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CN-121975065-A - PH responsive MOF material, composite photosensitive resin system containing same and application of composite photosensitive resin system in dental appliance

CN121975065ACN 121975065 ACN121975065 ACN 121975065ACN-121975065-A

Abstract

The invention provides a pH response type MOF material, a composite photosensitive resin system containing the same and application of the pH response type MOF material in a dental appliance, wherein the pH response type MOF material is a multifunctional metal organic framework material (Guardian-MOF) with a core-shell-satellite structure, the MOF is chemically bonded into a photo-curing resin matrix to form an intelligent composite resin capable of being printed in 3D/4D, the manufactured appliance has the required mechanical property on the macroscopic aspect to complete an orthodontic function, is a distributed and intelligent 'micro clinic' on the microscopic aspect, can accurately respond to an oral pathogenic microenvironment (low pH), and cooperatively executes multiple antibacterial and targeted remineralization treatment, and has a remarkable application prospect.

Inventors

  • LIN JINRUI
  • MENG LONG
  • QIU XIANXING
  • LI YAN

Assignees

  • 信联聚科(上海)新材料有限公司

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. The pH response type MOF material is characterized in that the material is a core-shell structure material, a core layer is iron ion and/or ferrous ion doped zirconium-based porphyrin MOF, a shell layer is poly (2-diisopropylamino ethyl methacrylate) -block-poly (ethylene glycol methyl ether methacrylate), and the material is grafted on the surface of the core layer; the iron ion and/or ferrous ion doped zirconium-based porphyrin MOF is obtained by loading PCN-224 with iron ions and/or ferrous ions, and the molar ratio of iron to zirconium is 0.05-0.5; the shell layer carries an ionic therapeutic agent within the MOF pore channel, including a compound capable of providing one or more therapeutic ions selected from at least one of silver ions, fluoride ions, calcium ions, phosphate ions, and silicate ions.
  2. 2. The pH-responsive MOF material of claim 1, wherein the iron and/or ferrous ion doped zirconium-based porphyrin MOF is synthesized from an iron source, a zirconium source, and H 2 TCPP by solvothermal method; And/or the ionic therapeutic agent is loaded in the MOF pore canal of the shell layer through vacuum diffusion after silver tetrafluoroborate and mesoporous bioactive glass nano particles are subjected to ion exchange and recombination.
  3. 3. The pH-responsive MOF material of claim 1, wherein the shell layer is grafted by: amination modification is carried out on zirconium-based porphyrin MOF doped with iron ions and/or ferrous ions to obtain a modified nuclear layer material; taking nuclear layer material and RAFT reagent to perform condensation reaction under the action of condensing agent and catalyst to obtain intermediate with RAFT initiation point immobilized on surface; And grafting the intermediate and a monomer through a RAFT polymerization reaction to obtain a grafted core-shell structure material, wherein the monomer is 2-diisopropylamino ethyl methacrylate and ethylene glycol methyl ether methacrylate.
  4. 4. The pH-responsive MOF material according to claim 3, wherein the amination modification process is carried out by dispersing iron ion and/or ferrous ion doped zirconium-based porphyrin MOF, adding an amino-containing silane coupling agent, and reflux-reacting.
  5. 5. A pH-responsive MOF material according to claim 3, wherein the RAFT agent is 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid; And/or the condensing agent is N, N' -dicyclohexylcarbodiimide; And/or the catalyst is 4-dimethylaminopyridine.
  6. 6. The pH-responsive MOF material of claim 3, wherein the molar ratio of the total amount of monomers to the intermediate-immobilized RAFT functionalities is (100-500): 1; and/or the molar ratio of the 2-diisopropylamino ethyl methacrylate to the ethylene glycol methyl ether methacrylate is 1 (1-2); And/or azo initiator is used in the RAFT polymerization reaction, and the molar ratio of the RAFT functional group number immobilized by the intermediate to the azo initiator is (5-20): 1.
  7. 7. Use of the pH-responsive MOF material of any one of claims 1 to 6 for the preparation of a dental appliance.
  8. 8. A photocurable pH-responsive MOF material, characterized in that it is obtained by surface grafting photocurable groups onto a pH-responsive MOF material according to any one of claims 1-6.
  9. 9. A composite photosensitive resin system is characterized by comprising, by mass, 30-40% of aqueous polyurethane acrylate, 40-50% of methacryloylated gelatin, 5-25% of MOF material, 0.5-3% of photoinitiator and the balance of auxiliary agent, wherein the MOF material is the pH-responsive MOF material according to any one of claims 1-6 or the photocurable pH-responsive MOF material according to claim 7.
  10. 10. A dental appliance obtained by 3D printing light curing of a composite light sensitive resin system according to claim 9.

Description

PH responsive MOF material, composite photosensitive resin system containing same and application of composite photosensitive resin system in dental appliance Technical Field The invention relates to the technical field of dental appliances, in particular to a pH response MOF material, a composite photosensitive resin system containing the same and application of the composite photosensitive resin system in a dental appliance. Background The bracket-free invisible appliance has become one of the mainstream options for orthodontic treatment due to the attractive and comfortable advantages. However, the appliance can wrap teeth after being worn for a long time, a closed environment is formed, plaque accumulation is easy to occur, and complications such as tooth enamel demineralization (orthodontic white spots), caries and even periodontitis are caused. To address these problems, the prior art has mainly introduced antibacterial or remineralizing functions at the appliance surface or body, but the following limitations are prevalent: (1) The existing scheme is mainly focused on single function. For example, patent CN119707719a achieves fluoride ion release by adding a fluoride salt monomer to a 3D printing resin to prevent demineralization, but does not integrate an efficient antimicrobial mechanism. In contrast, some techniques (e.g., medical device patents with antimicrobial coatings) focus on achieving antimicrobial by silver ions, etc., but lack the ability to promote remineralization of enamel. The maintenance of oral health requires the synergistic effect of antibacterial and remineralization, and the linkage and synergy of the two functions are difficult to realize on the same platform in the prior art; (2) Non-controlled release and side effects risk most technologies use physical blending or simple coating to load functional agents (e.g. antimicrobial agents, fluorides) with early "burst release" problems. This results in a short effective time and an initial concentration that is too high may cause irritation to the oral tissue (e.g., the localized drug irritation risk mentioned in the background of the patent "invisible appliance for treating periodontal disease and preventing enamel demineralization"). Meanwhile, the uncontrolled release can not accurately provide medicines in the space and time which needs treatment, and the efficiency is low and the medicines are wasted; (3) Lack of intelligent responsiveness-traditional functionalized appliances cannot sense changes in the oral environment. For example, plaque metabolism produces acid which results in a local pH drop, which is a direct signal of caries occurrence, but for which existing appliance materials are "immaterial" and "on-demand therapy" cannot be achieved. Although research is attempted to develop a stimulus response material, the stimulus response material has the advantages of simple structure, single response mechanism and difficulty in coping with complex oral environments; (4) The challenges of structural stability and durability are that functional components are easy to fall off, lose efficacy or cause the performance of materials to be reduced under long-term use and complex oral environment whether a surface coating (such as a coating easy to fall off problem aimed at by a high-adhesion antibacterial film for an oral invisible appliance) or a physical blending functional agent. The bonding strength of the functional component and the matrix material is the key for ensuring the durability of the curative effect; (5) The difficulty of personalized manufacturing and function integration is that 3D printing technology provides possibility for personalized appearance manufacturing of the appliance, but integrating complex functions, particularly intelligent functions with space-time control capability, into printing resin and realizing high-precision manufacturing still remains a great challenge. The prior art is difficult to stably load and keep the activity of the functional material in the printing process, and the function can not be preset and triggered in the three-dimensional structure. Therefore, there is a need for an intelligent appliance material that integrates dual antimicrobial and remineralization functions, has pH-responsive controlled release capabilities, is structurally stable, and is compatible with personalized 3D printing manufacturing. By constructing a multifunctional cooperative platform, the gradient release of fluoride ions and antibacterial agents under the triggering of an acidic environment is realized. In recent years, metal-organic framework materials have shown potential in the field of drug delivery due to their high specific surface area, tunable pore structure and functionalized surfaces. However, the simple use of MOFs as drug carriers embedded in polymers still has difficulty in solving the problems of controlled release, synergy and smart response described above. Therefore, there is an urgent