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CN-121971317-A - Carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material and preparation method and application thereof

CN121971317ACN 121971317 ACN121971317 ACN 121971317ACN-121971317-A

Abstract

The invention relates to a carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material, a preparation method and application thereof, wherein the composite anticarious material is a composite gel system and comprises carboxymethyl chitosan, amorphous calcium phosphate and glycerin, and hydroxyapatite nanowires can be selectively added. The composite anticarious material successfully solves the problems of the prior fluoride-free remineralization material that the mineralization efficiency is to be improved, the clinical operability is poor and the like, and provides a new fluoride-free scheme which is safe, efficient and convenient to use for preventing and treating early caries.

Inventors

  • NIE HUALI
  • Guo Yingfan
  • QI YING
  • Su hongru
  • QIAO LU
  • ZHANG ZHENGHE
  • ZHANG GUORUI

Assignees

  • 东华大学
  • 上海市徐汇区口腔医院(上海市徐汇区牙病防治所)

Dates

Publication Date
20260505
Application Date
20260115

Claims (10)

  1. 1. The carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material is characterized in that the composite anticarious material is a composite gel system and comprises carboxymethyl chitosan, amorphous calcium phosphate and glycerin.
  2. 2. The carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material according to claim 1, wherein the content of carboxymethyl chitosan in the composite gel system is 1.0-10.0% and the content of amorphous calcium phosphate is 0.5-2% by mass fraction.
  3. 3. The carboxymethyl chitosan-amorphous calcium phosphate composite anticariogenic material according to claim 1, wherein the glycerol is added in an amount of 30% -70% of the total volume of the composite gel system.
  4. 4. The carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material according to claim 1, wherein the composite gel system comprises hydroxyapatite nanowires with a diameter of 10-100 nm and a length of 0.5-50 μm.
  5. 5. The carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material according to claim 4, wherein the mass ratio of the hydroxyapatite nanowire to the carboxymethyl chitosan is 1:10-1:50.
  6. 6. A method for preparing the carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material according to claim 1, comprising the following steps: (1) Dissolving carboxymethyl chitosan CMC in water, and stirring to form carboxymethyl chitosan hydrogel; (2) Sequentially adding a calcium source solution and a phosphorus source solution into the carboxymethyl chitosan hydrogel in the step (1), and stirring for reaction to form carboxymethyl chitosan-amorphous calcium phosphate CMC-ACP basic gel; (3) And (3) mixing glycerol with the CMC-ACP basic gel in the step (2) to form a composite gel system, thereby preparing the composite anticarious material.
  7. 7. The method according to claim 6, wherein the calcium source in the step (2) is at least one of calcium chloride, calcium nitrate and calcium gluconate, and the phosphorus source is at least one of dipotassium hydrogen phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the molar ratio of calcium ions to phosphate ions is in a range of 1.0:1-2.0:1.
  8. 8. The preparation method of claim 6, wherein the CMC-ACP base gel obtained in the step (2) is added with hydroxyapatite nanowires to form CMC-ACP-HAP composite gel, and then the CMC-ACP-HAP composite gel is uniformly mixed with glycerin in the step (3) to obtain the composite anticarious material.
  9. 9. Use of a carboxymethyl chitosan-amorphous calcium phosphate composite anticaries material according to claim 1, for the preparation of an oral care product that promotes remineralization of enamel, repair of early caries, or prevention of caries.
  10. 10. The use according to claim 9, wherein the application comprises directly coating the composite anticaries material onto the tooth surface, and leaving it for 1-30 minutes for removal or retention, wherein the coating means comprises brushing, dripping or syringe dispensing.

Description

Carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material and preparation method and application thereof Technical Field The invention belongs to the field of stomatology and biological materials, and particularly relates to a carboxymethyl chitosan-amorphous calcium phosphate composite anticarious material, a preparation method and application thereof. Background Caries, one of the most common chronic non-infectious diseases worldwide, especially in the childhood population, continues to climb in incidence, constituting a serious oral health challenge. It is counted that the prevalence of caries in children under 5 years old is high, but the proportion of untreated caries is particularly prominent in areas where oral care resources are relatively scarce. The primary teeth not only bear important functions such as chewing, pronunciation and the like in childhood, but also have more direct influence on the development and sprouting of subsequent permanent teeth, so that the primary teeth have important clinical significance and social value for effectively preventing and treating early caries of the primary teeth. In the occurrence and development of caries, the dynamic balance of demineralization and remineralization of enamel is broken down as a key link. Cariogenic bacteria in the oral cavity metabolize carbohydrates to produce acid, resulting in a local pH drop, and when the ambient acidity is below the critical pH of tooth enamel (deciduous tooth enamel is about 5.5), hydroxyapatite crystals in the enamel begin to dissolve, and calcium and phosphate ions are lost, forming early chalky spots and even cavities. Therefore, promoting remineralization of demineralized enamel, namely supplementing lost minerals and repairing crystal structure, is a core strategy for preventing and treating early caries and realizing minimally invasive treatment. Fluoride has long been widely used for caries prevention because of its ability to promote the formation of more stable minerals such as fluorapatite and reduce enamel solubility. Fluorine-containing toothpaste, mouthwash, professional fluorine coating and the like have become conventional clinical anticaries means. However, the use of fluoride is not without limitation. Excessive fluorine intake can lead to fluorosis, affecting tooth aesthetics, and there is also a risk of fluorosis during skeletal development. Especially for infants with imperfect swallowing control, special care is taken to use the fluorine-containing product. Furthermore, in high fluorine areas, the environmental background fluorine content has been higher and the benefit to risk ratio of additional fluorine exposure needs to be reevaluated. These factors have prompted researchers to continually explore safe and effective fluorine-free anticaries alternatives. In this context, fluorine-free remineralizing materials based on biomimetic mineralization principles have become a research hotspot. Among them, calcium phosphate materials, in particular nano amorphous calcium phosphate (Amorphous Calcium Phosphate, ACP), because of their chemical composition highly similar to enamel inorganic phase, can be used as a reservoir of calcium and phosphorus ions, release ions at the demineralized site and guide the deposition of hydroxyapatite (Hydroxyapatite, HAP), exhibiting good remineralization potential. Meanwhile, chitosan and its derivatives, particularly carboxymethyl chitosan (Carboxymethyl Chitosan, CMC), are receiving a great deal of attention in the field of stomatology due to their excellent biocompatibility, biodegradability, antibacterial activity and chelating ability for calcium ions. Functional groups such as carboxyl on CMC molecular chain can interact with ACP, hopefully stabilize ACP nano-particles, regulate ion release kinetics, and enhance the adhesiveness of materials on a moist tooth surface. Therefore, CMC and ACP are compounded to construct CMC-ACP composite material, and the advantages of the CMC-ACP composite material and the ACP composite material can be cooperatively exerted theoretically, so that more efficient and lasting enamel remineralization can be realized, and meanwhile, the potential risk of fluorine is avoided, thereby providing a promising thought for developing new-generation fluorine-free anticarious products. There have been reports in the prior art on the compounding of CMC with ACP for remineralization. For example, CMC-ACP composites were prepared by physical mixing or the like, and their remineralization effects in a model were verified. These studies initially confirm the feasibility of the application of the system. However, existing CMC-ACP composite systems still face a number of technical bottlenecks that need to be addressed. Firstly, the remineralization efficiency of a pure CMC-ACP compound is often to be improved, a new mineral layer induced by the pure CMC-ACP compound still has a gap with natural enamel in terms of structural or