CN108785106A - A kind of glue argentiferous calcium phosphate nanometer composite material and its preparation method and application - Google Patents
A kind of glue argentiferous calcium phosphate nanometer composite material and its preparation method and application Download PDFInfo
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- 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
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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Abstract
The present invention relates to a kind of gluey argentiferous calcium phosphate nanometer composite materials and its preparation method and application, and the preparation method includes：Using water-soluble Ca salt as calcium source, water soluble silver salt as silver-colored source, phosphorous biomolecule as phosphorus source, it is dissolved in solvent, obtains mixed solution, the phosphorous biomolecule is adenosine phosphate or/and adenosine phosphate salt；By gained mixed solution by solvent thermal reaction, the gluey argentiferous calcium phosphate nanometer composite material is obtained.
Description
Technical field
The present invention relates to a kind of gluey argentiferous calcium phosphate nanometer composite materials and its preparation method and application, belong to biological material
Expect preparation field.
Background technology
Saprodontia has very high incidence, often makes patient by injury of teeth, tooth as a kind of common dental disorder
The slight illness such as sensitivity, pain, inflammation, the health status of diet, digestion even spirit to influence patient in various degree etc. and life
Bioplasm amount.Currently, clinically common teeth repairing material mainly has a gold, ceramics, silver amalgam, resin etc., however these materials
Material because of defect existing for its own (such as：Hardness is too high, aesthetics is poor, toxic, mechanical strength is low etc.), have been unable to meet people
Increasingly higher demands.
The development of ideal dental biomaterial is a hot spot of current dentistry research.Novel dental is used
For the development of biomaterial, the ingredient and structure of bionical natural dental tissue are typically considered a kind of ideal selection.
Biomaterial and the similarity degree of natural biological tissue are higher, and the performances such as biocompatibility, bioactivity are better.Calcium phosphate
It is widely present in a kind of natural inorganic component in the sclerous tissues such as bone and the tooth of vertebrate, including unformed calcium phosphate, hydroxyl
The objects phases such as apatite (HA), calcium octahate phosphate.By taking the tooth of vertebrate as an example, it is the compound material bodies of an organic/inorganic
System, wherein enamel contains the hydroxyapatite of about 96wt.%.These hydroxyapatites and Fibrilla collagen are by from group
The mode of dress forms composite system, to meet the performances such as the required intensity of physiological function and toughness.
Calcium phosphate inorganic bio is considered to have a kind of ideal biomaterial of good biocompatibility.Mesh
Before, diversified calcium phosphate material has been used for the crowds such as bone defect healing, organizational project, medicine/gene carrier, Dental Erosion
More biomedical sectors.The preparation of calcium phosphate nanometer material, the regulation and control of structure/size/pattern and its application study are biological materials
One important research direction in material field has important scientific meaning and good application prospect.
In addition, the introducing of functional antibiosis element to the generation of saprodontia or it is secondary have inhibit well and protection is made
With.Silver nano-grain can slowly release silver ion, destroy the cell wall of bacterium so as to cause the apoptosis of bacterium, to gram
Negative bacterium and gram-positive bacteria have the effect for inhibiting growth well, to reduce the adherency and increasing of bacterium from source
It grows, protection is provided to the tooth of reparation.
Although have calcium phosphate biomaterial that lot of documents report prevents for saprodontia reparation and secondary caries and its
Preparation method, but having calcium phosphate material mostly is existed in the form of spherical, rodlike or random nano particle.These phosphoric acid
Calcium class material usually through with resin or other macromolecules it is compound after for saprodontia reparation.In addition, being produced between repair materials and tooth
Raw micro chink is also easy to grow bacterium and sends out saprodontia again.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of gluey argentiferous calcium phosphate nanometer composite material and preparation method thereof and
Using.
On the one hand, the present invention provides a kind of gluey argentiferous calcium phosphate nanometer composite material (gluey argentiferous calcium phosphate saprodontias
Composition for repairing) preparation method, including：Using water-soluble Ca salt as calcium source, water soluble silver salt as silver-colored source, phosphorous life
Object molecule is dissolved in solvent as phosphorus source, obtains mixed solution, and the phosphorous biomolecule is adenosine phosphate or/and adenosine phosphate
Salt；
By gained mixed solution by solvent thermal reaction, the gluey argentiferous calcium phosphate nanometer composite material is obtained.
The present invention (can in a solvent can be with water as phosphorus source using phosphorous biomolecule adenosine phosphate or/and adenosine phosphate salt
Solve phosphate radical and adenosine be provided), the wherein gland in the silver ion in water soluble silver salt and adenosine phosphate or/and adenosine phosphate salt
Glycosides molecule forms complex, generates phosphate anion using the hydrolysis properties of phosphorus source under the high temperature conditions, deposition generates in situ
Unformed calcium phosphate phase.Moreover, interaction forms the space networks of similar polymer between complex and unformed calcium phosphate phase
Network structure, extra free silver ion under hydrothermal conditions by reduction of ethylene glycol solvent reduction generate silver-colored simple substance be wrapped by or/
On the spacial framework of polymer similar with being dispersed in (from the point of view of scanning electron microscopic picture silver-colored simple substance be it is equably wrapped or
It is dispersed on dendritic calcium phosphate spatial network), finally macroscopically generate gelatinous argentiferous calcium phosphate nano composite wood
Material.
Preferably, the adenosine phosphate salt is adenosine disodium triphosphate and/or its hydrate.
Preferably, the water-soluble Ca salt be calcium nitrate and/or its hydrate, the water soluble silver salt be silver nitrate and/
Or its hydrate.
Preferably, the molar ratio of the water-soluble Ca salt and phosphorous biomolecule is 1:10~10:1, preferably 1:1~3:
1；The molar ratio of the water-soluble Ca salt and water soluble silver salt is 1:1~150:1, preferably 6:1~25:1.
Preferably, the solvent is the mixed solvent of water and alcohol, the volume ratio 5 of the water and alcohol:1~1:5, preferably 1:
1；Preferably, the alcohol is at least one of ethylene glycol, glycerine, ethyl alcohol, methanol.
Preferably, pH adjusting agent, which is added, makes the pH to 2~4 of the mixed solution；Preferably, the pH adjusting agent is urea
At least one of solution, sodium hydroxide solution, ammonium hydroxide；It is highly preferred that the molar concentration of urea is in the urea liquid
0.01~1 mol/L, preferably 0.05~0.2 mol/L.
Preferably, the molar concentration of the water-soluble Ca salt is 0.001~1 mol/L, preferably 0.01~0.1 mole/
It rises.
Preferably, the reaction temperature of the solvent thermal reaction is 100 DEG C~180 DEG C, preferably 120 DEG C, the reaction time 5
~60 minutes, preferably 10 minutes.Wherein, solvent thermal reaction mode of heating is unrestricted, it is preferred to use microwave heating.
On the other hand, the present invention also provides a kind of gluey argentiferous calcium phosphate nano composite woods prepared according to the above method
Material, the glue argentiferous calcium phosphate nanometer composite material have the microstructure of one-dimensional space network, and composition includes silver/adenosine
Complex, unformed calcium phosphate phase and silver nano-grain.Wherein, the unformed calcium phosphate of silver ion and organic phosphorus source molecule be not
Be simple mixture, but be together with each other, can substantially obtain the content of organic matter by thermogravimetric, but wherein silver or with
Simple substance form exists in the form of the silver oxide being oxidized to form, and is uniformly combined together with unformed calcium phosphate, bad boundary
The specific mass content of fixed specific each component, content of organics is between 20%~40%wt.
In the present invention, gluey argentiferous calcium phosphate nanometer composite material (gluey argentiferous calcium phosphate saprodontia composition for repairing)
Form with similar colloid can be directly used for smearing impaired tooth, has to block well to exposed dentinal tubule and make
With and mineralization can be generated.In addition, the introducing of silver ion also gives the good anti-microbial property of the material, it can be from source
Pass through the growth for inhibiting bacterium and the generation for adhering to pre- anti-caries.
In another aspect, the present invention also provides a kind of above-mentioned gluey argentiferous calcium phosphate nanometer composite materials to be repaiied in preparation dentistry
Application in multiple Material Field.
In the present invention, the preparation process of gluey argentiferous calcium phosphate nanometer composite material is simple and convenient to operate, and does not need complexity
Expensive equipment is expected to realize industrialized production.Prepared gluey argentiferous calcium phosphate nanometer composite material can be applied to dentistry
Saprodontia reparation and the prevention of secondary caries have the preparation and application that extend antibacterial calcium orthophosphate base saprodontia repair materials important
Scientific meaning and application value.
Description of the drawings
Fig. 1 is scanning (SEM) electromicroscopic photograph of the gluey argentiferous calcium phosphate nanometer composite material prepared by embodiment 1；
Fig. 2 is scanning (SEM) electromicroscopic photograph of the gluey argentiferous calcium phosphate nanometer composite material prepared by embodiment 2；
Fig. 3 is scanning (SEM) electromicroscopic photograph of the gluey argentiferous calcium phosphate nanometer composite material prepared by embodiment 3；
Fig. 4 is scanning (SEM) electromicroscopic photograph of the spherical porous unformed calcium phosphate material prepared by comparative example 1；
Fig. 5 is scanning (SEM) electricity of the silver-colored simple substance and silver ion and the composite material of adenosine molecule complex prepared by comparative example 2
Mirror photo；
Fig. 6 is prepared by unformed gluey argentiferous calcium phosphate nanometer composite material and comparative example 1 prepared by embodiment 1-3
Spherical porous unformed calcium phosphate material and comparative example 2 prepared by silver-colored simple substance and silver ion and adenosine molecule complex answer
X-ray diffraction (XRD) collection of illustrative plates of condensation material；
The spherical porous unformed calcium phosphate material and the gluey argentiferous phosphoric acid prepared by embodiment 1-3 that Fig. 7 is the preparation of comparative example 1
Antibacterial effect versus time curve of the calcium nanocomposite to Escherichia coli；
The spherical porous unformed calcium phosphate material and the gluey argentiferous phosphoric acid prepared by embodiment 1-3 that Fig. 8 is the preparation of comparative example 1
Calcium nanocomposite is behind 8 hours and 24 hours to the optical photograph of Escherichia coli antibacterial effect；
Fig. 9 is that the gluey argentiferous calcium phosphate nanometer composite material prepared by embodiment 2 is applied to exposed dentinal tubule surface
It is placed on and simulates mineralising 1 day in saliva, 3 days, 7 days scanning electron microscope (SEM) photo；
Figure 10 is that the gluey argentiferous calcium phosphate nanometer composite material prepared by embodiment 2 is applied to exposed dentinal tubule surface
Afterwards to scanning electron microscope (SEM) photo of streptococcus mutans antibacterial action.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments and attached drawing, it should be appreciated that following embodiments and attached drawing
It is merely to illustrate the present invention, is not intended to limit the present invention.
In the present invention, gluey argentiferous calcium phosphate nanometer composite material has the microstructure of one-dimensional space network, composition
Including silver/adenosine complex, unformed calcium phosphate phase and silver nano-grain.
In an embodiment of the present invention, use water-soluble Ca salt, water soluble silver salt and phosphorous biomolecule for raw material, i.e.,
It is mixed with water and ethylene glycol using water-soluble Ca salt as calcium source, water soluble silver salt as silver-colored source, phosphorous biomolecule as phosphorus source
Bonding solvent obtains the gluey argentiferous calcium phosphate saprodontia repair composite material by microwave fast heating.Wherein, with natural phosphorous
Biomolecule hydrolysis, which releases phosphate anion and reacted with the calcium ion in solution, prepares calcium phosphate, and innovatively by silver from
Son regulates and controls its structure and function, prepares the mucilage binding nanocomposite with one-dimensional reticulated microstructure.Prepared by the present invention
Gluey argentiferous calcium phosphate nanometer composite material has good antibacterial and promotes the performance of dentine remineralization, is led in dentistry
Domain has a good application prospect.
Illustrate to following exemplary the preparation method of gluey argentiferous calcium phosphate nanometer composite material.
Using water-soluble Ca salt as calcium source, water soluble silver salt as silver-colored source, phosphorous biomolecule as phosphorus source, it is dissolved in molten
Agent obtains mixed solution.Common water-soluble Ca salt or its hydrate are used as water-soluble Ca salt, such as：Ca(NO3)2·
4H2O etc..Common water soluble silver salt is used as water soluble silver salt, such as：AgNO3Deng.It can be used as phosphorous biomolecule
Adenosine phosphate or/and adenosine phosphate salt, such as most direct energy source adenosine disodium triphosphate in organism, i.e. ATP.?
In optional embodiment, the molar ratio of water-soluble Ca salt and phosphorous biomolecule can be 1:10~10:1, preferably 1:1~3:
1.In alternative embodiments, the molar ratio of water-soluble Ca salt and water soluble silver salt can be 1:1~150:1, preferably 6:1~
25:1.In alternative embodiments, solvent is the mixed solvent of water and alcohol, the volume ratio 5 of the water and alcohol:1~1:5, it is excellent
It is selected as 1:1.Preferably, alcohol can be ethylene glycol, glycerine, at least one of.It should be noted that preferably by water-soluble Ca salt, water-soluble
Property silver salt and phosphorous biomolecule are dissolved in the in the mixed solvent of water and alcohol jointly.It should be understood, however, that may be used other common mixed
Conjunction mode, such as water is not added simultaneously or successively for water-soluble Ca salt, water soluble silver salt and phosphorous biomolecule solid, but
Solution (the preferred deionized water of solvent) is respectively prepared in water-soluble Ca salt, water soluble silver salt and phosphorous biomolecule to remix, is stirred
It mixes to form mixed solution.
In alternative embodiments, pH adjusting agent is added wherein, pH adjusting agent can be molten for urea liquid, sodium hydroxide
At least one of liquid, ammonium hydroxide.For example, adjusting the pH of mixed solution using urea liquid, urea rubs in the urea liquid
Your concentration can be 0.01~1 mol/L, preferably 0.05~0.2 mol/L.
As an example, the preparation of liquid-phase reaction system：With Ca (NO3)2·4H2O、AgNO3And trinosin
Salt is raw material, using water and ethylene glycol as mixed solvent.Wherein, Ca (NO3)2·4H2The molar ratio of O and adenosine disodium triphosphate
It is 1:10~10:1, preferably 1:1~3:1.Ca(NO3)2·4H2O and AgNO3Molar ratio be 1:1~150:1, preferably 6:
1~25:1.Control Ca (NO3)2·4H2The molar concentration of O is 0.001~1 mol/L, preferably 0.01~0.1 mol/L.
And the pH of the reaction system is adjusted with urea, the molar concentration of urea is 0.01~1 mol/L, and preferably 0.05~0.2 rubs
You/liter, water and ethylene glycol volume ratio 5:1~1:5, preferably 1:1.Here, it is preferred that by water-soluble Ca salt, water soluble silver salt and containing
Phosphorus biomolecule is dissolved in water and ethylene glycol in the mixed solvent jointly.It should be understood, however, that other common hybrid modes, example may be used
If water not being added simultaneously or successively for water-soluble Ca salt, water soluble silver salt and phosphorous biomolecule solid, but will be water-soluble
Calcium salt, water soluble silver salt and phosphorous biomolecule are respectively prepared solution and remix, preferably deionized water, and it is molten that stirring forms mixing
Liquid, adds the ethylene glycol of same volume later, and urea is added and is adjusted.
By mixed solution by solvent thermal reaction, obtains the gluey argentiferous calcium phosphate saprodontia and repair nanocomposite.
Wherein, the reaction temperature of solvent thermal reaction can be 100 DEG C~180 DEG C, preferably 120 DEG C, the reaction time can be 5~60 minutes,
Preferably 10 minutes.Wherein, solvent thermal reaction mode of heating is unrestricted, preferably by microwave heating.
As an example, mixed solution is moved in microwave reaction kettle, microwave hydrothermal reaction, reaction is carried out at 120 DEG C
Time is 10 minutes.Using microwave heating, adenosine disodium triphosphate hydrolysis generates phosphate anion, and silver ion then with ATP
In adenosine molecule form complex, thus deposition generates unformed calcium phosphate phase, complex and unformed phase phosphoric acid in situ
Interaction forms the spacial framework of similar polymer between calcium, and extra free silver ion is reduced the silver-colored simple substance of generation,
Macroscopically generate gelatinous argentiferous calcium phosphate nanometer composite material.
Product after solvent thermal reaction is centrifuged.The product isolated is washed and is dried, i.e.,
Obtain argentiferous calcium phosphate nanometer composite material powder.Washing can be used that water (deionized water) is washed and/or ethyl alcohol (absolute ethyl alcohol) is washed.
Wherein, the mode of drying process can be freeze-drying etc..
Gluey argentiferous calcium phosphate nanometer composite material pattern prepared by the present invention is greatly different from traditional phosphoric acid calcisphere
Shape structure, show silver/adenosine complex, unformed calcium phosphate phase and silver nano-grain interweave jointly formed similar polymer
Spacial framework (referring to Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5), silver nano-grain grain size is about 5-20nm；
Gluey argentiferous calcium phosphate nanometer composite material prepared by the present invention is unformed phase (referring to Fig. 6), and with initial
The increase of concentration of silver ions is added, the content of organic molecule is also higher and higher in the composite material, is conducive to improve its biological
Can, it is the major reason with good biocompatibility；
Gluey argentiferous calcium phosphate nanometer composite material good fluidity prepared by the present invention, can be directly used for smearing；
Gluey argentiferous calcium phosphate nanometer composite material prepared by the present invention and traditional spherical 1 phase of calcium phosphate material comparative example
Than having good killing effect (referring to Fig. 7) to Escherichia coli, and with the increase of silver content, the antibacterial duration also gets over
Long (referring to Fig. 8)；
The unformed calcium phosphate phase in gluey argentiferous calcium phosphate nanometer composite material prepared by the present invention is conducive in simulation saliva
Mineralising (referring to Fig. 9) is carried out in liquid, and the release of silver ion is also beneficial to inhibit the growth of bacterium and proliferation (referring to Figure 10), is
The material that a kind of ideal dentistry saprodontia reparation and secondary caries are prevented.
Preparation process of the present invention is simple and convenient to operate, the equipment for not needing complex and expensive, is expected to realize industrialized production.
The gluey argentiferous calcium phosphate nanometer composite material that through the invention prepared by the preparation method can be applied to the reparation of dentistry saprodontia and
The prevention of secondary caries, to extend antibacterial calcium orthophosphate base saprodontia repair materials preparation and application have important scientific meaning and
Practical value.
With embodiment, the present invention will be described in detail further below.It will similarly be understood that following embodiment is served only for the present invention
It is further described, should not be understood as limiting the scope of the invention, those skilled in the art is according to the present invention
Some nonessential modifications and adaptations that the above is made all belong to the scope of protection of the present invention.For example, following embodiments with
Ca(NO3)2·4H2O、AgNO3With adenosine disodium triphosphate as starting material.The specific reaction temperature of following examples, when
Between, inventory etc. be also only an example in OK range, i.e. those skilled in the art can be closed by the explanation of this paper
Selection in suitable range, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
At room temperature, by 3.540 grams of Ca (NO3)2·4H2O is dissolved in formation A liquid in 100 ml deionized waters, by 3.300 gram of three phosphorus
Adenosine monophosphate disodium salt is dissolved in formation B liquid in 20 ml deionized waters, and 4.000 grams of urea are dissolved in 20 ml deionized waters and are formed
C liquid, by 0.400 gram of AgNO3It is dissolved in formation D liquid in 20 ml deionized waters.Take 15 milliliters of ethylene glycol and 1.5 ml deionized waters
It is mixed with 10 milliliters of A liquid and 2 milliliters of B liquid, and 1 milliliter of C liquid and 0.5 milliliter of D liquid is successively added under magnetic stirring, obtaining pH is
2.615 mixed solution.The mixed solution is transferred in microwave reaction kettle (capacity is 60 milliliters), 10 points are reacted at 120 DEG C
Clock.It after reaction system naturally cools to room temperature, takes out product and centrifuges, the product of separation is washed with deionized 3 times, uses
Absolute ethyl alcohol washs 1 time, freeze-drying, obtains the gluey argentiferous calcium phosphate composite material with spacial framework.
Embodiment 2
At room temperature, by 3.540 grams of Ca (NO3)2·4H2O is dissolved in formation A liquid in 100 ml deionized waters, by 3.300 gram of three phosphorus
Adenosine monophosphate disodium salt is dissolved in formation B liquid in 20 ml deionized waters, and 4.000 grams of urea are dissolved in 20 ml deionized waters and are formed
C liquid, by 0.400 gram of AgNO3It is dissolved in formation D liquid in 20 ml deionized waters.Take 15 milliliters of ethylene glycol and 1 ml deionized water with
10 milliliters of A liquid and 2 milliliters of B liquid mixing, and 1 milliliter of C liquid and 1 milliliter of D liquid is successively added under magnetic stirring, it is 2.501 to obtain pH
Mixed solution.The mixed solution is transferred in microwave reaction kettle (capacity is 60 milliliters), is reacted 10 minutes at 120 DEG C.Instead
After answering system to naturally cool to room temperature, takes out product and centrifuge, the product of separation is washed with deionized 3 times, and use is anhydrous
Ethyl alcohol washs 1 time, freeze-drying, obtains the gluey argentiferous calcium phosphate composite material with spacial framework (substantially from thermogravimetric
Show that content of organics is about 32.5%wt).
Embodiment 3
At room temperature, by 3.540 grams of Ca (NO3)2·4H2O is dissolved in formation A liquid in 100 ml deionized waters, by 3.300 gram of three phosphorus
Adenosine monophosphate disodium salt is dissolved in formation B liquid in 20 ml deionized waters, and 4.000 grams of urea are dissolved in 20 ml deionized waters and are formed
C liquid, by 0.400 gram of AgNO3It is dissolved in formation D liquid in 20 ml deionized waters.Take 15 milliliters of ethylene glycol and 10 milliliters of A liquid and 2 millis
The mixing of B liquid is risen, and 1 milliliter of C liquid and 2 milliliters of D liquid is successively added under magnetic stirring, obtains the mixed solution that pH is 2.351.It should
Mixed solution is transferred in microwave reaction kettle (capacity is 60 milliliters), is reacted 10 minutes at 120 DEG C.Reaction system naturally cools to
It after room temperature, takes out product and centrifuges, the product of separation is washed with deionized 3 times, is washed 1 time with absolute ethyl alcohol, freezing
It is dry, it obtains the gluey argentiferous calcium phosphate composite material with spacial framework and (substantially obtains content of organics about from thermogravimetric
For 35.4%wt).
Comparative example 1
At room temperature, by 3.540 grams of Ca (NO3)2·4H2O is dissolved in formation A liquid in 100 ml deionized waters, by 3.300 gram of three phosphorus
Adenosine monophosphate disodium salt is dissolved in formation B liquid in 20 ml deionized waters, and 4.000 grams of urea are dissolved in 20 ml deionized waters and are formed
C liquid, by 0.400 gram of AgNO3It is dissolved in formation D liquid in 20 ml deionized waters.Take 15 milliliters of ethylene glycol and 2 ml deionized waters with
10 milliliters of A liquid and 2 milliliters of B liquid mixing, and it is added with stirring 1 milliliter of C liquid in magnetic, obtain the mixed solution that pH is 2.733.It should
Mixed solution is transferred in microwave reaction kettle (capacity is 60 milliliters), is reacted 10 minutes at 120 DEG C.Reaction system naturally cools to
It after room temperature, takes out product and centrifuges, the product of separation is washed with deionized 3 times, is washed 1 time with absolute ethyl alcohol, freezing
It is dry, obtain the spherical porous unformed calcium phosphate material that traditional diameter is about 500 nanometers.
Comparative example 2
At room temperature, by 3.540 grams of Ca (NO3)2·4H2O is dissolved in formation A liquid in 100 ml deionized waters, by 3.300 gram of three phosphorus
Adenosine monophosphate disodium salt is dissolved in formation B liquid in 20 ml deionized waters, and 4.000 grams of urea are dissolved in 20 ml deionized waters and are formed
C liquid, by 0.400 gram of AgNO3It is dissolved in formation D liquid in 20 ml deionized waters.Take 15 milliliters of ethylene glycol and 11 ml deionized waters
It is mixed with 2 milliliters of B liquid, and 1 milliliter of C liquid and 1 milliliter of D liquid is successively added under magnetic stirring, it is molten to obtain the mixing that pH is 3.060
Liquid.The mixed solution is transferred in microwave reaction kettle (capacity is 60 milliliters), is reacted 10 minutes at 120 DEG C.Reaction system is certainly
After being so cooled to room temperature, takes out product and centrifuge, the product of separation is washed with deionized 3 times, and 1 is washed with absolute ethyl alcohol
Secondary, freeze-drying obtains being not added with the silver-colored simple substance of calcium generation and the composite material of silver ion and adenosine molecule complex.
Industrial applicability：The preparation process of the present invention is simple and convenient to operate, the equipment for not needing complex and expensive, is easy to real
Existing industrialized production.The gluey argentiferous calcium phosphate nanometer composite material that through the invention prepared by the preparation method can be applied to tooth
Section's saprodontia reparation and the prevention of secondary caries have the preparation and application that extend antibacterial calcium orthophosphate base saprodontia repair materials important
Scientific meaning and practical value.
Claims (10)
1. a kind of preparation method of glue argentiferous calcium phosphate nanometer composite material, which is characterized in that including：
Using water-soluble Ca salt as calcium source, water soluble silver salt as silver-colored source, phosphorous biomolecule as phosphorus source, it is dissolved in solvent, is obtained
To mixed solution, the phosphorous biomolecule is adenosine phosphate or/and adenosine phosphate salt；
By gained mixed solution by solvent thermal reaction, the gluey argentiferous calcium phosphate nanometer composite material is obtained.
2. preparation method according to claim 1, which is characterized in that the adenosine phosphate salt is adenosine disodium triphosphate
And/or its hydrate.
3. preparation method according to claim 1 or 2, which is characterized in that the water-soluble Ca salt be calcium nitrate and/or its
Hydrate, the water soluble silver salt are silver nitrate and/or its hydrate.
4. preparation method according to any one of claim 1-3, which is characterized in that the water-soluble Ca salt and phosphorous life
The molar ratio of object molecule is 1:10~10:1, preferably 1:1~3:1；The molar ratio of the water-soluble Ca salt and water soluble silver salt
It is 1:1~150:1, preferably 6:1~25:1.
5. according to the preparation method described in any one of claim 1-4, which is characterized in that the solvent is the mixing of water and alcohol
The volume ratio 5 of solvent, the water and alcohol:1~1:5, preferably 1:1；Preferably, the alcohol be ethylene glycol, glycerine, ethyl alcohol,
At least one of methanol.
6. preparation method according to any one of claims 1-5, which is characterized in that pH adjusting agent, which is added, makes the mixing
The pH to 2~4 of solution；Preferably, the pH adjusting agent is at least one of urea liquid, sodium hydroxide solution, ammonium hydroxide；More
Preferably, the molar concentration of urea is 0.01~1 mol/L, preferably 0.05~0.2 mol/L in the urea liquid.
7. according to the preparation method described in any one of claim 1-6, which is characterized in that the water-soluble Ca salt it is mole dense
Degree is 0.001~1 mol/L, preferably 0.01~0.1 mol/L.
8. according to the preparation method described in any one of claim 1-7, which is characterized in that the reaction temperature of the solvent thermal reaction
Degree is 100 DEG C~180 DEG C, is preferably 120 DEG C, and the reaction time is 5~60 minutes, preferably 10 minutes.
9. gluey argentiferous calcium phosphate nano composite wood prepared by a kind of preparation method according to any one of claim 1-8
Material, which is characterized in that the glue argentiferous calcium phosphate nanometer composite material has the microstructure of one-dimensional space network, composition
Including silver/adenosine complex, unformed calcium phosphate phase and silver nano-grain.
10. the gluey argentiferous calcium phosphate nanometer composite material described in a kind of claim 9 is in preparing dental prosthetic material field
Application.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810570110.XA CN108785106B (en) | 2018-06-05 | 2018-06-05 | Colloidal silver-containing calcium phosphate nanocomposite and preparation method and application thereof |
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| CN115645601A (en) * | 2022-10-28 | 2023-01-31 | 浙江医鼎医用敷料有限公司 | Gradient-structure antibacterial hydrogel dressing and preparation method and application thereof |
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