caries; it is inserted the damaged place of bad enamel of dental caries; its firming body 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 and form cement-like material, by the hydration reaction of material, finally generate fluor-apatite, so just can be at the controlled fluor-apatite of the direct composite structure of enamel defect surfaces, and it is damaged to repair the enamel that dark dental caries cause.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 controlledly synthesis to fluor-apatite, be expected to realize the direct regeneration of fluor-apatite on the human enamel surface, this will be a kind of brand-new hard tissue repair scheme, 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, is the photo that is filled with repair materials for not preprosthetic photo (b) (a).
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 2.66 gram tetracalcium phosphates and 1.36 gram calcium hydrogen phosphate powder uniform mixing, in mixed-powder, add 0.4 gram sodium fluoride again, uniform mixing in the mediation dish, the mixed-powder of three kinds of materials adds 4mL water, reconcile into cement slurry with key, further reconcile into colloid substance, place it in 37 ℃, in 100% humidity environment 3 days, the material that obtains is a fluor-apatite, use XRD, 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 1.33 gram tetracalcium phosphates and 0.68 gram calcium hydrogen phosphate powder uniform mixing; in mixed-powder, add 0.2 gram sodium fluoride again; uniform mixing in the mediation dish; the mixed-powder of three kinds of materials adds 2mL water, reconciles into cement slurry with key, further reconciles into colloid substance; 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 26.6 gram tetracalcium phosphates and 13.6 gram calcium hydrogen phosphate powder star ball mill uniform mixing; 4 gram sodium fluoride are added in the entry; form its solution; tetracalcium phosphate and calcium hydrogen phosphate mixed-powder are added 40mL water, reconcile into cement slurry, further reconcile into colloid substance 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 laboratory sample.
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 (8)

1. the compositions of a repairing dental enamel is characterized in that, is the mixing of tetracalcium phosphate, calcium hydrogen phosphate, sodium fluoride and water.
2. compositions as claimed in claim 1 is characterized in that, the consumption of tetracalcium phosphate and calcium hydrogen phosphate such as is at the mole proportioning.
3. compositions as claimed in claim 2 is characterized in that, the consumption of tetracalcium phosphate and sodium fluoride such as is at the mole proportioning.
4. compositions as claimed in claim 3 is characterized in that, the ratio of tetracalcium phosphate, calcium hydrogen phosphate and sodium fluoride mixed-powder and water is 1~4 (g/mL).
5. the preparation method of a fluor-apatite, it is characterized in that, tetracalcium phosphate, calcium hydrogen phosphate and sodium fluoride are mixed, wherein, the consumption of tetracalcium phosphate, calcium hydrogen phosphate and sodium fluoride such as is at the mole proportioning, adds entry, be in harmonious proportion and form cement-like material, at 35~38 ℃, under 100% humidity environment, solidified 1-3 days.
6. method as claimed in claim 5 is characterized in that, is that tetracalcium phosphate and the particle diameter of 1~20 μ m is 1~20 μ m calcium hydrogen phosphate with particle diameter, behind star ball mill uniform mixing, mixes with sodium fluoride again, adds entry then.
7. method as claimed in claim 6 is characterized in that, the ratio of tetracalcium phosphate, calcium hydrogen phosphate and sodium fluoride mixed-powder and water is 1~4 (g/mL).
8. the application of compositions in the bad enamel defect repair of dental caries medical material according to claim 1.
CN201010205839A 2010-06-22 2010-06-22 Combination for repairing dental enamel and method for preparing fluorapatite by using the same Pending CN101843560A (en)

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CN201010205839A CN101843560A (en) 2010-06-22 2010-06-22 Combination for repairing dental enamel and method for preparing fluorapatite by using the same
PCT/CN2010/001336 WO2011160265A1 (en) 2010-06-22 2010-09-02 Preparation method and application of fluorapatite
US13/256,617 US9090471B2 (en) 2010-06-22 2010-09-02 Method for producing fluorapatite and its application

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102961259A (en) * 2012-12-12 2013-03-13 郑荣荣 Hard coating material used for dental restoration and preparation method thereof
CN104016397A (en) * 2013-03-01 2014-09-03 中国科学院宁波材料技术与工程研究所 Preparation methods for fluorine-containing alpha-calcium sulfate hemihydrate powder and fluorine-containing calcium sulfate artificial bone material
CN112158820A (en) * 2020-09-06 2021-01-01 桂林理工大学 Preparation method and application of fluorapatite solid solution
CN115006263A (en) * 2022-06-24 2022-09-06 深圳市恒通栢能实业有限公司 Enamel repairing material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087807A (en) * 1992-12-11 1994-06-15 中南工业大学 Active fluorapatite biological ceramic and manufacture method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087807A (en) * 1992-12-11 1994-06-15 中南工业大学 Active fluorapatite biological ceramic and manufacture method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《硅酸盐通报》 20001028 曲海波等 氟磷灰石材料及其在生物医学方面的应用 , 第05期 2 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102961259A (en) * 2012-12-12 2013-03-13 郑荣荣 Hard coating material used for dental restoration and preparation method thereof
CN104016397A (en) * 2013-03-01 2014-09-03 中国科学院宁波材料技术与工程研究所 Preparation methods for fluorine-containing alpha-calcium sulfate hemihydrate powder and fluorine-containing calcium sulfate artificial bone material
CN104016397B (en) * 2013-03-01 2016-01-20 中国科学院宁波材料技术与工程研究所 The preparation method of fluorine-containing α-half-H 2 O calcium sulphate powder body and internal fixation material
CN112158820A (en) * 2020-09-06 2021-01-01 桂林理工大学 Preparation method and application of fluorapatite solid solution
CN115006263A (en) * 2022-06-24 2022-09-06 深圳市恒通栢能实业有限公司 Enamel repairing material
CN115006263B (en) * 2022-06-24 2024-03-26 深圳市恒通栢能实业有限公司 Enamel restoration material

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Application publication date: 20100929