CN115154331B - Dentin mineralization desensitizing material with mesoporous core-shell structure and preparation method thereof - Google Patents
Dentin mineralization desensitizing material with mesoporous core-shell structure and preparation method thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000013847 dentin mineralization Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 58
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 47
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 13
- 238000000586 desensitisation Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 230000002572 peristaltic effect Effects 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
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- 238000001035 drying Methods 0.000 claims description 7
- 239000012792 core layer Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 210000004268 dentin Anatomy 0.000 description 50
- 102000008186 Collagen Human genes 0.000 description 28
- 108010035532 Collagen Proteins 0.000 description 28
- 229920001436 collagen Polymers 0.000 description 28
- 239000002131 composite material Substances 0.000 description 24
- 210000005239 tubule Anatomy 0.000 description 24
- 239000000835 fiber Substances 0.000 description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000003592 biomimetic effect Effects 0.000 description 11
- 238000011282 treatment Methods 0.000 description 10
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- 230000000694 effects Effects 0.000 description 8
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- 239000013078 crystal Substances 0.000 description 7
- 201000002170 dentin sensitivity Diseases 0.000 description 7
- 102000012422 Collagen Type I Human genes 0.000 description 6
- 108010022452 Collagen Type I Proteins 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- -1 PAsp) Polymers 0.000 description 6
- 230000001680 brushing effect Effects 0.000 description 6
- 239000011707 mineral Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
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- 238000001000 micrograph Methods 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
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- 238000005115 demineralization Methods 0.000 description 3
- 230000002328 demineralizing effect Effects 0.000 description 3
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- 238000011534 incubation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000000120 Artificial Saliva Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000003239 periodontal effect Effects 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000395 remineralizing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 210000004357 third molar Anatomy 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/50—Preparations specially adapted for dental root treatment
- A61K6/54—Filling; Sealing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
- A61K6/75—Apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a dentin mineralization desensitizing material with a mesoporous core-shell structure and a preparation method thereof, wherein the method comprises the following steps: solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, and then dropwise adding isopropyl titanate and zirconium n-butoxide for reaction to obtain SiO 2 /TiZrO 2 A bilayer nanomaterial; the SiO is subjected to 2 /TiZrO 2 Removing the template of the double-layer nano material to obtain a mesoporous core-shell structure material; preparing PAH-ACP liquid phase mineralization precursor solution; dispersing the mesoporous core-shell structure material into PAH-ACP liquid phase mineralization precursor solution for loading, centrifuging, collecting precipitate, and washing to obtain dentin mineralization desensitization material PAH-ACP@SiO with mesoporous core-shell structure 2 /mTiZrO 2 . The dentin mineralization desensitization material with the mesoporous core-shell structure is high in repeatability, stable in structure, high in load rate, long in release period and high in mineralization rate.
Description
Technical Field
The invention relates to the technical field of biomedical engineering, in particular to a dentin mineralization desensitizing material with a mesoporous core-shell structure and a preparation method thereof.
Background
Dentinal sensitivity is one of the common diseases in oral clinical diagnosis and treatment, and is common in adults, and the average prevalence rate is as high as 33.5%. Dentinal sensitivity is generally manifested by exposure to dentin to brief, sharp pain under the stimulation of temperature, chemical, mechanical or osmotic factors, severely affecting quality of life. The most widely accepted hydrodynamic theory holds that the flow of fluid in the dentinal tubules caused by various stimuli is the basis for pain conduction. Thus, dentinal tubule physical occlusion is the main strategy of current clinical treatment, including application of tubule blocking agents (ions, mineral salts, proteins), dentinal blocking agents (glass ions, composite resins, adhesives), lasers, periodontal soft tissue transplantation. Although the above treatments all achieve good immediate results, they are difficult to maintain in a moist complex oral environment. To date, there is a lack of long-term effective treatments for dentin sensitivity.
An ideal dentinal desensitization treatment method is to simulate the biomineralization process to induce dentinal tubule occlusion and improve the resistance of dentin to mechanical and chemical stimulus. Dentin contains 30% of organic matter and 70% of inorganic minerals, wherein type I collagen fibers are the main organic components. The mineral inside and outside the fiber support the excellent mechanical property of dentin like steel bar and cement, so the natural hierarchical structure of dentin is recovered by the biomimetic mineralization of collagen, which is a viable scheme for closing dentin tubules for a long time. Recent studies have found that various polymers such as polyaspartic acid (poly aspartic acid, PAsp), polyacrylic acid (PAA), polyacrylamide hydrochloride (poly-allylamine hydrochloride, PAH) can induce liquid-liquid phase separation by mimicking non-collagen functions, forming amorphous calcium phosphate (amorphous calcium phosphate, ACP), which penetrates collagen and nucleates growth, achieving ordered mineralization within collagen fibers. ACP has good biological activity and biodegradability, and is a research hot spot in the field of biomimetic mineralization of hard tissues. However, clinical applications are quite limited due to thermodynamic instability and susceptibility to phase changes.
Inorganic mesoporous materials are often applied to the biomedical field in a carrier form because of extremely high specific surface area, regular and ordered pore channels and stable structures. Among these, mesoporous silicon is the most typical carrier in dentin tubule sealing materials. Although mesoporous silicon-based materials can effectively resist acidity, long-term pipe plugging effect cannot be provided due to high degradation rate.
Therefore, how to provide dentin mineralization desensitizing material with strong repeatability, stable structure, high loading rate, long release period and high mineralization rate and a preparation method thereof becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a dentin mineralization desensitization material with a mesoporous core-shell structure and a preparation method thereof, and the dentin mineralization desensitization material with the mesoporous core-shell structure is high in repeatability, stable in structure, high in load rate, long in release period and high in mineralization rate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method of preparing a dentin mineralization desensitizing material having a mesoporous core-shell structure, the method comprising:
solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, and then dropwise adding isopropyl titanate and zirconium n-butoxide for reaction to obtain SiO 2 /TiZrO 2 A bilayer nanomaterial;
the SiO is subjected to 2 /TiZrO 2 Removing the template of the double-layer nano material to obtain a mesoporous core-shell structure material;
preparing PAH-ACP liquid phase mineralization precursor solution; dispersing the mesoporous core-shell structure material into PAH-ACP liquid phase mineralization precursor solution for loading, centrifuging, collecting precipitate, and washing to obtain dentin mineralization desensitization material with mesoporous core-shell structure, namely PAH-ACP@SiO 2 /mTiZrO 2 。
Further, the diluent comprises one of absolute ethyl alcohol, methanol, n-propanol, ethyl acetate and diethyl ether; the surfactant comprises one of hexadecylamine, dodecylamine, octadecylamine and hexadecyltrimethylammonium bromide, and the catalyst comprises one of concentrated ammonia water, urea and ammonium bicarbonate.
Further, the solid SiO 2 Mass (g) of nanospheres, titaniumThe ratio of the volume of isopropyl acid ester (μl) to the volume of zirconium n-butoxide (μl) is (0.7-0.9): (600-700): (300-400).
Further, the template removing process includes:
the SiO is subjected to 2 /TiZrO 2 Dispersing the double-layer nano material in ammonia water solution, reacting at 150-170 ℃ for 15-17 hours, centrifugally collecting and washing precipitate, drying and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 Mesoporous core-shell structure material.
Further, the obtaining of the PAH-ACP liquid-phase mineralized precursor solution comprises:
dissolving calcium phosphate dihydrate in TBS buffer solution to obtain calcium solution;
dissolving disodium hydrogen phosphate in TBS buffer solution to obtain phosphorus solution;
PAH is added into the calcium solution, and an equal volume of the phosphorus solution is added through a peristaltic pump, so that PAH-ACP liquid phase mineralization precursor solution is obtained.
Further, the concentration of the calcium solution is 17-19 mM, and the concentration of the phosphorus solution is 8-9 mM; the mass volume ratio of the PAH to the calcium solution is 0.8-1.2 mg/mL.
Further, the rate of adding the equal volume of the phosphorus liquid by a peristaltic pump is 2-3 mL/min.
Further, the mesoporous core-shell structure material is dispersed in the PAH-ACP liquid phase mineralization precursor solution for loading, and comprises the following steps:
injecting PAH-ACP liquid phase mineralized precursor solution into the SiO at a rate of 0.7-0.8 mL/min through a peristaltic pump 2 /TiZrO 2 Stirring the mixture in the double-layer nano material for 5 to 16 hours.
In a second aspect of the invention, there is provided a dentin mineralization desensitizing material with a mesoporous core-shell structure prepared by the method.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
the invention provides a dentin mineralization desensitizing material with a mesoporous core-shell structure and a preparation method thereof, and the dentin mineralization desensitizing material has the advantages of simple preparation process, low cost and high qualityDentin mineralization desensitizing material with mesoporous core-shell structure is based on SiO 2 /mTiZrO 2 PAH-ACP loaded material with core-shell structure (namely PAH-ACP@SiO) 2 /mTiZrO 2 ) On one hand, the solid silicon dioxide can provide better acid resistance than mesoporous silicon, and maintain the sealing effect of the tubule in a complex oral cavity environment; on the other hand, the shell layer of the medium Kong Taigao with both hydrolysis resistance and mechanical brushing resistance can protect and release the loaded medicine for a long time, and the sealing degree of the small tube is enhanced by prolonging the action time. The composite material can restore dentin hierarchical structure through collagen biomimetic mineralization, thereby achieving the purpose of treating dentin sensitivity for a long time, in particular:
(1) The dentin mineralization desensitization material with the mesoporous core-shell structure has the advantages of stable structure, uniform particle size and good dispersibility; the loading rate of the liquid phase mineralized precursor is up to 21.36%, and the ion release period is up to 28 days; the collagen fiber can be mineralized in a bionic way, and the mineralization degree is high; can realize the long-acting closure of dentinal tubules, has the characteristics of acid resistance and wear resistance, and is an excellent mode for treating dentin sensitivity.
(2) The preparation method has simple process and easily controlled process parameters.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a solid SiO of the present invention 2 Nanospheres (FIG. 1 a), siO 2 /TiZrO 2 Double-layer nano material (figure 1 b), siO 2 /mTiZrO 2 Mesoporous core-shell structure (FIG. 1 c), PAH-ACP@SiO 2 /mTiZrO 2 The composite material (fig. 1d, fig. 1 e) is a transmission electron microscope image.
FIG. 2 is a SiO of the present invention 2 /mTiZrO 2 Mesoporous core-shell structure and PAH-ACP@SiO 2 /mTiZrO 2 Fourier transform infrared spectrum results of the composite material.
FIG. 3 is a PAH-ACP@SiO of the present invention 2 /mTiZrO 2 Calcium and phosphorus ion release curve graph of the composite material.
FIG. 4 is a PAH-ACP@SiO of the present invention 2 /mTiZrO 2 A transmission electron microscope image and a selected area diffraction result image of mineralization in the type I collagen fiber induced by the composite material; wherein, fig. 4a shows a characteristic cross-grain structure of staggered gap regions and overlapping regions for self-assembled type I collagen fibers; FIG. 4b shows the results of mineralization of collagen fibers for 4 days; FIG. 4c shows the composition of the ink
PAH-ACP@SiO 2 /mTiZrO 2 Results after 7 days incubation in mineralization of the composite.
FIG. 5 is a PAH-ACP@SiO of the present invention 2 /mTiZrO 2 Scanning electron microscope pictures of biomimetic remineralization of composite material induced demineralization dentin. Wherein fig. 5a and 5b show the results of demineralized dentin collagen fibers from which minerals are removed and typical periodic transverse lines are observed, and fig. 5c and 5d show the results of dentin collagen fibers with increased widths and in a continuous state; FIGS. 5e and 5f show the mineralization results of demineralized dentin collagen fibers both inside and outside.
FIG. 6 is a PAH-ACP@SiO of the present invention 2 /mTiZrO 2 The composite material is used for a scanning electron microscope image of dentin tubule sealing and acid and wear resistance testing. Wherein, fig. 6a and 6b show that dentin sheet surface tubules are in an open state without desensitization treatment; FIGS. 6c and 6d illustrate the use of PAH-ACP@SiO containing particles 2 /mTiZrO 2 Results after 28 days of composite-treated dentin sheet surface; FIGS. 6e and 6f show the results after soaking in citric acid; fig. 6g and 6h show the results after mechanical brushing.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, etc., used in the present invention are commercially available or may be obtained by existing methods.
The embodiment of the invention provides a dentin mineralization desensitizing material with a mesoporous core-shell structure, which has the following overall thought:
according to an exemplary embodiment of the present invention, there is provided a method for preparing a dentin mineralization desensitizing material having a mesoporous core-shell structure, the method comprising:
s1, solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, and then dropwise adding isopropyl titanate and zirconium n-butoxide for reaction to obtain SiO 2 /TiZrO 2 A bilayer nanomaterial;
in the step S1 of the above-mentioned process,
the solid SiO 2 The nanospheres can be purchased directly or prepared by the following method:
mixing absolute ethyl alcohol, deionized water and concentrated ammonia water to obtain a mixed aqueous solution; adding tetraethoxysilane into the mixed aqueous solution for reaction, and centrifugally precipitating, washing and drying after the reaction is finished to obtain solid SiO 2 A nanosphere.
The diluent comprises one of absolute ethyl alcohol, methanol, n-propanol, ethyl acetate and diethyl ether; the surfactant comprises one of hexadecylamine, dodecylamine, octadecylamine and hexadecyltrimethylammonium bromide, and the catalyst comprises one of concentrated ammonia water, urea and ammonium bicarbonate.
The solid SiO 2 The ratio of the mass (g) of the nanospheres, the volume (mu L) of the isopropyl titanate and the volume (mu L) of the zirconium n-butoxide is (0.7-0.9): (600-700): (300-400). The ratio range is favorable for generating a uniform mesoporous structure.
S2, the SiO is processed 2 /TiZrO 2 Removing the template of the double-layer nano material to obtain a mesoporous core-shell structure material;
the template removing process comprises the following steps:
the SiO is subjected to 2 /TiZrO 2 Dispersing the double-layer nano material in ammonia water solution, reacting at 150-170 ℃ for 15-17 hours, centrifugally collecting and washing precipitate, drying and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 Mesoporous core-shell structure material.
The template removing treatment is to form mesoporous channels with ordered internal cavities and shells through alkali etching and calcining, so that liquid phase mineralization precursors are conveniently loaded.
S3, preparing PAH-ACP liquid phase mineralization precursor solution; dispersing the mesoporous core-shell structure material into PAH-ACP liquid phase mineralization precursor solution for loading, centrifuging, collecting precipitate, and washing to obtain dentin mineralization desensitization material with mesoporous core-shell structure, namely PAH-ACP@SiO 2 /mTiZrO 2 。
In the step S3 of the above-mentioned process,
the PAH-ACP liquid phase mineralization precursor solution comprises:
dissolving calcium phosphate dihydrate in TBS buffer solution to obtain calcium solution;
dissolving disodium hydrogen phosphate in TBS buffer solution to obtain phosphorus solution;
PAH is added into the calcium solution, and an equal volume of the phosphorus solution is added through a peristaltic pump, so that PAH-ACP liquid phase mineralization precursor solution is obtained.
The PAH is specifically polyacrylamide hydrochloride (poly-allylamine hydrochloride, PAH).
The concentration of the calcium solution is 17-19 mM, and the concentration of the phosphorus solution is 8-9 mM; controlling the speed of forming the ACP clusters by adopting the reason or the advantage of the concentration, wherein the too large or too small concentration is unfavorable for forming stable ACP clusters;
the mass volume ratio of the PAH to the calcium solution is 0.8-1.2 mg/mL. The mass-to-volume ratio is favorable for stabilizing the ACP clusters and inhibiting phase transition, and the volume of the phosphorus liquid is equal to that of the calcium liquid.
The rate of adding the equal volume of the phosphorus liquid by a peristaltic pump is 2-3 mL/min. The adoption of the speed is beneficial to controlling the forming speed and the particle size of the ACP clusters, the too small speed has the large and nonuniform particle size of the ACP clusters, the load is unfavorable, and the too large speed has the small and nonuniform particle size of the ACP clusters and the stability is reduced.
The mesoporous core-shell structure material is dispersed in PAH-ACP liquid phase mineralization precursor solution for loading, and comprises the following components:
injecting PAH-ACP liquid phase mineralized precursor solution into the SiO at a rate of 0.7-0.8 mL/min through a peristaltic pump 2 /TiZrO 2 Stirring the mixture in the double-layer nano material for 5 to 16 hours.
The reason for injecting the mixture at the rate of 0.7-0.8 mL/min by a peristaltic pump is that the mixture is beneficial to the SiO2/TiZrO of the ACP clusters 2 Even loading in the double-layer nano material has adverse effects such as uneven loading due to too small speed, and adverse effects such as too large speed and too small loading.
The dentin mineralization desensitization material (PAH-ACP@SiO) with mesoporous core-shell structure prepared by the invention 2 /mTiZrO 2 ) Is obtained by loading liquid phase mineralized precursor with mesoporous core-shell structure, wherein the mesoporous core-shell structure is SiO 2 /mTiZrO 2 Core-shell structure, said SiO 2 /mTiZrO 2 The core-shell structure comprises a core layer and a shell layer wrapping the core layer, wherein the core layer is solid SiO 2 The solid SiO 2 The particle size of the polymer is 180-220 nm, the thickness of the shell layer is 23-27 nm, the shell layer is provided with an internal cavity, and the diameter of the internal cavity is 48-52 nm. The internal cavity is loaded with the liquid phase mineralization precursor PAH-ACP.
The shell layer is provided with ordered mesoporous channels, so that liquid phase mineralization precursors can be conveniently loaded. The loading of the liquid phase mineralization precursor is to induce the biomimetic mineralization of the collagen fibrillar internal mineralization and demineralized dentin.
The core is made of solid SiO 2 The reason for (1) is SiO 2 Has excellent acid resistance, can resist acidic stimulation in oral environment, and the shell layer is mesoporous mTiZrO 2 The reason is that the titanium-zirconium element has both hydrolysis resistance and mechanical brushing resistance, and can protect and release the load medicine for a long timeAnd (3) an object.
Dentin mineralization desensitizing material with mesoporous core-shell structure (namely
PAH-ACP@SiO 2 /mTiZrO 2 ) The dentin tubules can be sealed for a long time by biomimetic remineralization of mineralized and demineralized dentin in collagen fibers. Particularly, after the dentin tubule sealing sample is subjected to citric acid etching and mechanical brushing, the tubule sealing effect is not obviously reduced, and the dentin tubule sealing sample is an excellent mode for treating dentin sensitivity.
A dentin mineralization desensitizing material with a mesoporous core-shell structure according to the present application will be described in detail with reference to examples and experimental data.
Example 1
The embodiment of the invention provides a method for preparing dentin mineralization desensitization material with a mesoporous core-shell structure, which comprises the following steps:
(1) Solid SiO 2 Is synthesized by the following steps: 110mL of absolute ethanol, 40mL of deionized water and 22.6mL of concentrated ammonia were mixed, stirred at 35℃for 30 minutes, and then 1mL of tetraethylorthosilicate (Tetraethyl orthosilicate, TEOS) was added rapidly to the above mixed solution. After 30 minutes, 8.68mL TEOS was added dropwise and reacted for 2 hours. Centrifuging at 4000rpm for 15 minutes, washing twice with deionized water and ethanol, and drying to obtain solid SiO 2 A nanosphere.
(2)SiO 2 /TiZrO 2 Is synthesized by the following steps: 0.8g of solid SiO synthesized as described above 2 Nanospheres were sonicated in 97.4mL absolute ethanol, 1.0g hexadecylamine and 2mL concentrated ammonia were added, and stirred at 35℃for 30 minutes. Then 660. Mu.L of isopropyl titanate and 340. Mu.L of zirconium n-butoxide were simultaneously slowly added dropwise, and reacted for 2 hours. Centrifuging, collecting precipitate, washing with deionized water and ethanol twice, and drying to obtain SiO 2 /TiZrO 2 A bilayer nanomaterial.
(3)SiO 2 /mTiZrO 2 Is synthesized by the following steps: the synthesized SiO is subjected to 2 /TiZrO 2 The bilayer nanomaterial was dispersed in 0.5M aqueous ammonia solution and reacted in a reaction kettle at 160 ℃ for 16 hours, and the precipitate was collected by centrifugation and washed. Drying, placing in a muffle furnace, calcining at 600 ℃ for 4 hours to obtain SiO 2 /mTiZrO 2 Mesoporous core-shell structure.
(4) Load of PAH-ACP: 0.132g of calcium phosphate dihydrate and 0.15g of disodium hydrogen phosphate were dissolved in 50mL of TBS buffer, respectively, to give 18mM calcium solution and 8.4mM phosphorus solution. 50mg of PAH was added to 50mL of calcium solution, and 50mL of phosphorus solution was added at a rate of 2.5mL/min by peristaltic pump to prepare PAH-ACP liquid phase mineralized precursor solution. 100mg SiO 2 /mTiZrO 2 The mesoporous core-shell structure was dispersed in 10mL of PAH-ACP solution, leaving 90mL of PAH-ACP solution to be added to the beaker by peristaltic pump at a rate of 0.75mL/min and stirred overnight. Centrifuging at 15000rpm for 15 min, washing with TBS twice, and collecting PAH-ACP@SiO 2 /mTiZrO 2 The composite material is dentin mineralization desensitizing material with mesoporous core-shell structure.
Experimental example 1 characterization of dentin mineralization desensitizing Material
Solid SiO obtained by the method of example 1 2 Nanospheres, siO 2 /TiZrO 2 Double-layer nano material, siO 2 /mTiZrO 2 Mesoporous core-shell structure and PAH-ACP@SiO 2 /mTiZrO 2 The composite material has an ultrastructural view through a transmission electron microscope, and the results are shown in fig. 1a, 1b, 1c and 1d respectively. Solid SiO 2 Particle diameter is about 200nm, mTiZrO 2 The thickness of the mesoporous shell layer is about 25nm, and the diameter of the internal cavity is about 50 nm. The corresponding electron microscope image shows that the prepared nano particles have regular morphology and good dispersibility.
Fig. 2 shows fourier transform infrared spectrum results. With SiO 2 /mTiZrO 2 Compared with a mesoporous core-shell structure, PAH-ACP@SiO 2 /mTiZrO 2 The composite material is 1638cm -1 A stronger peak (c=o stretching vibration) is shown. At-543 cm -1 The unimodal without splitting is the characteristic peak of ACP, which proves that the liquid phase mineralization precursor is still in an amorphous state. The characteristic peak is from-580 cm due to the doping of PAH -1 Where the offset occurs. The above results indicate that PAH-ACP is successfully loaded on SiO 2 /mTiZrO 2 Mesoporous core-shell structure.
FIG. 3 shows the release curves of calcium and phosphorus ions. PAH-ACP@SiO 2 /mTiZrO 2 Composite materialThe material released calcium and phosphorus ions rapidly within 24 hours, then released slowly and continuously for 28 days. The accumulated release concentration of calcium and phosphorus ions is 13.7mM and 5.5mM respectively, which are obviously higher than that of the prior researches, which shows that the mesoporous core-shell structure effectively improves the load capacity of PAH-ACP.
Experimental example 2, dentin mineralization desensitizing Material Performance test
1. Induced collagen intra-fiber mineralization performance test
In this example, a monolayer type I collagen fiber model was used to detect PAH-ACP@SiO 2 /mTiZrO 2 The ability of the composite to induce mineralization within the collagen fibers. 50mg of PAH-ACP@SiO 2 /mTiZrO 2 The composite material was dispersed in 10mL TBS buffer and shaken on a horizontal shaker for 20 minutes to give mineralized solution and transferred to a 6cm dish. The nickel screen loaded with the monolayer type I collagen fiber model floats on the upper surface of mineralized liquid and is placed in a 37 ℃ incubator for incubation. And taking out the nickel screen on the 7 th day, washing and air-drying the nickel screen by using deionized water, and performing TEM and selected area electron diffraction detection.
As shown in fig. 4a, the self-assembled type I collagen fibers exhibit a characteristic striation structure in which the gap regions and the overlap regions are staggered. The SAED results (inset of fig. 4 a) also did not show crystal diffraction rings. Figure 4b shows the result of 4 days of mineralization of collagen fibrils, most of the amorphous precursor having been converted to needle-like crystals within the collagen fibrils, which appear as discontinuous partial mineralization in their entirety. In addition, the spherical PAH-ACP visible under the mirror continues to be formed from PAH-ACP@SiO 2 /mTiZrO 2 The composite dissolves and penetrates into the collagen fibers, indicating that mineralization is proceeding. In the presence of PAH-ACP@SiO 2 /mTiZrO 2 After 7 days incubation in mineralization solution of the composite, fig. 4c shows that collagen fibers are fully mineralized, and that the formation of internal crystals leads to a significant increase in electron density. SAED results (FIG. 4c inset) show polycrystalline diffraction rings characteristic of the (002), (211) and (004) crystal planes, demonstrating PAH-ACP@SiO 2 /mTiZrO 2 The crystals formed by the composite material inducing mineralization in the collagen are hydroxyapatite. The above results directly demonstrate that PAH-ACP@SiO 2 /mTiZrO 2 The ability of the composite to induce mineralization within the collagen fibers.
2. Biomimetic remineralization performance test of induced demineralization dentin
After cleaning the caries-free third molar, the enamel of the crown was removed and a 1.0mm thick dentin sheet was prepared. After sanding with a sand paper gradient, the plaque was cleaned by ultrasonic and etched with 37% phosphoric acid for 20 seconds to expose dentin tubules and demineralized dentin matrix. The dentin sheet prepared in the above manner simultaneously simulates a demineralized dentin matrix model and a dentin sensitivity model. In this example, 50mg of PAH-ACP@SiO was used as the demineralized dentin biomimetic remineralizing solution 2 /mTiZrO 2 The composite material was dispersed in 10mL of TBS buffer and shaken on a horizontal shaker for 20 minutes to obtain remineralised solution. Demineralized dentin sheet (n=3) was immersed in remineralisation solution and incubated in an incubator at 37 ℃. Dentin sheets were removed on day 21, fixed in 2.5wt% glutaraldehyde solution for 24 hours, rinsed again with deionized water, dehydrated with ethanol gradient, and vacuum dried for 1 hour. And (5) observing the dentin sheet after metal spraying by using a field emission scanning electron microscope.
As shown in fig. 5a, b, both the internal and external minerals of the demineralized dentin collagen fibers were removed, and typical periodic transverse lines were observed. At the same time, the collagen fibers are broken due to the lack of inorganic mineral crystal support. After 7 days of immersion in remineralisation solution, figures 5c, d show an increase in dentin collagen fiber width and a continuous state, indicating that the formation of internal minerals re-supports the collagen network. In addition, due to PAH-ACP@SiO 2 /mTiZrO 2 The nano-hybrids release calcium and phosphorus ions for a long time, and many spherical PAH-ACPs adhere to the surface of collagen and aggregate into larger spheres. As the remineralization time extended to 21 days, fig. 5e, f show mineralization of both the inside and outside of the demineralized dentin collagen fibers, even partially occluding the dentinal tubules. The above results confirm that PAH-ACP@SiO 2 /mTiZrO 2 The composite material can successfully induce biomimetic remineralization in a three-dimensional demineralized dentin matrix model.
3. Closed dentin tubule and acid and wear resistance test
Preparing dentin sheets and establishing a dentin sensitivity model according to the method in the induced demineralization dentin biomimetic remineralization performance test, and repeatedly flushing the surface with deionized water before experiments. PA (Polyamide)H-ACP@SiO 2 /mTiZrO 2 The ratio of the composite material to TBS buffer solution is 25mg:1mL of dentin desensitizing liquid is prepared, a proper amount of dentin desensitizing liquid is dipped by a polishing brush and polished for 1 minute perpendicular to dentin slices. The desensitized dentin sheet was stored in artificial saliva for 28 days with a single fluid change over three days. Before the sealing performance test, dentin sheets were subjected to three treatments: the first is deionized water rinsing, a subset of desensitizing treatments; the second is to soak in 6% citric acid solution for 1 minute, namely acid-resistant subgroup; the third is the mechanical brushing of the soft bristle toothbrush for 3 minutes, the antiwear subgroup. All dentin sheets were washed several times with deionized water and gently blown to a slight dryness parallel to the surface, followed by gradient dehydration, vacuum drying, and dentin permeability detection. After the metal spraying, the dentin tubule was observed for occlusion by FESEM.
As is clear from the results of FIG. 6, the dentin sheet surface tubules which were not desensitized were in an open state (FIGS. 6a, b). The 28 day storage hydrolyzes dentin demineralized collagen fibrils, revealing a more porous demineralized collagen network. And PAH-ACP@SiO-containing is used 2 /mTiZrO 2 The composite-treated dentin sheet surface was observed to have all small spouts tightly closed after 28 days (fig. 6c, d). In particular, the longitudinal section shows the structure of spherical dentin mineralization desensitizing material wrapped in a tubule by newly formed crystals, resembling inter-tubular dentin. After immersion in citric acid, only small amounts of mineral dissolution occurred in the dentinal tubules, while the sealing effect in the tubules was not affected (fig. 6e, f). After mechanical brushing, the dentinal tubules remain in a tightly closed state (fig. 6g, h). The above results directly demonstrate that PAH-ACP@SiO 2 /mTiZrO 2 The composite material can be used for sealing dentin tubules in a long-acting manner through induction of biomimetic mineralization, is acid-resistant and wear-resistant, and is very suitable for dentin sensitivity treatment.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. A method for preparing dentin mineralization desensitizing material with mesoporous core-shell structure, which is characterized by comprising the following steps:
solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, and then dropwise adding isopropyl titanate and zirconium n-butoxide for reaction to obtain SiO 2 /TiZrO 2 A bilayer nanomaterial; wherein the catalyst is selected from one of concentrated ammonia water, urea or ammonium bicarbonate;
the SiO is subjected to 2 /TiZrO 2 Removing the template of the double-layer nano material to obtain a mesoporous core-shell structure material; wherein, the template removing process comprises: the SiO is subjected to 2 /TiZrO 2 Dispersing the double-layer nano material in ammonia water solution, reacting for 15-17 hours at 150-170 ℃, centrifugally collecting and washing precipitate, drying and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 Mesoporous core-shell structural materials;
preparing a PAH-ACP liquid phase mineralization precursor solution comprising: dissolving calcium phosphate dihydrate in TBS buffer solution to obtain calcium solution; dissolving disodium hydrogen phosphate in TBS buffer solution to obtain phosphorus solution; adding polyacrylamide hydrochloride into the calcium solution, and adding an equal volume of the phosphorus solution through a peristaltic pump to obtain a polyacrylamide hydrochloride-amorphous calcium phosphate (PAH-ACP) liquid-phase mineralized precursor solution;
dispersing the mesoporous core-shell structure material into PAH-ACP liquid phase mineralization precursor solution for loading, centrifuging, collecting precipitate and washing to obtain the dentin mineralization desensitization material with the mesoporous core-shell structure, namely PAH-ACP@SiO 2 /mTiZrO 2 。
2. The method for preparing dentin mineralization desensitizing material with mesoporous core-shell structure according to claim 1, wherein the diluent is one of absolute ethyl alcohol, methanol, n-propanol, ethyl acetate or diethyl ether; the surfactant is selected from one of hexadecylamine, dodecylamine, octadecylamine or hexadecyl trimethyl ammonium bromide, and the catalyst is selected from one of concentrated ammonia water, urea or ammonium bicarbonate.
3. The method for preparing dentin mineralization desensitizing material with mesoporous core-shell structure according to claim 1, wherein the solid SiO 2 The ratio of the mass (g) of the nanospheres, the volume (mu L) of the isopropyl titanate and the volume (mu L) of the zirconium n-butoxide is (0.7-0.9): (600-700): (300-400).
4. The method for preparing dentin mineralization desensitizing material with mesoporous core-shell structure according to claim 1, wherein the concentration of the calcium solution is 17-19 mM, and the concentration of the phosphorus solution is 8-9 mM; the mass volume ratio of the PAH to the calcium solution is 0.8-1.2 mg/mL.
5. The method for preparing dentin mineralization desensitizing material with mesoporous core-shell structure according to claim 1, wherein the rate of adding the equal volume of the phosphor liquid by peristaltic pump is 2-3 mL/min.
6. The method for preparing a dentin mineralization desensitizing material with a mesoporous core-shell structure according to claim 1, wherein the mesoporous core-shell structure material is dispersed in a PAH-ACP liquid phase mineralization precursor solution for loading, comprising:
injecting PAH-ACP liquid phase mineralized precursor solution into the SiO through a peristaltic pump at a rate of 0.7-0.8 mL/min 2 /mTiZrO 2 Stirring the mesoporous core-shell structure material for 5 to 16 hours.
7. A dentin mineralization desensitizing material with a mesoporous core-shell structure prepared by the method of any one of claims 1-6.
8. The dentin mineralization desensitizing material with mesoporous core-shell structure according to claim 7, wherein the dentin mineralization desensitizing material (PAH-acp@sio 2 /mTiZrO 2 ) Is obtained by loading liquid phase mineralized precursor with mesoporous core-shell structure, wherein the mesoporous core-shell structure is SiO 2 /mTiZrO 2 Core-shell structure, said SiO 2 /mTiZrO 2 The core-shell structure comprises a core layer and a shell layer wrapping the core layer, wherein the core layer is solid SiO 2 The solid SiO 2 The particle size of the liquid phase mineralization precursor PAH-ACP is 180-220 and nm, the thickness of the shell layer is 23-27 nm, the shell layer is provided with an inner cavity, the diameter of the inner cavity is 48-52 nm, and the inner cavity is loaded with the liquid phase mineralization precursor PAH-ACP.
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