CN112062114A - Trivalent manganese ion doped hydroxyapatite material and preparation method and application thereof - Google Patents
Trivalent manganese ion doped hydroxyapatite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a trivalent manganese ion doped hydroxyapatite material and a preparation method and application thereof, wherein the general formula of the composition of the trivalent manganese ion doped hydroxyapatite material is Ca10‑xMnx(PO4)6(OH)2‑xOxWherein x is more than 0 and less than or equal to 1, and the valence state of Mn in the trivalent manganese ion doped hydroxyapatite material is + 3.
Description
Technical Field
The invention relates to a trivalent manganese ion doped hydroxyapatite material, a preparation method and application thereof, belonging to the field of chemistry.
Background
Hard tissue implant materials are important biomedical materials for repair and reconstruction of hard tissue damage. Due to the influence of diseases, aging, frequent traffic accidents and other factors, the demand of hard tissue implant materials is increasing day by day. Hydroxyapatite Ca10(PO4)6(OH)2(HA) is a bioactive material, is the main component of human hard tissue, and can form close combination with human soft and hard tissue after being implanted into human body to induce new bone tissue to generate on the surface. Becomes one of the most widely used hard tissue substitute materials in clinical application at present. However, the tendency of bacteria to adhere to and concentrate on the surface of hydroxyapatite materials leads to infection problems. Therefore, it is a general knowledge that the antibacterial property of the implant material is improved, and the implant material is now studied.
The inorganic component HA of natural bone tissue contains many other ions, such as F-、CO3 2-、Sr2+、Zn2+、Al3+、 Si4+、Na+And the like. Studies have shown that these trace elements play an important role in the biochemical role of bone. For example, silicon-doped hydroxyapatite is more prone to degradation and absorption in vivo, and promotes osteogenesis. The fluorine-doped hydroxyapatite can improve the crystallinity and stability of the hydroxyapatite and can inhibit bacterial adhesion. Zinc-doped hydroxyapatite capable of promoting hydroxyapatite crystalsAnd the growth of the bone can be promoted, the crystal grains are enlarged, and the growth and the calcification of the bone can be promoted. The magnesium-doped hydroxyapatite is beneficial to osteoblast proliferation and osteogenesis promotion. The strontium-doped hydroxyapatite can promote the proliferation and differentiation of osteoblasts, enhance bone healing and promote bone regeneration. Therefore, the artificially synthesized hydroxyapatite can have more excellent biological activity such as osteogenic property, compatibility, bacteriostatic property and the like through doping modification.
Manganese is one of the essential trace elements in normal organisms, and is one of the important trace elements essential to human bodies. The research on manganese-doped hydroxyapatite materials is widely progressed at present. Robles-Aguila et al report a sol-gel microwave assisted method for the preparation of metal ion doped hydroxyapatite, wherein Mn is divalent (Structural analysis of metal-doped (Mn, Fe, Co, Ni, Cu, Zn) calcium hydroxide synthesized by a sol-gel microwave-assisted method). Protein adsorption behaviour of divalent manganese ion doped hydroxyapatite (Protein adsorption from Mn (II) -doped calcium hydroxide particles with differential morphology) was reported by Kandori, k. Patent 1 (publication No. CN110272271A) discloses a hydrothermal preparation method of divalent manganese doped hydroxyapatite. Patent 2 (chinese publication No. CN109529109A) discloses a method for preparing a metal ion-doped hydroxyapatite fiber material with an ultra-long structure, wherein the manganese source is Mn (NO)3)2The manganese in the obtained product is divalent. Studies have shown that the introduction of divalent manganese into hydroxyapatite improves bone/implant adhesion and promotes bone tissue regeneration. At present, the valence states of manganese in the research of manganese element doped hydroxyapatite are divalent, and trivalent manganese ion doped hydroxyapatite is not reported yet.
Trivalent manganese has high oxidizability and is often used as a catalyst in the fields of organic synthesis, pollutant treatment and the like. In addition, Mn is reported3+Can catalyze bacteria to generate active oxygen free radicals in vivo, destroy membrane structure and genetic factor of bacteria, and has significant lethal effect on bacteria. However, Mn3+Is unstable in aqueous solution and is easily diverged into Mn2+And MnO2Thus, the trivalent manganese ion is stabilized in the hydroxyl groupThe apatite structure remains a significant challenge.
Disclosure of Invention
Therefore, the invention provides a trivalent manganese ion doped hydroxyapatite material, and a preparation method and application thereof.
In one aspect, the invention provides a trivalent manganese ion doped hydroxyapatite material, and the composition general formula of the trivalent manganese ion doped hydroxyapatite material is Ca10-xMnx(PO4)6(OH)2-xOxWherein x is more than 0 and less than or equal to 1, and the valence state of Mn in the trivalent manganese ion doped hydroxyapatite material is + 3.
Preferably, x is more than 0 and less than or equal to 0.2, so that the material has good biocompatibility and good antibacterial property.
On the other hand, the invention provides a preparation method of the trivalent manganese ion doped hydroxyapatite material, which is to dope divalent manganese ions with hydroxyapatite Ca10-xMnx(PO4)6(OH)2The material is placed in an air atmosphere or an oxygen atmosphere, and is sintered for 2-10 hours at 400-800 ℃ to obtain the trivalent manganese ion doped hydroxyapatite material.
In the invention, firstly, the high-purity divalent manganese ion doped hydroxyapatite [ Ca ] without impurity ions is prepared by adopting a liquid phase method10-xMnx(PO4)6(OH)2]Then placing the mixture in air atmosphere or oxygen atmosphere for heat treatment to prepare the trivalent manganese ion doped hydroxyapatite material [ Ca10-xMnx(PO4)6(OH)2-xOx]. Specifically, during the heat treatment process (sintering), divalent manganese is oxidized to trivalent manganese while OH in hydroxyapatite is simultaneously oxidized-Dehydrogenation reaction occurs, and O in the air2Generation of H2O is discharged, and the reaction formula is as follows: ca10-xMnx(PO4)6(OH)2+0.25xO2→Ca10-xMnx(PO4)6(OH)2-xOx+0.5xH2O ≈ ≈ O ≈ er. Thus, the invention is achieved by reacting a carboxylic acid with a hydroxy groupTrivalent manganese is introduced into the apatite, so that the high-efficiency antibacterial property of the hydroxyapatite is realized.
Preferably, the divalent manganese source, the calcium source and the phosphorus source are respectively weighed according to the stoichiometric ratio m (Ca + Mn)/n (P) of 1.67, dissolved in water, and subjected to hydrothermal reaction at 0-250 ℃ for 10-76 hours to obtain the divalent manganese ion doped hydroxyapatite material.
Preferably, the calcium source is at least one selected from the group consisting of calcium hydroxide, calcium oxide, calcium phosphate, calcium monohydrogen phosphate, and calcium dihydrogen phosphate.
Preferably, the phosphorus source is at least one selected from phosphoric acid, calcium phosphate, calcium monohydrogen phosphate and calcium dihydrogen phosphate.
Preferably, the divalent manganese source is a divalent manganese compound, preferably at least one of manganese oxide, manganese hydroxide, manganese phosphate, manganese monohydrogen phosphate and manganese dihydrogen phosphate.
Preferably, the dynamic hydrothermal reaction is carried out in a rotatable homogeneous reactor; the rotational speed of the rotatable homogeneous reactor is below 20 revolutions per minute.
In another aspect, the invention also provides an application of the trivalent manganese ion doped hydroxyapatite material in preparation of hard tissue repair materials, catalytic materials and environmental water treatment materials.
Has the advantages that:
(1) according to the trivalent manganese ion doped hydroxyapatite material, unstable trivalent manganese ions are stabilized in a hydroxyapatite structure for the first time, and the hydroxyapatite is endowed with high-efficiency catalytic property and antibacterial property;
(2) the divalent manganese sources (manganese oxide, manganese hydroxide, manganese phosphate, manganese monohydrogen phosphate and manganese dihydrogen phosphate) selected and used for preparation can provide manganese, can also be used as reactants to participate in the reaction, and is more favorable for manganese ions to enter hydroxyapatite HA crystal lattices;
(3) the by-product of the invention is only water, and no exogenous ions except manganese are introduced into the hydroxyapatite structure of the product, and no exogenous ions such as Cl brought in by reactants-、CO3 2-、Na+、NO3 -、NH4 +The mixed ions enter an HA crystal structure, so that the influence of impurity ions can be eliminated;
(4) the reaction system used by the invention can accurately control the content of Mn, realize doping with the content as low as ppm level, eliminate the toxic effect caused by high-concentration doping, and the content is far lower than that of the prior art;
(5) the preparation method has simple process and high yield. The used raw materials have low cost, are suitable for large-scale production and have industrial application prospect and value.
Drawings
FIG. 1 shows Mn3-HA [ Ca ] with different Mn doping amounts10-xMnx(PO4)6(OH)2-xOx]Wherein (a) x is 0.2; (b) x is 0.1(c) x is 0.02(d) x is 0.002(e) x is 0.0002(f) x is 0;
FIG. 2 shows Mn3-HA [ Ca ] with different Mn doping amounts10-xMnx(PO4)6(OH)2-xOx]The manganese content of (d);
FIG. 3 is a Mn2p XPS spectrum (a) for a 0.1Mn3-HA sample and an O1s XPS spectrum (b) for pure HA and a 0.1Mn3-HA sample;
FIG. 4 shows Mn2-HA [ Ca ] with different Mn doping amounts10-xMnx(PO4)6(OH)2]And Mn3-HA [ Ca ]10-xMnx(PO4)6(OH)2- xOx]The color rendering property of (1);
FIG. 5 is the color development of Mn3-HA (x 0.2) at different heat treatment temperatures;
fig. 6 shows XRD patterns and color rendering of Mn3-HA (x ═ 0.5, x ═ 1).
FIG. 7 shows zeta potential values (a) for Mn3-HA samples, contact angles (b) for Mn3-HA samples, protein adsorption (c) for Mn3-HA nanocrystals and surface feature mechanistic maps (d) for Mn3-HA samples (p <0.05), p < 0.01);
FIG. 8 is a histogram showing the colony plate count of Escherichia coli (a) cultured on the surface of Mn3-HA ceramic sheet for 24 hours, the SEM photograph of Escherichia coli (b) cultured on the surface of Mn3-HA bioceramic sheet for 24 hours, the colony plate count of Staphylococcus aureus (c) cultured on the surface of Mn3-HA ceramic sheet for 24 hours, and the SEM photograph of Staphylococcus aureus (d) on the surface of Mn3-HA bioceramic sheet, showing the antibacterial ratio of Mn3-HA bioceramic: (e) escherichia coli, (f) staphylococcus aureus;
FIG. 9 shows the results of cell proliferation of mouse embryonic osteoblasts (MC3T3-E1) cultured on the surface of Mn3-HA bioceramic for 1, 4 and 7 days (a) and the results of alkaline phosphatase (ALP) activity assay after 7 and 14 days of co-culture (b);
FIG. 10 shows the osteogenesis-related gene expression of MC3T3-E1 cultured on the surface of Mn3-HA for 7 and 14 days: (a) BMP-2, (b) Runx 2;
FIG. 11 is a graph showing color development of Mn3-HA (x. sub.2) at different heat treatment temperatures;
fig. 12 is an XRD pattern of Mn3-HA (x ═ 2) after heat treatment at 700 ℃.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the chemical composition of the trivalent manganese ion doped hydroxyapatite is Ca10-xMnx(PO4)6(OH)2-xOxWherein x is more than 0 and less than or equal to 1, and preferably x is more than 0 and less than or equal to 0.2. As the trivalent manganese ion doped hydroxyapatite material contains strong oxidizing trivalent manganese ions, the material has catalytic property, bactericidal property and osteogenesis property, and has important application value in the aspects of being used as hard tissue repair materials, catalysis, environmental water treatment materials and the like. If x is excessive, trivalent manganese in the obtained trivalent manganese ion doped hydroxyapatite material begins to decompose to generate mixed phases.
The preparation method of the trivalent manganese ion doped hydroxyapatite of the invention is exemplified as follows. In one embodiment of the invention, trivalent manganese is stabilized in a hydroxyapatite structure for the first time through a liquid-solid phase two-step method, and the method has the advantages of simple process, high yield and suitability for large-scale production.
Specifically, a divalent manganese source, a calcium source and a phosphorus source are weighed according to a stoichiometric ratio, water is added to the mixture to be uniformly mixed, hydrothermal reaction is carried out, and then the mixture is subjected to suction filtration and drying to obtain the divalent manganese ion doped hydroxyapatite powder. And further sintering in an air atmosphere to obtain the trivalent manganese ion doped hydroxyapatite material.
And (3) preparing the divalent manganese ion doped hydroxyapatite powder. Weighing a divalent manganese source, a calcium source and a phosphorus source according to the metering ratio (molar ratio) m (Ca + Mn)/n (P) ═ 1.67, and adding water and stirring uniformly to obtain a mixed solution. Or respectively preparing bivalent manganese source precursor suspension, calcium source precursor suspension and phosphorus source precursor suspension, and then mixing and stirring uniformly to obtain a mixed solution. Wherein the calcium source can be calcium hydroxide, calcium oxide, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, etc. The phosphorus source can be phosphoric acid, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, etc. The manganese source is a divalent manganese compound, preferably manganese oxide, manganese hydroxide, manganese phosphate, manganese monohydrogen phosphate, manganese dihydrogen phosphate, or the like.
And carrying out hydrothermal reaction on the mixed solution at 0-250 ℃, preferably 50-250 ℃, more preferably 100-200 ℃ for 10-76 hours, preferably 20-30 hours, so as to obtain the divalent manganese ion doped hydroxyapatite. The reaction process can be as follows: (7-x) Ca (OH)2+3Ca(H2PO4)2·H2O+xMnO→Ca10-xMnx(PO4)6(OH)2+(15-x)H2And O. As an example of a hydrothermal reaction, the mixed solution is transferred into a teflon container. And carrying out hydrothermal reaction on the mixed solution, fixing the mixed solution in a homogeneous reactor by using a stainless steel container, wherein the rotating speed is less than 20 revolutions per minute, and the reaction condition is that the mixed solution is reacted for 10-76 hours at the temperature of 50-250 ℃. And after the reaction is finished, carrying out suction filtration on the product, and drying to obtain the divalent manganese ion doped hydroxyapatite material powder.
And (3) carrying out heat treatment (sintering) on the divalent manganese ion doped hydroxyapatite material in a box type furnace in an air atmosphere to obtain the trivalent manganese ion doped hydroxyapatite material. The heat treatment temperature may be 400-800 ℃, preferably 400-700 ℃. The heat treatment time may be 2 to 10 hours. During the heat treatment (sintering), the divalent manganese is oxidized to trivalent manganese, while the OH in the hydroxyapatite is simultaneously oxidized-Dehydrogenation reaction occurs, and O in the air2Generation of H2O is discharged, and the reaction formula is as follows: ca10-xMnx(PO4)6(OH)2+0.25xO2→Ca10-xMnx(PO4)6(OH)2-xOx+0.5xH2O ≈ ≈ O ≈ er. When the sintering temperature is lower, the oxidation of bivalent manganese into trivalent manganese is not enough, the product is still the hydroxyapatite doped with bivalent manganese ions, and the material has no antibacterial property. When the sintering temperature is higher, trivalent manganese ions can be continuously oxidized, and materials are decomposed to generate tricalcium phosphate and mangano-manganic oxide Mn3O4Phase, the pure hydroxyapatite phase cannot be maintained.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) According to the following chemical formula Ca9.9998Mn0.0002(PO4)6(OH)1.998O0.0002The stoichiometric ratio of (A) 0.0007094g MnO (0.07094 g MnO was first weighed to prepare a homogeneous suspension, and 1/100 was diluted to weigh the corresponding volume) and 3.7808g Ca (H) were accurately weighed2PO4)2·H2O、2.5931g Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.9998Mn0.0002(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.9998Mn0.0002(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.9998Mn0.0002(PO4)6(OH)1.9998O0.0002。
Example 2
(1) According to the following chemical formula Ca9.998Mn0.002(PO4)6(OH)1.998O0.002The stoichiometric ratio of (A) 0.007094 g MnO (0.07094 g MnO was first weighed to prepare a homogeneous suspension, and 1/10 was diluted to weigh the corresponding volume) and 3.7808g Ca (H) were accurately weighed2PO4)2·H2O、2.5924g Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.998Mn0.002(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.998Mn0.002(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.998Mn0.002(PO4)6(OH)1.998O0.002。
Example 3
(1) According to the following chemical formula Ca9.98Mn0.02(PO4)6(OH)1.98O0.020.07094g MnO and 3.7808g Ca (H) were accurately weighed in the stoichiometric ratio2PO4)2·H2O、2.5857Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.98Mn0.02(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.98Mn0.02(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.98Mn0.02(PO4)6(OH)1.98O0.02。
Example 4
(1) According to the following chemical formula Ca9.9Mn0.1(PO4)6(OH)1.9O0.1The stoichiometric ratio of (A) is 0.0355g MnO and 3.7808g Ca (H)2PO4)2·H2O、2.5561Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.9Mn0.1(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.9Mn0.1(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.9Mn0.1(PO4)6(OH)1.9O0.1。
Example 5
(1) According to the following chemical formula Ca9.8Mn0.2(PO4)6(OH)1.8O0.20.7094g of MnO,3.7808g Ca(H2PO4)2·H2O、2.5191g Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.8Mn0.2(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.8Mn0.2(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.8Mn0.2(PO4)6(OH)1.8O0.2。
Example 6
(1) According to the following chemical formula Ca9.5Mn0.5(PO4)6(OH)1.8O0.51.7735g MnO and 3.7808g Ca (H) were accurately weighed in the stoichiometric ratio2PO4)2·H2O、2.4079g Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9.5Mn0.5(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.5Mn0.5(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9.5Mn0.5(PO4)6(OH)1.8O0.5。
Example 7
(1) According to the following chemical formula Ca9Mn1(PO4)6(OH)1.8O13.5470g MnO and 3.7808g Ca (H) were accurately weighed in the stoichiometric ratio2PO4)2·H2O、2.2227g Ca(OH)2Adding water and stirring uniformly;
(2) the reaction solution was transferred to a polytetrafluoroethylene container. Fixing the stainless steel container in a homogeneous reactor at a rotation speed of 20 rpm under the reaction condition of 150 ℃ for 24 hours;
(3) after the reaction is finished, wet powder is obtained by suction filtration, and divalent manganese doped hydroxyapatite powder Ca is obtained by drying9Mn1(PO4)6(OH)2；
(4) Doping the obtained divalent manganese ions with hydroxyapatite Ca9.8Mn0.5(PO4)6(OH)2Performing heat treatment in the air atmosphere of a box furnace at the temperature of 600 ℃ for 6 hours to obtain the trivalent manganese ion doped hydroxyapatite Ca9Mn0.2(PO4)6(OH)1.8O1。
Example 8
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the embodiment 6 is as shown in the embodiment 5, and the difference is that: the sintering temperature was 400 ℃.
Example 9
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the embodiment 7 is as shown in the embodiment 5, and the difference is that: the sintering temperature was 500 ℃.
Example 10
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the embodiment 8 is as shown in the embodiment 5, except that: the sintering temperature was 700 ℃.
Comparative example 1
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the comparative example 1 is as shown in example 5, and the difference is that: the sintering temperature was 300 ℃.
Comparative example 2
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the comparative example 2 is as shown in example 5, and the difference is that: the sintering temperature was 800 ℃.
Comparative example 3
The preparation process of the trivalent manganese ion doped hydroxyapatite material in the comparative example 3 is as shown in example 1, and the difference is that: x is 2; the temperatures for the heat treatment were 300 ℃, 500 ℃ and 700 ℃.
FIG. 1 is an XRD pattern of HA with different Mn doping amounts in example 1(a), example 2(b), example 3(c), example 4(d) and example 5 (e). Wherein each diffraction peak in the product belongs to HA phase (JCPDS No. 09-0432), which shows that the product still maintains the crystal structure of HA. As the amount of Mn doping increases, the diffraction peak position of HA shifts to the right, indicating that Mn doping enters the HA lattice and shrinks the HA lattice. This is because of Mn3+(0.06nm) radius less than Ca2+(0.10nm) radius, resulting in shrinkage of the HA lattice and a smaller lattice parameter.
FIG. 2 is the Mn content of the products of examples 1-5. It can be seen that the Mn content in each sample was as expected, and the actual Mn content in example 5 was 9.8ppm, the theoretical doping amount was 10.94ppm, and the doping efficiency was 90%. The actual doping amount of manganese in example 2 was 0.412 w%, the theoretical doping amount was 0.546 w%, and the doping efficiency was 75%. The lower the Mn content, the higher the doping efficiency. The invention realizes continuous control of Mn doping amount and realizes the ppm level doping of Mn content.
FIG. 3 (a) shows the Mn2p spectrum obtained from a sample of Mn3-HA powder. Mn2p doublets of Mn3-HA powder samples were 653.7eV and 642.0eV, corresponding to Mn3+Binding energy of Mn2p1/2 and Mn2p3/2 in the ions. Therefore, the valence of the doped manganese in the HA lattice can be judged to be + 3. In FIG. 3(b), the O1s spectrum of the Mn3-HA sample HAs a peak at the 529.4eV position, which is the peak of lattice oxygen. This demonstrates that hydroxyl groups in hydroxyapatite are dehydrogenated to form lattice oxygen during the preparation of Mn 3-HA.
Fig. 4 is a graph showing the change in color rendering of manganese-doped hydroxyapatite before and after heat treatment in examples 1 to 5. It can be seen that the valence state of Mn in the sample before heat treatment was +2, and the color of the sample appeared as a meat pink color of divalent Mn ions. After the heat treatment, the color changed from meat pink to blue due to the change of the valence state of Mn from +2 to +3, and the color deepened as the Mn content increased. When the Mn content is high (x ═ 0.2), the color further darkens, showing a greenish black color. The valence state of the Mn element in the sample can be judged from the color rendering property of the sample.
FIG. 5 shows the color developability of examples 5, 8, 9, and 10 and comparative examples 1 and 2. It can be seen that the heat treatment temperature HAs a large influence on the valence and color rendering of Mn in the 0.2Mn-HA sample. After the heat treatment at 300 ℃, the sample still maintains the pink color of the meat, which indicates that the valence state of Mn in the sample after the heat treatment at 300 ℃ is not changed and is still + 2. After the heat treatment at 400-700 ℃, the color of the sample is changed into green, which indicates that the valence state +2 of Mn in the sample is changed into + 3. After the heat treatment at 800 ℃, the color of the sample turns brown, which is caused by decomposing manganomanganic oxide Mn in the sample3O4And (4) phase(s).
FIG. 6 is an XRD pattern and color rendering of examples 6, 7. It can be seen that when the manganese content is further increased to x ═ 0.5, 1, the XRD pattern still belongs to the HA phase, indicating that the resulting product still maintains the crystalline structure of HA and no impurity phase appears. 0.5MnHA and 1MnHA showed a dark green color, indicating that the manganese ion therein was still +3 valent.
FIG. 7 is the surface properties of Mn 3-HA. The surface properties of the material have a very important influence on its cell compatibility, protein adsorption properties and the proliferation and adhesion of cells on the surface of the sample. As shown in FIG. 7 (a), with Mn3+The Zeta potential value gradually increases with the increase of the content. As shown in (b) of FIG. 7, it is revealed that different Mn are present3+Protein adsorption histogram of HA nanocrystals at content. It can be seen that, with Mn3+The amount of protein adsorbed on the hydroxyapatite nanocrystals increases. As shown in FIG. 7 (c), the contact angles of the Mn3-HA ceramic sheets are all below 24 °, and with Mn3+The content is increased, the hydrophilicity of the surface of the ceramic chip is gradually increased, good surface hydrophilicity is shown, cell proliferation on the surface is facilitated, and the biological activity is improved. As shown in FIG. 7 (d), Mn is contained in the material3+Preferential substitution of the Ca (2) positionPoint, proton vacancy in adjacent OH-Site generation. Proton vacancy V'HIs a negative charge center, provides a proton acceptor site, increases surface hydrophilicity, and allows cells to better adhere, proliferate and differentiate. Mn3+Is a positively charged center, negatively charged R-COO in bovine serum albumin-Group and Mn on sample surface3+The electrostatic interaction between the sites makes the sites adsorbed on the surface of Mn3-HA, thereby improving the bioactivity. Thus Mn indicated by Mn3-HA3+And V'HThe active sites are formed as positive charge centers and negative charge centers respectively, and the surface activity and the biological activity of the material are improved.
Fig. 8 shows the antibacterial property test results. It can be seen that the antibacterial property is gradually enhanced as the amount of manganese doped increases. Mn3+The introduction of (2) gives HA good antibacterial properties. In particular, the 0.1Mn3-HA samples showed an antimicrobial rate of over 90% for both S.aureus and E.coli.
FIG. 9 shows the effect of Mn3-HA material on osteoblasts. It can be seen that the cell activity gradually increased after 4 days and 7 days of culture. 0.002Mn3-HA (manganese content about 100ppm) showed 50% higher cell proliferation on the surface than pure HA, indicating a trace of Mn3+The doping enhances the proliferative capacity of osteoblasts. After osteoblast co-culture with Mn3-HA samples for 7 days and 14 days, the cells were incubated with Mn3+The content is increased, and the activity of alkaline phosphatase (ALP) of osteoblasts is increased. It is shown that Mn3+ promotes osteoblast differentiation.
FIG. 10 shows the expression of osteoblast genes on Mn3-HA samples. On days 7 and 14 of inoculation, BMP-2 and Runx2 gene expression was significantly up-regulated for the trace Mn-doped HA (10-1000ppm, x ═ 0.0002, 0.002, 0.02) group. When the content continues to increase, the gene expression is down-regulated. Indicates Mn3+The introduction of (A) increases the expression of the osteogenesis related gene and increases the level of osteogenic differentiation.
FIG. 11 is a color development of comparative example 3 in which the powder was prepared at different temperatures. It can be seen that after the sample Mn3-HA (x ═ 2) is subjected to heat treatment at 300-700 ℃, the color of the sample changes into brown or even brownish red, because the manganous manganic oxide Mn is decomposed from the sample3O4And (4) phase(s).
FIG. 12 is an XRD pattern of Mn3-HA (x ═ 2) after heat treatment at 700 ℃, and it can be seen that the main phase in the sample is manganese-doped Ca3(PO4)2Phase and a small amount of Mn3O4And (4) phase(s). The higher Mn content indicates that the hydroxyapatite is more likely to be decomposed to generate Ca under high-temperature treatment3(PO4)2Phase and a small amount of Mn3O4Phase, so that the sample shows Mn3O4(brownish red) a similar brown or brownish yellow color.
The results show that the trivalent manganese ion doped hydroxyapatite material has high antibacterial property, bioactivity and osteogenesis performance and has important application values as a hard tissue repair material, a catalysis material, an environmental water treatment material and the like.
Claims (9)
1. The trivalent manganese ion doped hydroxyapatite material is characterized by having a composition general formula of Ca10-xMnx(PO4)6(OH)2-xOxWherein x is more than 0 and less than or equal to 1, and the valence state of Mn in the trivalent manganese ion doped hydroxyapatite material is + 3.
2. The trivalent manganese ion doped hydroxyapatite material according to claim 1, wherein 0 < x ≦ 0.2.
3. A method for preparing a trivalent manganese ion doped hydroxyapatite material according to claim 1 or 2, characterized in that divalent manganese ions are doped with hydroxyapatite Ca10-xMnx(PO4)6(OH)2The material is placed in an air atmosphere or an oxygen atmosphere, and is sintered for 2-10 hours at 400-800 ℃ to obtain the trivalent manganese ion doped hydroxyapatite material.
4. The preparation method according to claim 3, wherein the divalent manganese source, the calcium source and the phosphorus source are respectively weighed according to a stoichiometric ratio m (Ca + Mn)/n (P) =1.67, dissolved in water, and subjected to hydrothermal reaction at 0-250 ℃ for 10-76 hours to obtain the divalent manganese ion-doped hydroxyapatite material.
5. The method according to claim 4, wherein the calcium source is at least one selected from the group consisting of calcium hydroxide, calcium oxide, calcium phosphate, calcium monohydrogen phosphate, and calcium dihydrogen phosphate.
6. The method according to claim 4 or 5, wherein the phosphorus source is at least one selected from phosphoric acid, calcium phosphate, calcium monohydrogen phosphate, and calcium dihydrogen phosphate.
7. The method according to any one of claims 4 to 6, wherein the divalent manganese source is a divalent manganese compound, preferably at least one of manganese oxide, manganese hydroxide, manganese phosphate, manganese monohydrogen phosphate, and manganese dihydrogen phosphate.
8. The production method according to any one of claims 4 to 7, characterized in that the dynamic hydrothermal reaction is carried out in a rotatable homogeneous reactor; the rotational speed of the rotatable homogeneous reactor is below 20 revolutions per minute.
9. Use of a trivalent manganese ion doped hydroxyapatite material according to claim 1 or 2 in the preparation of hard tissue repair materials, catalytic materials and environmental water treatment materials.
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