阅读说明：本技术 一种基于生物活性玻璃/壳聚糖的复合活髓保存材料及其制备方法与应用 (It is a kind of that material and the preparation method and application thereof is saved based on the compound vital pulp of bioactivity glass/chitosan ) 是由 陈晓峰 曾诗涵 刘聪 唐凤玲 欧阳鹿 田婷 王刚 曾蕾 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种基于生物活性玻璃/壳聚糖的复合活髓保存材料及其制备方法与应用。该基于生物活性玻璃/壳聚糖的复合活髓保存材料由固体粉末和调和液两部分组成,将固体粉末与调和液分开包装,使用时进行现场调和,混合均匀后覆盖于牙髓暴露处对牙髓进行保存,固体粉末与调和液的调拌比例为1.0-2.0g/mL。其中,固体粉末为溶胶-凝胶法结合模板剂法制备的SiO-CaO-P<Sub>2</Sub>O<Sub>5</Sub>三元系统为基础的微纳米球形生物活性玻璃,调和液为壳聚糖-磷酸盐缓冲溶液。本发明的活髓保存材料可以保护牙髓免受外界环境的刺激,具有良好的生物活性。同时,本发明制备工艺与设备简单,操作简便,成本较低,易于推广,具有良好的应用前景。(Material and the preparation method and application thereof is saved based on the compound vital pulp of bioactivity glass/chitosan the invention discloses a kind of.This saves material based on the compound vital pulp of bioactivity glass/chitosan and is made of solid powder and distiller liquor two parts, solid powder is separately packed with distiller liquor, live reconciliation is carried out when use, it is covered at dental pulp exposure after mixing and dental pulp is saved, it is 1.0-2.0g/mL that the tune of solid powder and distiller liquor, which mixes ratio,.Wherein, solid powder is the SiO-CaO-P of sol-gel method combination template agent method preparation 2 O 5 Micro-nano spherical bioactivity glass based on ternary system, distiller liquor is chitosan-phosphate buffer solution.Vital pulp of the invention, which saves material, can protect dental pulp from the stimulation of external environment, have good bioactivity.Meanwhile manufacturing technique of the present invention is simple, and easy to operate, cost is relatively low, and it is easy to spread, it has a good application prospect.)

1. a kind of save material based on the compound vital pulp of bioactivity glass/chitosan, which is characterized in that by solid powder and tune It is formed with liquid two parts；The solid powder is the SiO of sol-gel method combination template agent method preparation₂-CaO-P₂O₅Ternary system Micro-nano spherical bioactivity glass based on system；The distiller liquor is chitosan-phosphate buffer solution.

2. according to claim 1 a kind of based on the compound vital pulp preservation material of bioactivity glass/chitosan, feature It is, it is 1.0-2.0g/mL that the tune of the solid powder and distiller liquor, which mixes ratio,.

3. according to claim 1 a kind of based on the compound vital pulp preservation material of bioactivity glass/chitosan, feature It is, the SiO₂-CaO-P₂O₅In micro-nano spherical bioactivity glass based on ternary system, SiO₂, CaO and P₂O₅'s Molar ratio is 60:36:4.

4. according to claim 1 a kind of based on the compound vital pulp preservation material of bioactivity glass/chitosan, feature It is, the SiO₂-CaO-P₂O₅The partial size of micro-nano spherical bioactivity glass based on ternary system is 200-800nm.

5. it is according to claim 1 a kind of based on the compound vital pulp preservation material of bioactivity glass/chitosan, it is special Sign is, in the chitosan-phosphate buffer solution, the mass-volume concentration of chitosan is 0.005-0.02mg/ml, phosphoric acid The molar concentration of salt is 1-5mol/L.

6. it is described in any item a kind of based on the compound vital pulp preservation material of bioactivity glass/chitosan to prepare claim 1-5 The method of material, which comprises the steps of:

(1) SiO₂-CaO-P₂O₅The preparation of micro-nano spherical bioactivity glass based on ternary system: template is dissolved in It in the mixed solution of second alcohol and water, stirs evenly, then sequentially adds ethyl orthosilicate, triethyl phosphate, four water-calcium nitrate, shape At milky white solution, white depositions sufficiently are obtained after reaction, is then centrifuged for, dries, being heat-treated and obtain required SiO₂-CaO- P₂O₅Micro-nano spherical bioactive glass powder based on ternary system；

(2) chitosan-phosphate buffer solution preparation: being dissolved in acetic acid for chitosan, stir to clear viscous shape solution, then plus Enter dipotassium hydrogen phosphate and sodium dihydrogen phosphate, obtains chitosan-phosphate buffer solution；

(3) bioactivity glass/chitosan vital pulp saves the preparation of material: by SiO₂-CaO-P₂O₅It is micro- based on ternary system Nanometer spherical bioactive glass powder is separately packed with chitosan-phosphate buffer solution, and it is equal that scene mixing is carried out when use It is even, it obtains and material is saved based on the compound vital pulp of bioactivity glass/chitosan.

7. preparation method as claimed in claim 6, which is characterized in that in step (1), the template is lauryl amine, the second Volume ratio of the alcohol and water in mixed solution is 3-6: 1, and entire reaction process takes heating water bath, and reaction temperature is controlled in 30- 50℃。

8. preparation method as claimed in claim 6, which is characterized in that in step (1), be added ethyl orthosilicate, triethyl phosphate, The time interval of four water-calcium nitrate is 20-40min；Standing obtained white depositions drying condition is 50-80 DEG C of dry 24- 36h；The heat treatment is 600-700 DEG C of processing 3-4h.

9. claim 1-5 is described in any item a kind of to save material based on the compound vital pulp of bioactivity glass/chitosan Using, which is characterized in that the material is used as pulp-cap.

10. application according to claim 9, which is characterized in that in use, solid powder and distiller liquor are carried out live tune Be covered at dental pulp exposure after mixing and dental pulp protected.

Technical field

The invention belongs to vital pulps to save Material Field, and in particular to a kind of compound based on bioactivity glass/chitosan Vital pulp saves material and the preparation method and application thereof.

Background technique

Dental pulp is unique soft tissue in tooth, the nutrition being responsible for needed for providing to pulp cells, odontoblast etc. And oxygen, while it can constantly form dentine.In daily life, since the factors such as wound, saprodontia, operation can all lead to tooth Marrow exposure, because dental pulp is non-renewable, vital pulp preservation is the treatment optimal means of dental pulp exposure.At present clinically most often Lid marrow material has calcium hydroxide, mineral trioxide aggregate, but due to the deficiency that it is individually present, can't fully meet Ideal vital pulp saves the requirement of material.

Calcium hydroxide has been widely used in clinically, but its there is also some side effects.Calcium hydroxide is a kind of highly basic Property material, when it is directly contacted with dental pulp surface, can make contact site pH increase, cause dental pulp to generate due to strong basicity Inflammatory reaction even leads to pulp necrosis, has biggish toxicity for cell.Meanwhile for the dental pulp with inflammation There is no antiinflammation.

Mineral trioxide aggregate largely applies to vital pulp preservation in recent years, but its operability is poor, setting time is up to 4h, This considerably increases the time costs of doctor and patient；And it is expensive, limit its use scope；In addition, three oxide minerals Condensate can not degrade, and belong to nondegradable alternative material, cannot carry out in-situ immobilization to lid marrow position.

Bioactivity glass has controllable pattern and structure, can pass through change preparation process and the content of each component It is adjusted, meet different clinical requirements.In addition, bioactivity glass has good bioactivity, in body fluid A large amount of ion can be released stimulate cell certain specific genes expression to control the behavior of cell.Bio-vitric The alkalinity of grain is smaller than calcium hydroxide lid marrow material more, thus directly contact dental pulp when will not generate stimulation pulp tissue and cause The situation of pulp inflammation even pulp tissue's necrosis.Bioactivity glass also has good biocompatibility and mineralising shape At the ability of hydroxyapatite, be conducive to accelerate to form reparative dentin.

There is research to treat bioactivity glass applied to lid marrow in recent years, as passed through in patent application CN104644455A Change glass ingredient to adjust the physical and chemical performance of material.But the glass prepared in the patent application is not that general ingredient contains Amount, and its design component differs larger with real composition, and component is unstable, is not suitable for clinical expansion, therefore the present invention is with logical Material is saved with vital pulp based on the micro-nano spherical glass of component and stable components, is prepared for.

Summary of the invention

The purpose of the present invention is saving condensation of materials time long deficiency for existing vital pulp, provide a kind of based on biology The compound vital pulp of activity glass/chitosan saves material and the preparation method and application thereof, when which condenses when being used as pulp-cap Between it is short, have good biocompatibility and induced synthesis reparative dentin layer ability, tissue repair can be promoted.Together When, manufacturing technique of the present invention is simple, and easy to operate, cost is relatively low, and it is easy to spread, it has a good application prospect.

To achieve the goals above, the present invention is realized at least through one of following technical scheme.

It is a kind of that material is saved based on the compound vital pulp of bioactivity glass/chitosan, by solid powder and distiller liquor two It is grouped as；The solid powder is the SiO of sol-gel method combination template agent method preparation₂-CaO-P₂O₅Based on ternary system Micro-nano spherical bioactivity glass；The distiller liquor is chitosan-phosphate buffer solution.

Further, it is 1.0-2.0g/mL that the tune of the solid powder and distiller liquor, which mixes ratio,.

Further, the SiO₂-CaO-P₂O₅In micro-nano spherical bioactivity glass based on ternary system, SiO₂, CaO and P₂O₅Molar ratio be 60:36:4.

Further, the SiO₂-CaO-P₂O₅The partial size of micro-nano spherical bioactivity glass based on ternary system For 200-800nm.

Further, in the chitosan-phosphate buffer solution, the mass-volume concentration of chitosan is 0.005- 0.02mg/ml, phosphatic molar concentration are 1-5mol/L.

A kind of above-described preparation method that material is saved based on the compound vital pulp of bioactivity glass/chitosan, packet Include following steps:

(1) SiO₂-CaO-P₂O₅The preparation of micro-nano spherical bioactivity glass based on ternary system: template is dissolved in It in the mixed solution of second alcohol and water, stirs evenly, then sequentially adds ethyl orthosilicate, triethyl phosphate, four water-calcium nitrate, shape At milky white solution, white depositions sufficiently are obtained after reaction, is then centrifuged for, dries, being heat-treated and obtain required SiO₂-CaO- P₂O₅Micro-nano spherical bioactive glass powder based on ternary system；

(2) chitosan-phosphate buffer solution preparation: being dissolved in acetic acid for chitosan, stir to clear viscous shape solution, then plus Enter dipotassium hydrogen phosphate and sodium dihydrogen phosphate, obtains chitosan-phosphate buffer solution；

(3) bioactivity glass/chitosan vital pulp saves the preparation of material: by SiO₂-CaO-P₂O₅It is micro- based on ternary system Nanometer spherical bioactive glass powder is separately packed with chitosan-phosphate buffer solution, and it is equal that scene mixing is carried out when use Even, gained paste obtains saving material based on the compound vital pulp of bioactivity glass/chitosan after solidifying.

Further, in step (1), the template is lauryl amine.

Further, in step (1), its volume ratio is 3-6: 1 in the mixed solution of the ethyl alcohol and deionized water.

Further, in step (1), entire reaction process takes heating water bath, and reaction temperature is controlled at 30-50 DEG C.

Further, in step (1), be added ethyl orthosilicate, triethyl phosphate, four water-calcium nitrate time interval be 20-40min。

Further, in step (1), the white depositions drying condition stood is 50-80 DEG C of dry 24-36 h.

Further, in step (1), the heat treatment is 600-700 DEG C of processing 3-4 h.

A kind of above-described application that material is saved based on the compound vital pulp of bioactivity glass/chitosan, feature It is, which is used as pulp-cap.

Further, in use, solid powder and distiller liquor are carried out live reconciliation, it is sudden and violent that it is covered in dental pulp after mixing Dental pulp is protected at dew.

The solidification for the paste that the composite material tune mixes acquisition is related to bioactivity glass, phosphate and chitosan three Between interaction.Therefore, can be by changing solid-to-liquid ratio, each component concentration etc. adjusts every object of composite material in distiller liquor Change performance.Bio-vitric can be quickly generated a large amount of hydroxyapatite in phosphate solution between glass particle, secondly its meeting So that solution alkaline causes the gelation of chitosan, while having the combination of chemical bond between chitosan and hydroxyapatite, with The collective effect of upper reaction results in the solidification of material.

Compared with prior art, the invention has the advantages that and effect:

(1) solid powder chosen of the present invention is bioactivity glass, have good bioactivity and biocompatibility and Mineralising formed hydroxyapatite ability, in fluid environment can also by the release of ion, promote pulp cells at Dentin cell's induction forms reparative dentin layer.

(2) bioactivity glass and chitosan can be degradable in human body fluid, to form biological tissue In-situ immobilization.

(3) when saving condensation of the material as pulp-cap the present invention is based on the compound vital pulp of bioactivity glass/chitosan Between it is short, reduce the time cost of doctor and patient.

(4) manufacturing technique of the present invention is simple, easy to operate, and cost is relatively low, easy to spread, has good application Prospect.

Detailed description of the invention

Fig. 1 is in embodiment 1 using the micro-nano bioactivity glass microballoon of template combination sol-gel method preparation Tungsten filament scanning electron microscope (SEM) photograph.

Fig. 2 a is respectively obtained based on the compound vital pulp preservation of bioactivity glass/chitosan in the embodiment of the present invention 2 Material conserves the tungsten filament scanning electron microscope (SEM) photograph of 3 d rear surface microstructures.

Fig. 2 b, Fig. 2 c are respectively obtained based on the compound vital pulp of bioactivity glass/chitosan in the embodiment of the present invention 2 It saves material and conserves X ray diffracting spectrum and FTIR spectrum figure after 3 d.

Fig. 3 is obtained feeding based on the compound vital pulp preservation material of bioactivity glass/chitosan in the embodiment of the present invention 2 It protects after 3 d and is immersed in the tungsten filament scanning electron microscope (SEM) photograph of material surface microstructure after 1 day in simulated body fluid.

Fig. 4 is obtained feeding based on the compound vital pulp preservation material of bioactivity glass/chitosan in the embodiment of the present invention 2 It protects after 3 d and is immersed in the tungsten filament scanning electron microscope (SEM) photograph of material surface microstructure after 7 days in simulated body fluid.

Specific embodiment

Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention

It is without being limited thereto, for not specifically specified technological parameter, it can refer to routine techniques progress.