CN115154331A - Dentin mineralization desensitization material with mesoporous core-shell structure and preparation method thereof - Google Patents
Dentin mineralization desensitization material with mesoporous core-shell structure and preparation method thereof Download PDFInfo
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- CN115154331A CN115154331A CN202210686134.8A CN202210686134A CN115154331A CN 115154331 A CN115154331 A CN 115154331A CN 202210686134 A CN202210686134 A CN 202210686134A CN 115154331 A CN115154331 A CN 115154331A
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Images
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
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- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a dentin mineralization desensitization 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, dropwise adding isopropyl titanate and n-butyl zirconium, and reacting to obtain SiO 2 /TiZrO 2 A double-layer nanomaterial; subjecting the SiO 2 /TiZrO 2 Template removing treatment of double-layer nano materialObtaining a mesoporous core-shell structure material; preparing a PAH-ACP liquid-phase mineralization precursor solution; then dispersing the mesoporous core-shell structure material in a PAH-ACP liquid phase mineralization precursor solution for loading, centrifuging, collecting precipitate and washing to obtain the dentin mineralization desensitization material PAH-ACP @ SiO with the mesoporous core-shell structure 2 /mTiZrO 2 . The prepared dentin mineralization desensitization material with the mesoporous core-shell structure has the advantages of strong repeatability, stable structure, high load rate, long release period and high mineralization rate.
Description
Technical Field
The invention relates to the technical field of biomedical engineering, in particular to a dentin mineralization desensitization material with a mesoporous core-shell structure and a preparation method thereof.
Background
Dentine sensitivity is one of the common diseases in oral clinical diagnosis and treatment, is ubiquitous in adults, and has an average prevalence rate of up to 33.5%. Dentinal hypersensitivity is usually manifested by transient, sharp pain formation of exposed dentin under stimuli of temperature, chemical, mechanical or osmotic factors, which severely affects quality of life. The most widely accepted hydrodynamics holds that the fluid flow within the dentinal tubules caused by various types of stimuli is the basis for pain transmission. Therefore, the physical occlusion of dentinal tubules is the main strategy of clinical treatment at present, including the application of tubule occluding agents (ions, mineral salts, proteins), dentin occluding agents (glass ions, composite resins, adhesives), laser, periodontal soft tissue transplantation. Although good immediate results are obtained with all of the above treatments, they are difficult to maintain in a moist, complex oral environment. To date, there is a lack of long-term effective treatments for dentinal hypersensitivity.
The ideal dentinal desensitization therapy is to simulate the biomineralization process to induce dentinal tubule occlusion and improve dentin resistance to mechanical and chemical stimuli. Dentin contains 30% organic matter and 70% inorganic minerals, with type I collagen fibers being the major organic component. The fiber inner and outer minerals support dentin as steel bars and cement, so that the restoration of the natural hierarchical structure of dentin through the biomimetic mineralization of collagen is a feasible scheme for long-term sealing of dentin tubules. Recent research has found that various polymers such as polyaspartic acid (PAsp), polyacrylic acid (PAA), polyallylamine hydrochloride (PAH) can induce liquid-liquid phase separation by simulating the function of non-collagen to form Amorphous Calcium Phosphate (ACP), which permeates into collagen and nucleates and grows to achieve ordered mineralization in collagen fibers. ACP has good biological activity and biodegradability, and is a research hotspot in the field of biomimetic mineralization of hard tissues. However, clinical use is very limited due to thermodynamic instability and susceptibility to phase transition.
Inorganic mesoporous materials are often applied to the biomedical field in the form of carriers due to their extremely high specific surface area, regular and ordered pore channels and stable structure. Among them, mesoporous silicon is the most typical carrier in dentinal tubule blocking materials. Although the mesoporous silica-based material can effectively resist acidity, the mesoporous silica-based material cannot provide a long-term pipe plugging effect due to high degradation rate.
Therefore, how to provide a dentin mineralization desensitization material with strong repeatability, stable structure, high loading rate, long release period and fast 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.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a method for 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 dropwise adding isopropyl titanate and n-butyl zirconium for reaction to obtain SiO 2 /TiZrO 2 A double-layer nano material;
subjecting the SiO 2 /TiZrO 2 Carrying out template removal treatment on the double-layer nano material to obtain a mesoporous core-shell structure material;
preparing a PAH-ACP liquid-phase mineralization precursor solution; then dispersing the mesoporous core-shell structure material in a 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 。
Further, the diluent comprises one of absolute ethyl alcohol, methanol, n-propanol, ethyl acetate and diethyl ether; the surfactant comprises one of hexadecyl amine, dodecyl amine, octadecyl amine and hexadecyl trimethyl ammonium bromide, and the catalyst comprises one of strong ammonia water, urea and ammonium bicarbonate.
Further, 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 n-butyl alcohol zirconium is (0.7-0.9): (600-700): (300-400).
Further, the de-template process includes:
subjecting the SiO to 2 /TiZrO 2 Dispersing the double-layer nano material in ammonia water solution, reacting for 15-17 hours at 150-170 ℃, centrifugally collecting precipitate, washing, drying, and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 A mesoporous core-shell structure material.
Further, the obtaining of the liquid-phase mineralization precursor solution of PAH-ACP 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;
adding PAH into the calcium liquid, and adding the phosphorus liquid with the same volume through a peristaltic pump to obtain a PAH-ACP liquid-phase mineralization precursor solution.
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 liquid is 0.8-1.2 mg/mL.
Further, the rate of adding the equal volume of the phosphorus liquid through the peristaltic pump is 2-3 mL/min.
Further, the mesoporous core-shell structure material is dispersed in a PAH-ACP liquid phase mineralization precursor solution for loading, and comprises:
injecting the PAH-ACP liquid phase mineralization precursor solution into the SiO by a peristaltic pump at the speed of 0.7-0.8 mL/min 2 /TiZrO 2 Stirring 5-16 in the double-layer nano materialh。
In a second aspect of the invention, the dentin mineralization desensitization material with the mesoporous core-shell structure prepared by the method is provided.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a dentin mineralization desensitization material with a mesoporous core-shell structure and a preparation method thereof 2 /mTiZrO 2 Core-shell structure PAH-ACP-loaded material (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 tubules in the complex oral environment; on the other hand, the mesoporous titanium zirconium shell layer with hydrolysis resistance and mechanical brushing can protect and release the loaded drug for a long time, and the degree of tubule closure is enhanced by prolonging the action time. The composite material can restore dentin hierarchical structure through collagen biomimetic mineralization, thereby achieving the purpose of long-acting treatment of dentin sensitivity, and specifically comprises the following components:
(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 load rate of the liquid-phase mineralized precursor is up to 21.36 percent, and the release period of the ions is up to 28 days; can biomimetically mineralize collagen fibers and has high mineralization degree; can realize long-term sealing of the dentin tubule, 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 in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a solid SiO of the present invention 2 Nanospheres (FIG. 1 a), siO 2 /TiZrO 2 Double-layer nano material (FIG. 1 b), siO 2 /mTiZrO 2 Mesoporous core-shell structure (FIG. 1 c), PAH-ACP @ SiO 2 /mTiZrO 2 Transmission electron microscopy images of the composite (fig. 1d, fig. 1 e).
FIG. 2 is SiO according to the present invention 2 /mTiZrO 2 Mesoporous core-shell structure, PAH-ACP @ SiO 2 /mTiZrO 2 Fourier transform infrared spectrum result chart of the composite material.
FIG. 3 is a diagram of the present invention PAH-ACP @ SiO 2 /mTiZrO 2 The release curve of calcium and phosphorus ions of the composite material.
FIG. 4 is PAH-ACP @ SiO of the present invention 2 /mTiZrO 2 A transmission electron microscope image and a selected area diffraction result image of the composite material for inducing mineralization in the I-type collagen fibers; wherein FIG. 4a is a schematic representation of a characteristic striation pattern of self-assembled type I collagen fibers with alternating interstitial and overlapping regions; FIG. 4b is the results of collagen fiber mineralization for 4 days; FIG. 4c is a schematic representation of a graph including
PAH-ACP@SiO 2 /mTiZrO 2 Results after incubation in the mineralized solution of the composite for 7 days.
FIG. 5 shows PAH-ACP @ SiO of the present invention 2 /mTiZrO 2 Scanning electron microscope images of biomimetic remineralization of demineralized dentin induced by the composite material. Wherein, fig. 5a and 5b show the result that the mineral substances inside and outside the demineralized dentin collagen fibers are removed and typical periodic striations can be observed, and fig. 5c and 5d show the result that the width of the demineralized dentin collagen fibers is increased and the demineralized dentin collagen fibers are in a continuous state; FIGS. 5e and 5f show the results of mineralization both inside and outside the demineralized dentin collagen fibers.
FIG. 6 shows PAH-ACP @ SiO of the present invention 2 /mTiZrO 2 The composite material is used for scanning electron microscope images of dentinal tubule sealing and acid and wear resistance tests. Wherein, fig. 6a and 6b show that the surface tubule of the dentin sheet is in an open state without desensitization treatment; FIG. 6c and FIG. 6d show the use of SiO containing PAH-ACP @ 2 /mTiZrO 2 Results 28 days after composite treated dentin sheet surface; FIGS. 6e and 6f show the results of citric acid soaking; fig. 6g and 6h show the results after mechanical brushing.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings 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. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by an existing method.
The embodiment of the invention provides a dentin mineralization desensitization material with a mesoporous core-shell structure, and the general idea is as follows:
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, mixing solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, dropwise adding isopropyl titanate and n-butyl zirconium, and reacting to obtain SiO 2 /TiZrO 2 A double-layer nanomaterial;
in the step S1, the first step is performed,
the solid SiO 2 The nanosphere can be purchased directly or prepared by the following method:
mixing absolute ethyl alcohol, deionized water and strong ammonia water to obtain a mixed aqueous solution; adding tetraethoxysilane into the mixed aqueous solution for reaction, and after the reaction is finished, centrifugally precipitating, washing and drying to obtain solid SiO 2 Nanospheres.
The diluent comprises one of absolute ethyl alcohol, methanol, n-propanol, ethyl acetate and diethyl ether; the surfactant comprises one of hexadecyl amine, dodecyl amine, octadecyl amine and hexadecyl trimethyl ammonium bromide, and the catalyst comprises one of strong 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 n-butyl alcohol zirconium is (0.7-0.9): (600-700): (300-400). This ratio range is favorable for the generation of a uniform mesoporous structure.
S2, mixing the SiO 2 /TiZrO 2 Carrying out template removal treatment on the double-layer nano material to obtain a mesoporous core-shell structure material;
the template removing treatment comprises the following steps:
subjecting the SiO 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 the precipitate, drying, and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 A mesoporous core-shell structure material.
The template removing treatment is to form mesoporous channels with ordered internal cavities and shells through alkali etching and calcination, so that the liquid phase mineralized precursor can be conveniently loaded.
S3, preparing a PAH-ACP liquid-phase mineralization precursor solution; then dispersing the mesoporous core-shell structure material in a 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 。
In the step S3, the first step is performed,
the PAH-ACP liquid phase mineralized 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 PAH into the calcium liquid, and adding the phosphorus liquid with the same volume through a peristaltic pump to obtain a PAH-ACP liquid-phase mineralization precursor solution.
The PAH is polyacrylamide hydrochloride (PAH).
The concentration of the calcium liquid is 17-19 mM, and the concentration of the phosphorus liquid is 8-9 mM; the reasons or advantages of the concentration are adopted to control the forming speed of the ACP cluster, and the stable ACP cluster is not formed due to the excessively high or excessively low concentration;
the mass volume ratio of the PAH to the calcium liquid is 0.8-1.2 mg/mL. The mass-to-volume ratio is favorable for stabilizing ACP clusters and inhibiting phase transformation, and the volumes of the phosphorus liquid and the calcium liquid are equal.
The rate of adding the phosphorus liquid with the same volume through the 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 cluster, when the speed is too low, the ACP cluster has large and non-uniform particle size and is not beneficial to loading, and when the speed is too high, the ACP cluster has small and non-uniform particle size and is reduced in stability.
The mesoporous core-shell structure material is dispersed in a PAH-ACP liquid-phase mineralization precursor solution for loading, and comprises the following components:
injecting the PAH-ACP liquid phase mineralization precursor solution into the SiO by a peristaltic pump at the speed of 0.7-0.8 mL/min 2 /TiZrO 2 Stirring the double-layer nano material for 5 to 16 hours.
The reason why injection by a peristaltic pump at a rate of 0.7 to 0.8mL/min is advantageous for ACP clusters in SiO2/TiZrO 2 The double-layer nanometer material is uniformly loaded, the rate is too low, the load is not uniform, and the like, and the rate is too high, the load is too low, and the like.
Dentin mineralization desensitization material (PAH-ACP @ SiO) with mesoporous core-shell structure prepared by the invention 2 /mTiZrO 2 ) The material is obtained by loading a liquid phase mineralized precursor by a mesoporous core-shell structure, wherein the mesoporous core-shell structure is SiO 2 /mTiZrO 2 Core-shell structure of said SiO 2 /mTiZrO 2 The core-shell structure comprises a core layer and a shell layer wrapped on the periphery of the core layer, wherein the core layer is solid SiO 2 Said solid SiO 2 The particle size of the shell is 180-220 nm, the thickness of the shell is 23-27 nm, the shell 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 mineralized precursor PAH-ACP.
The shell layer is provided with ordered mesoporous channels, so that the liquid phase mineralized precursor can be conveniently loaded. Loading of the liquid phase mineralization precursor is to induce biomimetic mineralization of mineralized and demineralized dentin within the collagen fibers.
The inner core is made of solid SiO 2 The reason for (A) is SiO 2 Has excellent acid resistance, can resist acid stimulation in the oral environment, and the shell layer is selected from mesoporous mTiZrO 2 The reason for this is that the titanium zirconium element has both hydrolysis resistance and mechanical brushing resistance, and can protect and release the loaded drug for a long time.
The dentin mineralization desensitization material (namely the dentin mineralization desensitization material with the mesoporous core-shell structure) prepared by the invention
PAH-ACP@SiO 2 /mTiZrO 2 ) Can seal dentinal tubules for a long time by mineralization in collagen fibers and biomimetic remineralization of demineralized dentin. 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 method is an excellent mode for treating dentin sensitivity.
The dentin mineralization desensitizing material with the mesoporous core-shell structure is described in detail below by combining examples and experimental data.
Example 1
The embodiment of the invention provides a method for preparing a dentin mineralization desensitization material with a mesoporous core-shell structure, which comprises the following steps:
(1) Solid SiO 2 The synthesis of (2): 110mL of absolute ethanol, 40mL of deionized water, and 22.6mL of concentrated aqueous ammonia were mixed, stirred at 35 ℃ for 30 minutes, and then 1mL of Tetraethyl orthosilicate (TEOS) was rapidly added to the above mixed solution. After 30 minutes, 8.68mL of TEOS was added dropwise and the reaction was continued for 2 hours. Centrifuging the precipitate at 4000rpm for 15 minutes, washing the precipitate with deionized water and ethanol twice, and drying the washed precipitate to obtain solid SiO 2 Nanospheres.
(2)SiO 2 /TiZrO 2 The synthesis of (2): 0.8g of solid SiO synthesized as described above 2 The nanospheres were ultrasonically dispersed in 97.4mL of absolute ethanol, 1.0g of hexadecylamine and 2mL of concentrated ammonia water 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 slowly added dropwise simultaneously and reacted for 2 hours. Centrifugal collectionCollecting the precipitate, washing twice with deionized water and ethanol, and drying to obtain SiO 2 /TiZrO 2 Double-layer nano material.
(3)SiO 2 /mTiZrO 2 The synthesis of (2): the above synthesized SiO 2 /TiZrO 2 The double-layer nano material is dispersed in 0.5M ammonia water solution, reacts for 16 hours at 160 ℃ in a reaction kettle, and precipitates are collected by centrifugation and washed. Drying, placing in a muffle furnace, and calcining at 600 ℃ for 4 hours to obtain SiO 2 /mTiZrO 2 A mesoporous core-shell structure.
(4) Loading of PAH-ACP: 0.132g of calcium phosphate dihydrate and 0.15g of disodium phosphate were dissolved in 50mL of TBS buffer to obtain 18mM calcium solution and 8.4mM phosphorus solution, respectively. 50mg of PAH is added into 50mL of calcium liquid, and 50mL of phosphorus liquid is added at the speed of 2.5mL/min by a peristaltic pump to prepare the PAH-ACP liquid-phase mineralization 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 0.75mL/min and stirred overnight. Centrifuging the precipitate at 15000rpm for 15 minutes, washing with TBS twice, and collecting PAH-ACP @ SiO 2 /mTiZrO 2 The composite material is dentin mineralization desensitization material with a mesoporous core-shell structure.
Experimental example 1 characterization of dentinal mineralization desensitizing Material
Solid SiO obtained by the preparation method of example 1 2 Nanospheres, siO 2 /TiZrO 2 Double-layer nano material, siO 2 /mTiZrO 2 Mesoporous core-shell structure, PAH-ACP @ SiO 2 /mTiZrO 2 The composite material was observed for the ultrastructure by transmission electron microscopy, and the results are shown in fig. 1a, 1b, 1c, and 1d, respectively. Solid SiO 2 Particle diameter of 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 prepared nano particles have regular shape and good dispersity as can be seen from a corresponding electron microscope image.
Figure 2 shows the fourier transform infrared spectroscopy 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 Show strongerPeak of (C = O stretching vibration). At-543 cm -1 The undisrupted single peak is the characteristic peak of ACP, which proves that the liquid-phase mineralized precursor is still amorphous. Due to the doping of PAH, the characteristic peak is from 580cm -1 Is shifted. The above results indicate that PAH-ACP is successfully loaded on SiO 2 /mTiZrO 2 A mesoporous core-shell structure.
FIG. 3 shows the release curves of calcium and phosphorus ions. PAH-ACP @ SiO 2 /mTiZrO 2 The composite material rapidly releases calcium and phosphorus ions within 24 hours and then slowly and continuously releases the calcium and phosphorus ions for 28 days. The cumulative release concentrations of calcium and phosphorus ions are respectively 13.7mM and 5.5mM, and the concentrations are obviously higher than the previous researches, which shows that the mesoporous core-shell structure effectively improves the load capacity of the PAH-ACP.
Experimental example 2 Performance test of dentin mineralization desensitizing Material
1. Test for mineralization property in induced collagen fiber
In this example, the 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, shaken on a horizontal shaker for 20 minutes to obtain a mineralized solution and transferred to a 6cm petri dish. Floating the nickel net loaded with the single-layer I-type collagen fiber model on the upper surface of the mineralized liquid, and placing the mineralized liquid in a 37 ℃ incubator for incubation. And taking out the nickel screen on the 7 th day, washing with deionized water, air-drying, and performing TEM and selective area electron diffraction detection.
As shown in fig. 4a, the self-assembled collagen fibers of type I exhibit a characteristic striated structure with alternating interstitial and overlapping regions. The SAED results (inset in FIG. 4 a) also showed no crystalline diffraction rings. Figure 4b shows the results of 4 days of mineralization of the collagen fibrils, most of the amorphous precursors having been converted to needle-like crystals within the collagen fibrils, the entirety of which appears as discrete partial mineralization. In addition, spherical PAH-ACP can be seen under the mirror to continue from PAH-ACP @ SiO 2 /mTiZrO 2 The composite material dissolved and penetrated into collagen fibers indicating that mineralization was ongoing. In the presence of PAH-ACP @ SiO 2 /mTiZrO 2 After 7 days incubation in the mineralized liquid of the composite, FIG. 4c shows that collagen fibers are completely generatedFully mineralized, internal crystal formation results in a significant increase in electron density. The SAED results (FIG. 4c inset) show polycrystalline diffraction rings characteristic of the (002), (211) and (004) crystallographic planes, demonstrating PAH-ACP @ SiO 2 /mTiZrO 2 The crystal formed by the composite material inducing mineralization in the collagen is 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. Induced demineralization dentin biomimetic remineralization performance test
After the third molars without caries were cleaned, the enamel of the crown portion was removed, and a dentin sheet with a thickness of 1.0mm was prepared. After gradient sanding polishing with sandpaper, ultrasonic cleaning and acid etching with 37% phosphoric acid for 20 seconds to expose dentinal tubules and demineralized dentin matrix. The dentin sheet prepared by the method can simultaneously simulate a demineralized dentin matrix model and a dentin sensitivity model. The preparation method of the demineralized dentin biomimetic remineralization liquid in the embodiment is the same as that of the demineralized dentin biomimetic remineralization liquid, and 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 obtain a remineralization solution. Demineralized dentin disks (N = 3) were immersed in remineralization fluid and incubated in an incubator at 37 ℃. On day 21 the dentin discs were removed, fixed in 2.5wt% glutaraldehyde solution for 24 hours, rinsed again with deionized water, gradient dehydrated with ethanol and vacuum dried for 1 hour. And (4) observing the dentin sheet by using a field emission scanning electron microscope after gold spraying.
As shown in fig. 5a, b, both the inner and outer minerals of demineralized dentin collagen fibers were removed, and typical periodic striations were observed. At the same time, collagen fibers are broken due to lack of inorganic mineral crystal support. After 7 days of soaking in the remineralisation solution, fig. 5c, d shows that the dentin collagen fibrils increased in width and appeared in a continuous state, indicating that the formation of internal minerals re-supported the collagen network. In addition, since PAH-ACP @ SiO 2 /mTiZrO 2 The nano hybrid releases calcium and phosphorus ions for a long time, and a plurality of spherical PAH-ACP are attached to the surface of collagen and are aggregated into larger spheres. As the remineralization time is prolonged to 21 days, fig. 5e, f show that the demineralized dentin collagen fibers are mineralized inside and outside and even partially blocked dentin is smallA tube. The above results confirm that PAH-ACP @ SiO 2 /mTiZrO 2 The composite material can successfully induce bionic remineralization in a three-dimensional demineralized dentin matrix model.
3. Closed dentinal tubules and acid and wear resistance test
Preparing dentin sheets and establishing a dentin sensitive model according to the method in the induced demineralization dentin biomimetic remineralization performance test, and repeatedly washing the surface with deionized water before the experiment. PAH-ACP @ SiO 2 /mTiZrO 2 Mixing the composite material with TBS buffer solution according to the powder-liquid ratio of 25mg:1mL of the dentin desensitizing liquid is prepared, and a polishing brush is used for dipping a proper amount of the dentin desensitizing liquid and polishing the dentin desensitizing liquid vertical to a dentin sheet for 1 minute. Desensitized dentin discs were stored in artificial saliva for 28 days, and the fluid was changed once every three days. Before the sealing performance test, the dentin sheet was subjected to three treatments: the first is a deionized water rinse, i.e., desensitization treatment subgroup; the second is soaking in 6% citric acid solution for 1 min, i.e. antacid subgroup; the third is the mechanical brushing of the soft bristle toothbrush for 3 minutes, i.e., the anti-wear subgroup. All dentin sheets were washed several times with deionized water and lightly blown parallel to the surface to slightly dry, followed by gradient dehydration, vacuum drying and dentin permeability detection. Dentinal tubule occlusion was observed using FESEM after gold blasting.
As is clear from the results of FIG. 6, the tubules on the surface of the dentin sheet without desensitization treatment were in an open state (FIGS. 6a, b). Storage for 28 days hydrolyzed dentin demineralized collagen fibers, showing a more porous demineralized collagen network. While using SiO containing PAH-ACP @ SiO 2 /mTiZrO 2 On the surface of the composite-treated dentin plate, it was observed that all small orifices were tightly closed after 28 days (FIG. 6c, d). In particular, the longitudinal cross-sectional view shows that the spherical dentinal mineralization desensitizing material is encapsulated within the tubules by the newly formed crystals, resembling the structure of the dentin between the tubules. After citric acid soaking, only a small amount of mineral dissolution occurred in the dentinal tubule orifice, while the sealing effect in the tubules was not affected (fig. 6e, f). After mechanical brushing, the dentinal tubules remained tightly closed (fig. 6g, h). The above results directly demonstrate PAH-ACP @ SiO 2 /mTiZrO 2 The composite material can be sealed for a long time by inducing biomimetic mineralizationThe dentin tubule is acid-resistant and wear-resistant, and is very suitable for dentin sensitivity treatment.
Finally, it should also be 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. Therefore, it is intended that the appended claims be interpreted as including 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 changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a dentin mineralization desensitizing material with a mesoporous core-shell structure is characterized by comprising the following steps:
solid SiO 2 Dispersing the nanospheres in a diluent, adding a surfactant and a catalyst, stirring, dropwise adding isopropyl titanate and n-butyl zirconium, and reacting to obtain SiO 2 /TiZrO 2 A double-layer nanomaterial;
subjecting the SiO 2 /TiZrO 2 Carrying out template removal treatment on the double-layer nano material to obtain a mesoporous core-shell structure material;
preparing a PAH-ACP liquid-phase mineralization precursor solution; dispersing the mesoporous core-shell structure material in a 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 the dentin mineralization desensitizing material with the mesoporous core-shell structure according to claim 1, wherein the diluent comprises one of absolute ethyl alcohol, methanol, n-propyl alcohol, ethyl acetate and diethyl ether; the surfactant comprises one of hexadecyl amine, dodecyl amine, octadecyl amine and hexadecyl trimethyl ammonium bromide, and the catalyst comprises one of strong ammonia water, urea and ammonium bicarbonate.
3. The method for preparing the dentin mineralization desensitizing material with the mesoporous core-shell structure according to claim 1, wherein the solid SiO is 2 The ratio of the mass (g) of the nanosphere to the volume (mu L) of the isopropyl titanate to the volume (mu L) of the n-butyl alcohol zirconium is (0.7-0.9): (600-700): (300-400).
4. The method for preparing the dentin mineralization desensitizing material with the mesoporous core-shell structure according to claim 1, wherein the template removing treatment comprises:
subjecting the SiO 2 /TiZrO 2 Dispersing the double-layer nano material in ammonia water solution, reacting for 15-17 hours at 150-170 ℃, centrifugally collecting precipitate, washing, drying, and calcining at 580-620 ℃ to obtain SiO 2 /mTiZrO 2 A mesoporous core-shell structure material.
5. The method for preparing the dentin mineralization desensitizing material with the mesoporous core-shell structure according to claim 1, wherein the preparing of 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;
adding PAH into the calcium liquid, and adding the phosphorus liquid with the same volume through a peristaltic pump to obtain a PAH-ACP liquid-phase mineralization precursor solution.
6. The method for preparing the dentin mineralization desensitization material with the mesoporous core-shell structure according to claim 5, 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 liquid is 0.8-1.2 mg/mL.
7. The method for preparing the dentin mineralization desensitizing material with the mesoporous core-shell structure according to claim 5, wherein the rate of adding the equal volume of the phosphorus liquid by a peristaltic pump is 2-3 mL/min.
8. The method for preparing the dentin mineralization desensitization material with the 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, and the method comprises the following steps:
injecting the PAH-ACP liquid phase mineralization precursor solution into the SiO by a peristaltic pump at the speed of 0.7-0.8 mL/min 2 /TiZrO 2 Stirring the double-layer nano material for 5 to 16 hours.
9. A dentin mineralization desensitizing material with a mesoporous core-shell structure prepared by the method of any one of claims 1-8.
10. The dentinal mineralization desensitization material with a mesoporous core-shell structure of claim 9, wherein the dentinal mineralization desensitization material (PAH-acp @ sio) is provided 2 /mTiZrO 2 ) The material is obtained by loading a liquid phase mineralized precursor by a mesoporous core-shell structure, wherein the mesoporous core-shell structure is SiO 2 /mTiZrO 2 Core-shell structure of said SiO 2 /mTiZrO 2 The core-shell structure comprises a core layer and a shell layer wrapped on the periphery of the core layer, wherein the core layer is solid SiO 2 Said solid SiO 2 The particle size of the shell layer is 180-220 nm, the thickness of the shell layer is 23-27 nm, the shell layer is provided with an internal cavity, the diameter of the internal cavity is 48-52 nm, and the inner cavity isThe liquid phase mineralization precursor PAH-ACP is loaded in the cavity.
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