CN114538398A - Chiral multilevel structure biological ceramic material and preparation method thereof - Google Patents

Chiral multilevel structure biological ceramic material and preparation method thereof Download PDF

Info

Publication number
CN114538398A
CN114538398A CN202210171578.8A CN202210171578A CN114538398A CN 114538398 A CN114538398 A CN 114538398A CN 202210171578 A CN202210171578 A CN 202210171578A CN 114538398 A CN114538398 A CN 114538398A
Authority
CN
China
Prior art keywords
chiral
bioceramic
calcium
acid
multilevel structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210171578.8A
Other languages
Chinese (zh)
Other versions
CN114538398B (en
Inventor
范存义
周超
车顺爱
刘珅
许彬彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Sixth Peoples Hospital
Original Assignee
Shanghai Sixth Peoples Hospital
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Sixth Peoples Hospital filed Critical Shanghai Sixth Peoples Hospital
Priority to CN202210171578.8A priority Critical patent/CN114538398B/en
Publication of CN114538398A publication Critical patent/CN114538398A/en
Application granted granted Critical
Publication of CN114538398B publication Critical patent/CN114538398B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/325—Preparation by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/24—Alkaline-earth metal silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to a biological ceramic material for forming a chiral multilevel structure, wherein soluble chiral molecules, namely an asymmetric damage inducer, are added in the preparation process of the biological ceramic material to induce the crystal lattice of the biological ceramic material to twist or rotate in the forming process, so that the biological ceramic material with the chiral multilevel structure is formed.

Description

Chiral multilevel structure biological ceramic material and preparation method thereof
Technical Field
The invention relates to the field of biological ceramic materials, in particular to a chiral multilevel structure biological ceramic material and a preparation method thereof.
Background
Chirality is a fundamental property of nature, is ubiquitous in organisms, and is closely related to vital activities, such as DNA, proteins, cells, tissues, etc. of various helical structures. Multilevel structure is a phenomenon commonly occurring in nature, and as the material has a multi-level organization structure, the material is endowed with unexpected properties.
The living body is a chiral multilevel structure and has specific selectivity to chiral environment. If chiral drugs exert different effects in the living body, the reaction is the most typical example, and some chiral pesticides also have different insecticidal effects. At present, the relationship between chiral substances and living bodies also becomes a research hotspot.
Bioceramics are a class of ceramic materials with specific biological or physiological functions, i.e., ceramic materials that are used directly in the human body or in biological, medical, biochemical, etc. directly related to the human body. For example, calcium-based bioceramics, have a great demand in bone tissue engineering. The calcium-based bioceramic comprises: calcium phosphate compounds, calcium silicate compounds, calcium borate compounds, calcium sulfate compounds, and the like. These calcium-based compounds have been widely used in the domestic and industrial fields, mainly as materials for fertilizers, fluorescent substances, catalysts, absorbents, humidity sensors, and electronic components. In the biomedical field, hydroxyapatite, β -tricalcium phosphate, amorphous calcium phosphate, etc. among calcium phosphate compounds have been used as artificial bones, dental roots, biological coating layers, artificial vascular stents, tracheal stents, biotechnological materials, etc. Calcium silicate in the calcium silicate compound also acts as a bioactive ingredient to control the rate of degradation of the artificial bone. Calcium borate in the calcium borate compound is a good bioactive catalyst and can catalyze some unique physiochemical reactions. Calcium carbonate in calcium carbonate compounds is also a common material in life and is also a major component of many organisms, such as shells.
The zirconia bioceramic in the zirconium-based bioceramic is an almost inert bioceramic formed by high-purity zirconia. Is prepared by high-purity zirconium dioxide containing a small amount of stabilizing agent (calcium oxide, magnesium oxide or yttrium oxide) through high-temperature sintering. It has excellent wear resistance, physical corrosion resistance and biocompatibility, and its fracture toughness and strength are superior to those of alumina ceramic. Is mainly used for repairing and replacing hard tissues of human joints, dental implants and the like.
The alumina bioceramic in the aluminum-based ceramic is a near-inert bioceramic formed by high-purity (> 99.5%) alpha-alumina (alpha-Al 2O3), and cannot be corroded or dissolved in a biological environment. The alumina bioceramics can also be used as dental implants, otohearing bone restoration bodies, bone screws and drug release carriers, and have the main defects of much higher elastic modulus than natural bones, poor mechanical compatibility and low tensile strength, and can be aged and fatigued under the action of biological environment, so the alumina bioceramics are not suitable to be used as bone replacement materials for bearing complex stress.
However, the existing bioceramic materials are all prepared by conventional techniques, for example, CN 103935973 a discloses a method for preparing nano-hydroxyapatite with radial multilevel structure under neutral condition, that is, soluble calcium salt and soluble phosphate are used as main raw materials, alkyl phosphate (salt) and soluble citrate are used as additives, and nano-hydroxyapatite with radial multilevel structure is prepared by hydrothermal reaction under neutral condition; CN 111115598A discloses a method for ketone-oriented synthesis of hydroxyapatite with multi-stage structure, that is, (1) 30 parts of calcium salt-water-ketone mixed solution are taken; (2) taking 30 parts of sodium hydroxide-water-phosphorus source mixed solution; (3) adding the mixed solution prepared in the step (2) into the reactor in the step (1), and carrying out reflux reaction for 1-4 hours; (4) then heating the mixture obtained in the step (3) to 110-180 ℃, and carrying out hydrothermal reaction for 2-36 hours under autogenous pressure; (5) standing the stock solution at room temperature for 0-3 days, then washing, centrifuging and drying in vacuum to obtain white powder which is porous nano hydroxyapatite: CN 1931713 a discloses a preparation method of calcium phosphate nanoparticles: slowly dripping a solution containing calcium ions into a mixed solution containing phosphate ions and Cetyl Trimethyl Ammonium Bromide (CTAB), dripping an alkali solution to adjust the pH value to obtain calcium phosphate sol, and filtering, washing and drying after the reaction is finished to obtain the calcium phosphate nano-particles. CN 102897733 a discloses a preparation method of mesoporous nano hydroxyapatite film: with soluble calcium salt and P2O5Preparing sol by effective combination of template method and sol-gel method, preparing sol film on the surface of medical metal alloy material by dipping and pulling method, gelatinizing, drying to form dry gel film, and electrically dryingHeat treatment is carried out in a furnace, thus obtaining the mesoporous nano hydroxyapatite film. (Y.Wang et al/Materials Letters 60(2006) 1484-1487) discloses the hydrothermal synthesis of hydroxyapatite nanopowders using cationic surfactants as templates. (L. -X.Yang et al./Ceramics International 38(2012) 495-502) discloses hydrothermal synthesis of graded hydroxyapatite.
The bioceramic particles synthesized by the conventional methods do not have chiral structures which are mutually recognized and interacted with organisms, and do not have chiral microenvironments which play biological functions.
Disclosure of Invention
According to the detailed description and various exemplary embodiments of the present invention, the present invention relates to a bioceramic material forming a chiral multilevel structure, which is prepared by adding a soluble chiral molecule, i.e., an asymmetric defect inducer, during the preparation process to induce the crystal lattice of the bioceramic material to twist or rotate during the formation process, thereby forming the bioceramic material of the chiral multilevel structure.
The bioceramic material of the present invention refers to a ceramic material used for specific biological or physiological functions, i.e. ceramic materials directly used for organisms or organisms-related biology, medical use, biochemistry, etc. Specifically, the barium-based bioceramic may be included: such as BaX, X is an acid radical; magnesium-based bioceramic: such as MgX, X is an acid radical; calcium-based bioceramics: including various calcium-based ceramics such as: hydroxyapatite, beta-tricalcium phosphate, calcium silicate, calcium borate, calcium carbonate, and various calcium phosphates; glass-ceramic bioceramic: such as CaO- -Al2O3- -SiO2, beta- -CaO. SiO2, SiO2- -Al2O3- -B2O3, SiO2- -Al2O3- -ZnO, SiO2- -Al2O3- -BaO, SiO2- -Al2O3- -Na2O, SiO2- -Al2O3- -K2O, SiO2- -Al2O3- -Fe2O3, or SiO2- -Al2O3- -Sb2O 3; alumina bioceramic: alumina ceramics, activated alumina ceramics, neutral alumina ceramics, acidic alumina ceramics; fluorapatite bioceramics: such as Ca5F (PO4) 3; aluminosilicate bioceramic: such as olivine-island silicates, curtain (green tetrahedra) island silicates, tourmaline (rings of tetrahedra) cyclic silicates, pyroxene (single chain) chain silicates, amphibole (double chain) chain silicates, mica, and white clay (peel) layered silicates; oxide bioceramic: such as Al2O3, ZrO2, magnesium oxide, barium oxide, silicon oxide, titanium oxide; nitride bioceramics: such as silicon nitride, boron nitride, aluminum nitride, gallium nitride, titanium nitride; carbide bioceramic: such as titanium carbide, zirconium carbide, tungsten carbide, silicon carbide; boride bioceramic: such as titanium boride, tantalum boride, vanadium boride, chromium boride, zirconium boride, tungsten boride, molybdenum boride, niobium boride, hafnium boride; silicide bioceramic: such as manganese silicide, iron silicide, cobalt silicide, nickel silicide, titanium silicide, zirconium silicide, niobium silicide, vanadium silicide, niobium silicide, tantalum silicide, molybdenum silicide, tungsten silicide, barium silicide, and the like.
The acid radical in the present invention refers to an acid radical ion, i.e., an anion generated when an acid is ionized. Comprises phosphate radical, silicate radical, borate radical, carbonate radical, strontium acid radical, titanate radical, niobate radical, molybdate radical, tungstate radical, manganese acid radical, ferrite radical, vanadate radical and the like.
The chiral molecules used in the present invention may be: chiral organic acids, such as tartaric acid, malic acid, lactic acid, camphorsulfonic acid, phenylglycine, cyclohexylglycine, tranexamic acid, cis-3-aminocyclohexanecarboxylic acid, and/or ascorbic acid; chiral amino acids: such as histidine, arginine, lysine, isoleucine, phenylalanine, leucine, tryptophan, alanine, methionine, proline, cysteine, aspartic acid, valine, serine, glutamine, tyrosine, aspartic acid, glutamic acid, glutamine, and/or threonine; chiral saccharides: such as glucose, fructose, galactose, ribose, deoxyribose, furanose, pyranose, maltose, sucrose, lactose, and/or galactose; chiral alcohol: such as mannitol, xylitol, sorbitol, paclitaxel, resveratrol, ginkgo biloba polyprenol, (R) - (+) -1-phenyl-1-propanol, (S) - (-) -1-phenyl-1-propanol, amphetamine, iditol, 2-amino-1-propanol, and/or galactitol. Chiral esters: such as diethyl tartrate, and/or methyl lactate; chiral salts: such as histidinol dihydrochloride, ammonium tartrate, sodium ascorbate, carnitine hydrochloride, cysteine ethyl ester hydrochloride, sodium tartrate, and/or sodium potassium tartrate; other chiral molecules: such as microcrystalline cellulose, penicillium ammonium, glutathione, lincomycin, tetracycline, levodopa, biphenyl, and/or spiroalkene molecules, and the like. In one embodiment of the present invention, the amount of chiral molecules added to the bioceramic during its preparation is related to the amount of positive ions added, the amount of positive ions added: the addition amount of the chiral molecules is 1:0.05-10, and the addition amount of the cations is preferably as follows: the addition amount of the chiral molecules is 1:0.1-10, and the addition amount of the cations is further optimized: the amount of chiral molecules added is 1:0.1-5, and the amount of cations added is more preferred: the addition amount of the chiral molecules is 1: 0.2-5. (the amount ratio here is a molar ratio)
In one embodiment of the present invention, the preparation method of the bioceramic is the existing methods such as hydrothermal reaction method, high temperature calcination method, solvent thermal reaction method, etc., and the chiral molecules are added in the existing preparation method process as asymmetric fragmentation inducer to obtain the chiral multilevel structure bioceramic material of the present invention.
Drawings
FIG. 1: the invention relates to a digital photo of chiral multi-stage structure hydroxyapatite powder.
FIG. 2: the invention discloses a scanning electron microscope image for amplifying L-type chiral multi-stage structure hydroxyapatite powder step by step.
FIG. 3: the invention discloses a scanning electron microscope image for amplifying D-type chiral multi-stage structure hydroxyapatite powder step by step.
FIG. 4 is a schematic view of: the high-power transmission electron microscope image of the L-type chiral multi-stage structure hydroxyapatite powder is shown.
FIG. 5: the invention relates to an electron diffraction pattern of L-type chiral multi-level structure hydroxyapatite powder.
FIG. 6: the invention relates to a circular dichroism model diagram of L-type chiral multistage structure hydroxyapatite powder.
FIG. 7: scanning electron microscope images of the chiral multi-stage structure beta-tricalcium phosphate powder.
FIG. 8: the invention discloses a scanning electron microscope image of chiral multi-level structure calcium silicate powder.
FIG. 9: the invention discloses a scanning electron microscope image of chiral multi-level structure calcium borate powder.
FIG. 10: the invention discloses a scanning electron microscope image of chiral multi-stage structure calcium carbonate powder.
FIG. 11: the invention discloses a photo of a mesostructured hydroxyapatite film.
FIG. 12: the invention discloses an adhesion proliferation microscopic picture of L929 cells on a chiral mesoscopic hydroxyapatite film.
FIG. 13 is a schematic view of: the invention discloses an adhesion proliferation microscopic picture of 3T3 cells on a chiral mesostructured hydroxyapatite film.
FIG. 14: the chiral mesostructured hydroxyapatite film is used for a microphotograph of adipogenic differentiation of mesenchymal stem cells of fat sources.
FIG. 15 is a schematic view of: the chiral mesostructured hydroxyapatite film is used for the microscopic picture of osteogenic differentiation of adipose-derived mesenchymal stem cells.
Detailed Description
The present invention will be described in more detail with reference to specific examples. The examples are merely illustrative of the invention and are not to be construed as limiting the invention. The embodiments are practical examples and can be easily grasped and verified by those skilled in the art. If certain changes are made in the invention, then it is not beyond the scope of the invention.
Example 1: chiral multilevel structure hydroxyapatite powder
The chiral multistage structure hydroxyapatite powder is obtained by adding chiral molecules in the preparation process of general hydroxyapatite powder. The preparation method is exemplified as follows:
(1) calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) dissolving in water, and fully stirring and dissolving to form a solution A;
(2) respectively adding tartaric acid (C) as chiral inducer4H6O6) Dissolving the mixture in water, and fully stirring and dissolving the mixture to form a solution B;
(3) ammonium dihydrogen phosphate ((NH)4)H2PO4) And urea (CH)4N2O) dissolving in water, and fully stirring to dissolve to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 5 minutes;
(5) slowly dropping C into the AB mixed solution under the condition of vigorous stirring at room temperature to form a mixed reaction solution, and continuing stirring for 60 minutes.
(6) Then transferring the mixture into a reaction kettle, and reacting for 12 hours at 160 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel structure hydroxyapatite powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of calcium nitrate tetrahydrate, ammonium dihydrogen phosphate, tartaric acid, urea and water is 1: 0.6: 0.625: 1.336: 1658.
meanwhile, in the preparation process of this example, D-type and L-type tartaric acid molecules are respectively adopted in step (2) to synthesize the chiral multi-level structure hydroxyapatite powder, and the synthesized chiral multi-level structure hydroxyapatite powder materials are hereinafter respectively referred to as D-type powder and L-type powder (see fig. 1).
Fig. 1 is a photograph of chiral multistage structure hydroxyapatite powder of the present invention, fig. 2 is a scanning electron microscope image of L-type chiral multistage structure hydroxyapatite powder of the present invention magnified stepwise, fig. 3 is a scanning electron microscope image of D-type chiral multistage structure hydroxyapatite powder of the present invention magnified stepwise, fig. 4 is a high power transmission electron microscope image of L-type chiral multistage structure hydroxyapatite powder of the present invention, and fig. 5 is an electron diffraction image of L-type chiral multistage structure hydroxyapatite powder of the present invention.
As can be seen from fig. 1, the L-type chiral multi-stage hydroxyapatite powder of the present invention has a particle structure as observed by naked eyes; as can be seen from FIG. 2, the L-type chiral multistage hydroxyapatite powder of the present invention has a microstructure in the shape of a sector arranged flake, has a uniform morphology, and exhibits a multistage chiral structure.
As can be seen from FIG. 3, the D-type chiral multistage hydroxyapatite powder of the present invention has a flower-like microstructure in staggered and orderly arrangement, uniform morphology, and exhibits a multistage chiral structure; as can be seen from FIG. 4, the L-shaped powder has regular flake shape, uniform main body portion without fracture and breakage, and staggered saw-toothed structure with regular arrangement and different lengths on the edge.
In addition, as can be seen from fig. 5, the crystal structure in the scaffold is hexagonal, the space group is Pm/63, and it corresponds to the crystal structure of hydroxyapatite. Fig. 6 is a circular dichroism spectrum of the chiral multi-stage structure hydroxyapatite powder of the present invention, which demonstrates that the chiral multi-stage structure hydroxyapatite powder of the present invention both exhibit circular dichroism, indicating that both are formed with a chiral mesostructure and have corresponding optical characteristics.
Example 2: chiral multilevel structure hydroxyapatite powder
The chiral multilevel structure hydroxyapatite powder of the invention is exemplarily obtained by the following preparation method:
(1) anhydrous calcium chloride (CaCl)2) Dissolving in water, and fully stirring and dissolving to form a solution A;
(2) adding chiral inducer aspartic acid (C)4H7NO4) Dissolving in water, and fully stirring to dissolve to form a solution B;
(3) sodium phosphate (N)a3PO4) And urea (CH)4N2O) dissolving in water, and fully stirring to dissolve to form a solution C;
(4) then, at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 5 minutes;
(5) then, C was slowly added dropwise to the AB mixed solution under vigorous stirring at room temperature to form a mixed reaction solution, and stirring was continued for 120 minutes.
(6) Then transferring the mixture into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel structure hydroxyapatite powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of the anhydrous calcium chloride to the sodium phosphate to the aspartic acid to the urea to the water is 1: 0.6: 1: 1.5: 1800.
example 3: chiral multi-stage structure beta-tricalcium phosphate powder
The chiral multilevel structure hydroxyapatite powder of the invention is exemplarily obtained by the following preparation method:
(1) calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) dissolving in water, and fully stirring and dissolving to form a solution A;
(2) adding glucose (C) as chiral inducer6H12O6) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) mixing disodium hydrogen phosphate (N)a2 H PO4) Dissolving in water, and fully stirring to dissolve to form a solution C;
(4) then, at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 5 minutes;
(5) then, C was slowly added dropwise to the AB mixed solution under vigorous stirring at room temperature to form a mixed reaction solution, and stirring was continued for 60 minutes.
(6) Then transferring the mixture into a reaction kettle, and reacting for 12 hours at 160 ℃. After the reaction is finished, natural cooling and centrifugal separation are carried out, deionized water and ethanol are used for alternately washing for 3 times, and then drying is carried out at 40 ℃ to obtain the chiral multi-stage structure beta-tricalcium phosphate precursor.
(7) Then calcined in a muffle furnace at 950 ℃ for 2 hours. Finally, the chiral multi-level structure beta-tricalcium phosphate powder is obtained.
In the process, the adding amount proportion of each raw material is as follows: the molar ratio of calcium nitrate tetrahydrate, disodium hydrogen phosphate, glucose and water is 1.5: 1: 0.9: 1725.
fig. 7 is a scanning electron micrograph of the chiral multi-stage β -tricalcium phosphate powder synthesized in this example. From the figure, it can be seen that the beta-tricalcium phosphate presents a lamellar structure, and the sheets are arranged in a staggered manner to form a multilevel chiral structure.
Example 4: chiral multi-stage structure beta-tricalcium phosphate powder
The chiral multilevel beta-tricalcium phosphate powder of the invention is exemplarily obtained by the following preparation method:
(1) mixing calcium carbonate (CaCO)3) The powder is dispersed inFully stirring and dissolving in water to form a solution A;
(2) adding chiral inducer mannitol (C)6H14O6) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) phosphoric acid (H)3 PO4) Dissolving in water, and fully stirring to dissolve to form a solution C;
(4) then, at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 10 minutes;
(5) slowly dropping C into the AB mixed solution under mild stirring at room temperature to form a mixed reaction solution, and continuing stirring for 60 minutes.
(6) Standing and aging for 12 hours. After the reaction is finished, centrifugal separation is carried out, deionized water and ethanol are used for alternately washing for 3 times, and then drying is carried out at 40 ℃ to obtain the chiral multi-stage structure beta-tricalcium phosphate precursor.
(7) Then calcined in a muffle furnace at 950 ℃ for 2 hours. Finally, the chiral multi-level structure beta-tricalcium phosphate powder is obtained.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of calcium carbonate, phosphoric acid, mannitol and water is 1.5: 1: 3: 1888.
example 5: chiral multilevel structure calcium silicate powder
The chiral multilevel-structured calcium silicate powder of the invention is exemplarily obtained by the following preparation method:
(1) calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) dissolving in water, and fully stirring and dissolving to form a solution A;
(2) adding a chiral inducer asparagine (C)4H8N2O3) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) sodium silicate nonahydrate (N)a2(SiO3·9H2O)) is dissolved in water, and fully stirred and dissolved to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 8 minutes;
(5) and slowly dripping the C into the AB mixed solution at room temperature under the stirring condition to form a mixed reaction solution, and continuing stirring for 30 minutes.
(6) Then standing and aging for 14 days in a water bath environment at 60 ℃. After the reaction, the reaction mixture was centrifuged, washed with deionized water and ethanol alternately 3 times, and then dried at 60 ℃ to obtain a chiral multilevel structure calcium silicate powder (see FIG. 8).
In the process, the adding amount proportion of each raw material is as follows: the molar ratio of calcium nitrate tetrahydrate, sodium silicate nonahydrate, asparagine and water is 1: 1: 0.5: 1280.
fig. 8 is a scanning electron micrograph of the chiral multi-stage structure calcium silicate powder synthesized in this example. It can be seen from the figure that calcium silicate presents a lamellar structure, and the sheets are arranged in a staggered manner to form a multilevel chiral structure.
Example 6: chiral multilevel structure calcium silicate powder
The chiral multilevel-structured calcium silicate powder of the invention is exemplarily obtained by the following preparation method:
(1) dispersing calcium oxide (CaO) in water, and fully stirring and dissolving to form a solution A;
(2) adding glutamic acid (C) as chiral inducer5H9NO4) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) mixing silicon dioxide (SiO)2) ) dispersing the powder in water, and fully stirring to dissolve to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 6 minutes;
(5) and slowly dripping the C into the AB mixed solution at room temperature under the stirring condition to form a mixed reaction solution, and continuing stirring for 80 minutes.
(6) Transferring the mixture into a hydrothermal kettle, and reacting for 18 hours at 180 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 60 ℃ to obtain the chiral multilevel-structure calcium silicate powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of calcium oxide, silicon dioxide, glutamic acid and water is 1: 1: 1: 2000.
example 7: chiral multilevel structure calcium borate powder
The chiral multilevel-structured calcium borate powder of the present invention is illustratively obtained by the following preparation method:
(1) anhydrous calcium chloride (CaCl)2) Dissolving in water, and fully stirring and dissolving to form a solution A;
(2) adding sucrose (C) as chiral inducer12H22O11) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) reacting boric acid (H)3BO3) Dissolving in water, and stirring to dissolve completely to form solution C;
(4) then, at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 6 minutes;
(5) then, C was slowly added dropwise to the AB mixed solution at room temperature under stirring to form a mixed reaction solution, and stirring was continued for 90 minutes.
(6) Then the mixture is transferred into a reaction kettle and reacts for 24 hours at 160 ℃. After the reaction is finished, the mixture is naturally cooled, centrifugally separated, washed by deionized water and ethanol for 3 times alternately, and then dried at 80 ℃ to obtain the chiral multilevel-structure calcium borate powder (see figure 9).
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of the anhydrous calcium chloride, the boric acid, the sucrose and the water is 1.5: 1: 1: 1530.
fig. 9 is a scanning electron micrograph of the chiral multi-stage structure calcium borate powder synthesized in this example. It can be seen from the figure that calcium borate is in a sheet-like structure, and sheets are arranged in a staggered manner to form a multilevel chiral structure.
Example 8: chiral multilevel structure calcium borate powder
The chiral multilevel-structured calcium borate powder of the present invention is illustratively obtained by the following preparation method:
(1) calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) dissolving in water, and fully stirring and dissolving to form a solution A;
(2) mixing a chiral inducer ascorbic acid (C)6H8O6) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) sodium borate decahydrate (N)a2B4O7·4H2O)) is dissolved in water, and fully stirred and dissolved to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 9 minutes;
(5) and slowly dripping the C into the AB mixed solution at room temperature under the stirring condition to form a mixed reaction solution, and continuing stirring for 120 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 8 hours at 120 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing with deionized water and ethanol for 3 times, and then drying at 80 ℃ to obtain the chiral multilevel-structure calcium borate powder.
In the process, the adding amount proportion of each raw material is as follows: the molar ratio of calcium nitrate tetrahydrate, sodium borate decahydrate, ascorbic acid and water is 1.5: 1: 1.5: 1650.
example 9: chiral multilevel structure calcium carbonate powder
The chiral multilevel-structure calcium carbonate powder of the present invention is illustratively obtained by the following preparation method:
(1) anhydrous calcium chloride (CaCl)2) Dissolving in water, and fully stirring and dissolving to form a solution A;
(2) adding a chiral inducer phenylalaninol (C)9H13NO) is dissolved in water, and the solution B is formed by fully stirring and dissolving;
(3) sodium carbonate (N)aCO3) Dissolving in water, and stirring to dissolve completely to form solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 3 minutes;
(5) and slowly dripping the C into the AB mixed solution at room temperature under the stirring condition to form a mixed reaction solution, and continuing stirring for 30 minutes.
(6) Standing and aging for 36 hours at room temperature. After the reaction is finished, centrifugal separation is carried out, deionized water and ethanol are alternately washed for 3 times, and then drying is carried out at 40 ℃ to obtain the chiral multilevel structure calcium carbonate powder (see figure 10).
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of the anhydrous calcium chloride to the sodium carbonate to the phenylalanine alcohol to the water is 1: 1: 0.75: 2100.
fig. 10 is a scanning electron micrograph of the chiral multilevel structure calcium carbonate powder synthesized in this example. The calcium carbonate is shown in the figure to be in a small flake structure, and the flakes are arranged in a staggered mode and spirally assembled and stacked to form a multi-stage chiral structure.
Example 10: chiral multilevel structure calcium carbonate powder
The chiral multilevel-structure calcium carbonate powder of the present invention is illustratively obtained by the following preparation method:
(1) mixing calcium hydroxide (Ca (OH)2) Dispersing in water, fully stirring and dissolving to form a solution A;
(2) adding chiral inducer aspartic acid (C)4H7NO4) Dissolving in water, and fully stirring and dissolving to form a solution B;
(3) ammonium carbonate ((NH)4)2CO3) Dissolving in water, and stirring to dissolve completely to form solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 3 minutes;
(5) and slowly dripping C into the AB mixed solution under the stirring condition at 60 ℃ to form a mixed reaction solution, and continuing stirring for 45 minutes.
(6) After the reaction is finished, cooling, centrifugally separating, alternately washing 3 times by deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel-structure calcium carbonate powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of calcium hydroxide, ammonium carbonate, aspartic acid and water is 1: 1: 1.5: 2400.
example 11: chiral multilevel structure barium carbonate powder
The chiral multilevel structured barium carbonate powder of the present invention is exemplarily obtained by the following preparation method:
(1) dissolving barium chloride (BaCl2) in water, and fully stirring to dissolve to form a solution A;
(2) dissolving a chiral inducer malic acid (C4H6O5) in water, and fully stirring to dissolve to form a solution B;
(3) dissolving ammonium bicarbonate (NH 4H CO3) in water, and fully stirring to dissolve to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 5 minutes;
(5, slowly dropping C into the AB mixed solution under the condition of vigorous stirring at room temperature, dropping a certain amount of ammonia water (NH 4O H) to form a mixed reaction solution, and further continuing stirring for 30 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 24 hours at 120 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel-structure barium carbonate powder.
In the process, the adding amount proportion of each raw material is as follows: the mol ratio of barium chloride, ammonium bicarbonate, malic acid and water is 1: 1: 0.75: 1480.
example 12: chiral multilevel-structure magnesium phosphate powder
The chiral multilevel-structure magnesium phosphate powder of the invention is exemplarily obtained by the following preparation method:
(1) dispersing magnesium oxide (MgO) in water, and fully stirring and dissolving to form a solution A;
(2) dissolving a chiral inducer ascorbic acid (C6H8O6) in water, and fully stirring and dissolving to form a solution B;
(3) dissolving phosphoric acid (H3PO4) in water, and fully stirring to dissolve to form a solution C;
(4) at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 10 minutes;
(5) and slowly dripping the C into the AB mixed solution at room temperature under the condition of vigorous stirring to form a mixed reaction solution, and continuing stirring for 35 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 16 hours at 150 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel-structure magnesium phosphate powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of magnesium oxide, phosphoric acid, ascorbic acid and water is 1.5: 1: 1.5: : 1650.
example 13: chiral multilevel structure alumina powder
The chiral multilevel structure alumina powder of the invention is exemplarily obtained by the following preparation method:
(1) dissolving aluminum chloride (AlCl3) in water, and fully stirring and dissolving to form a solution A;
(2) dissolving chiral inducer potassium sodium tartrate (C4H4KNaO) in water, and fully stirring and dissolving to form solution B;
(3) dissolving ammonia water (NH4 OH) in water, and fully stirring to dissolve to form a solution C;
(4) rapidly adding the B into the A under the stirring condition at room temperature to form a mixed solution, and continuously stirring for 8 minutes;
(5) slowly dropping C into the AB mixed solution under the condition of vigorous stirring at room temperature to form a mixed reaction solution, and continuing stirring for 45 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 24 hours at 180 ℃. And after the reaction is finished, naturally cooling, performing centrifugal separation, alternately washing for 3 times by using deionized water and ethanol, and drying at 80 ℃ to obtain the chiral multilevel-structure aluminum hydroxide precursor.
(7) The calcination was carried out in a muffle furnace at 600 ℃ for 6 hours. Finally obtaining the alumina powder with chiral multilevel structure.
In the process, the adding amount ratio of the raw materials is as follows: the mol ratio of the aluminum chloride, the ammonia water, the potassium sodium tartrate and the water is 1: 3: 1: 600.
example 14: chiral multilevel structure silicon nitride powder
The chiral multilevel structure silicon nitride powder of the invention is exemplarily obtained by the following preparation method:
(1) dissolving silicon chloride (SiCl4) in water, and fully stirring to dissolve to form a solution A;
(2) dissolving chiral inducer glutathione (C10H17N3O6S) in water, and fully stirring to dissolve to form solution B;
(3) dissolving ammonia water (NH4 OH) in water, and fully stirring to dissolve to form a solution C;
(4) at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 10 minutes;
(5) slowly dropping C into the AB mixed solution under the condition of vigorous stirring at room temperature to form a mixed reaction solution, and continuing stirring for 30 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 48 hours at 200 ℃. After the reaction is finished, the mixture is naturally cooled, centrifugally separated, washed for 3 times by deionized water and ethanol alternately, and then dried at 80 ℃ to obtain the chiral multilevel-structure silicon nitride powder.
In the process, the adding amount ratio of the raw materials is as follows: the mol ratio of the silicon chloride, the ammonia water, the glutathione and the water is 1: 4: 1.2: 480.
example 15: chiral multilevel structure tantalum carbide powder
The chiral multilevel structure tantalum carbide powder of the invention is exemplarily obtained by the following preparation method:
(1) dispersing tantalum pentoxide (Ta2O5) in water, and fully stirring to dissolve the tantalum pentoxide to form a solution A;
(2) dissolving a chiral inducing agent tetracycline (C22H24N2O8) in water, and fully stirring to dissolve to form a solution B;
(3) dispersing carbon powder (C) in water, and fully stirring and dissolving to form a solution C;
(4) at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 10 minutes;
(5) and C is quickly dripped into the AB mixed solution under the condition of vigorous stirring at room temperature to form a mixed reaction solution, and the stirring is continued for 60 minutes.
(6) Transferring the mixture into a high-pressure vacuum reaction kettle, and reacting for 12 hours at 300 ℃. After the reaction is finished, naturally cooling, centrifugally separating, alternately washing for 3 times by using deionized water and ethanol, and then drying at 80 ℃ to obtain the chiral multilevel-structure tantalum carbide powder.
In the process, the adding amount ratio of the raw materials is as follows: the molar ratio of tantalum pentoxide to carbon powder to tetracycline to water is 1: 1.25: 1: 1200.
example 16: chiral multilevel structure carbon nitride powder
The chiral multilevel structure carbon nitride powder of the present invention is exemplarily obtained by the following preparation method:
(1) dissolving urea (CH4N2O) in water, and fully stirring to dissolve to form a solution A;
(2) dissolving chiral inducer ammonia (C5H11NO2S) in water, and fully stirring to dissolve to form solution B;
(3) dissolving ferric sulfate (Fe2(SO4)3) in water, and fully stirring to dissolve to form a solution C;
(4) at room temperature, rapidly adding the B into the A under the stirring condition to form a mixed solution, and continuously stirring for 10 minutes;
(5) slowly dropping C into the AB mixed solution under the condition of vigorous stirring at room temperature to form a mixed reaction solution, and continuing stirring for 50 minutes.
(6) Transferring the mixture into a reaction kettle, and reacting for 24 hours at 180 ℃. After the reaction is finished, the mixture is naturally cooled, centrifugally separated, washed for 3 times by deionized water and ethanol alternately, and then dried at 80 ℃ to obtain the carbon nitride powder with the chiral multilevel structure.
In the process, the adding amount ratio of the raw materials is as follows: the mol ratio of urea to ferric sulfate to the ammonia enzyme to the water is 1: 0.2: 1: 2520.
example 17: chiral mesostructured hydroxyapatite film
The embodiment provides a preparation method of a chiral mesostructured hydroxyapatite film, which specifically comprises the following steps:
(1) a soluble calcium source calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) is dissolved in water, and the solution A is formed by fully stirring and dissolving, wherein the content of calcium nitrate tetrahydrate in the solution A is 1.25 mmol.
(2) Adding tartaric acid (C) as a chiral inducer4H6O6) Dissolving in water, stirring thoroughly to dissolve to obtain solution B with tartaric acid content of 0.625 mmol.
(3) Dissolving soluble diammonium hydrogen phosphate ((NH) as phosphorus source4)2HPO4) And a nucleation controlling agent urea (carbamide: CH (CH)4N2O) is dissolved in water, and the solution C is formed by fully stirring and dissolving, wherein the content of diammonium hydrogen phosphate and the content of urea in the solution C are respectively 0.75mmol and 1.67 mmol.
(4) And quickly adding the solution B into the solution A at room temperature to form a mixed solution, and continuously stirring for 10 minutes to obtain an AB mixed solution.
(5) Slowly dropping the solution C into the AB mixed solution while vigorously stirring at room temperature to form a mixed reaction solution, and further stirring for 30 minutes.
(6) Transferring the mixed reaction solution into a reaction kettle, adding a pretreated substrate, reacting at 180 ℃ for 24 hours, naturally cooling, taking out the substrate, alternately washing with deionized water and ethanol for 3 times, and drying at 80 ℃ to obtain the chiral mesostructured hydroxyapatite film (see figure 11).
The substrate used in this embodiment is a mica substrate, which is pre-treated in advance to achieve activation, wherein the pre-treatment operation is: the mica was tear stripped with clear glue to give a fresh exposed surface.
In the process, the adding amount ratio of the raw materials is as follows: the mol ratio of the soluble calcium source to the soluble phosphorus source to the chiral inducer to the nucleation control agent to the water is 1: 0.6: 0.5: 1.336: 1667.
in the preparation process of this example, in step S2, a chiral mesostructured hydroxyapatite thin film was synthesized using D-type, L-type, and Racemic (i.e., meso-type, hereinafter abbreviated as Rac) tartaric acid, and the synthesized thin films are hereinafter referred to as D-type, L-type, and Rac-type films, respectively.
Example 18 cell adhesion proliferation assay of hydroxyapatite films
In this test example, the chiral mesostructured hydroxyapatite films of D type, L type and Racemic type in example 17 were used to perform cell adhesion proliferation experiments, and the cell lines used were L929 cells and 3T3 cells.
The specific operation process is as follows:
1) firstly, paving a sterilized and disinfected substrate at the bottom of a cell culture plate;
2) then respectively culturing the dispersed upper L929 cells and 3T3 cells on a chiral substrate;
3) after a period of incubation, the plates were removed, washed with PBS, and fixed with 4% PFA;
4) after fixation, washing the gel for a plurality of times by PBS, and then dyeing;
5) and finally, observing and photographing under a microscope.
FIG. 12 is a microscope photograph of the adhesion proliferation of L929 cells on the chiral mesostructured hydroxyapatite film of the present invention.
As shown in fig. 12, compared to the blank mica basement membrane of the prior art, the chiral mesostructured hydroxyapatite thin film of example 12 of the present invention can selectively promote cell adhesion and proliferation, wherein the L-type membrane is favorable for cell adhesion and proliferation, and the D-type membrane is unfavorable for cell adhesion and proliferation.
FIG. 13 is a microscope photograph of the adhesion proliferation of 3T3 cells on a chiral mesostructured hydroxyapatite film in accordance with the present invention.
As shown in fig. 13, compared to the blank mica basement membrane of the prior art, the chiral mesostructured hydroxyapatite film of example 1 of the present invention can selectively promote cell adhesion and proliferation. The L-type membrane contributes to cell adhesion and proliferation, while the D-type membrane is not conducive to cell adhesion and proliferation.
Example 19:
in this test example, the D-type, L-type, and Racemic chiral mesostructured hydroxyapatite films of example 17 were used to perform a stem cell differentiation experiment, and the used stem cells were adipose-derived mesenchymal stem cells.
The specific operation process is as follows:
1) firstly, extracting fat-derived mesenchymal stem cells from the inguinal fat of a mouse, and culturing and incubating;
2) then planting, paving the sterilized and disinfected substrate at the bottom of the cell culture plate;
3) culturing the dispersed Ad-MSC cell on a hydroxyapatite film substrate with a chiral mesostructure;
3) after a period of incubation, the plates were removed, washed with PBS, and fixed with 4% PFA;
4) washing with PBS for several times after fixing, and then carrying out oil red dyeing and ALP dyeing;
5) and finally, observing and photographing under a microscope.
Fig. 14 is a microphotograph of adipogenic differentiation of the adipose-derived mesenchymal stem cells of the present invention.
As shown in fig. 14, compared with the blank mica basement membrane in the prior art, the chiral mesostructured hydroxyapatite film of example 1 of the present invention can selectively induce stem cells to differentiate. The D-type membrane is helpful for inducing the stem cells to undergo adipogenic differentiation, while the L-type membrane is not beneficial for the stem cells to undergo adipogenic differentiation.
Fig. 15 is a microphotograph of osteogenic differentiation of adipose-derived mesenchymal stem cells of the present invention.
As shown in fig. 15, compared with the blank mica basement membrane in the prior art, the chiral mesostructured hydroxyapatite film of the present invention can selectively induce stem cells to differentiate. The L-type membrane helps induce the stem cells to undergo osteogenic differentiation, while the D-type membrane is not conducive to the osteogenic differentiation of the stem cells.
The chiral multilevel structure biological ceramic material is prepared by adopting the chiral molecules which are nontoxic and biodegradable and absorbable as the asymmetric defect inducer. Simple and easy operation, wide raw material source, low cost and large-scale production. The product has controllable size and uniform appearance, and due to the existence of large specific surface area and chiral multilevel structure, the calcium-based bioceramic is widely concerned in the fields of biological separation medium, chiral recognition medium, chiral adsorption material, chiral catalyst carrier and the like, wherein the calcium-based bioceramic is an important component of human or animal bones and teeth and is not dissolved by gastric juice and intestinal juice, so the chiral multilevel structure calcium-based bioceramic can be used for cell culture substrate, selective adhesion proliferation substrate of cells, selective differentiation induction substrate of stem cells, bone filling material, bone scaffold, 3D printing substrate material, carrier of targeted drugs and the like.

Claims (10)

1. A soluble chiral molecule, namely an asymmetric fragmentation inducer, is added in the preparation process of the biological ceramic material to induce the crystal lattice of the biological ceramic material to twist or rotate in the formation process, so that the biological ceramic material with the chiral multilevel structure is formed.
2. The chiral multilevel structure bioceramic material of claim 1, comprising one or more of a barium-based bioceramic, magnesium-based bioceramic, calcium-based bioceramic, microcrystalline glass bioceramic, alumina bioceramic, fluorapatite bioceramic, aluminosilicate bioceramic, oxide bioceramic, nitride bioceramic, carbide bioceramic, boride bioceramic, silicide bioceramic species.
3. The chiral multilevel structured bioceramic material of claim 2, wherein the calcium-based bioceramic comprises one or more of hydroxyapatite, β -tricalcium phosphate, calcium silicate, calcium borate, calcium carbonate, and calcium phosphate.
4. The bioceramic material of chiral multilevel structure of any one of claims 1-3, wherein the chiral molecules are selected from one or more of chiral organic acids, chiral amino acids, chiral sugars, chiral alcohols, chiral salts, chiral esters, and other chiral molecules.
5. The chiral multilevel structure bioceramic material of claim 4, wherein the chiral organic acid is selected from one or more of tartaric acid, malic acid, lactic acid, camphorsulfonic acid, phenylglycine, cyclohexylglycine, tranexamic acid, cis-3-aminocyclohexanecarboxylic acid, and ascorbic acid.
6. The bioceramic material of chiral multilevel structure of claim 4, wherein the chiral amino acids are selected from one or more of histidine, arginine, lysine, isoleucine, phenylalanine, leucine, tryptophan, alanine, methionine, proline, cysteine, aspartic acid, valine, serine, glutamine, tyrosine, aspartic acid, glutamic acid, glutamine, and threonine.
7. The chiral multilevel structure bioceramic material of claim 4, wherein the chiral sugars are selected from one or more of glucose, fructose, galactose, ribose, deoxyribose, furanose, pyranose, maltose, sucrose, lactose, and galactose.
8. The bioceramic material of chiral multilevel structure of claim 4, wherein the chiral alcohol is selected from one or more of mannitol, xylitol, sorbitol, paclitaxel, resveratrol, ginkgo biloba polyprenol, (R) - (+) -1-phenyl-1-propanol, (S) - (-) -1-phenyl-1-propanol, phenylalamine, iditol, 2-amino-1-propanol, and galactitol.
9. A preparation method of a biological ceramic material with a chiral multilevel structure is characterized in that soluble chiral molecules, namely an asymmetric fragmentation inducer, are added in the preparation process of the biological ceramic material to induce the molecules of the biological ceramic material to generate asymmetric rotation in the formation process, so that the biological ceramic material with the chiral multilevel structure is formed.
10. The method for preparing a bioceramic material with a chiral multilevel structure according to claim 9, wherein the chiral molecules are selected from one or more of chiral organic acids, chiral amino acids, chiral sugars, chiral alcohols, chiral salts, chiral esters and other chiral molecules.
CN202210171578.8A 2022-02-24 2022-02-24 Chiral multilevel structure biological ceramic material and preparation method thereof Active CN114538398B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210171578.8A CN114538398B (en) 2022-02-24 2022-02-24 Chiral multilevel structure biological ceramic material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210171578.8A CN114538398B (en) 2022-02-24 2022-02-24 Chiral multilevel structure biological ceramic material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114538398A true CN114538398A (en) 2022-05-27
CN114538398B CN114538398B (en) 2024-03-15

Family

ID=81676637

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210171578.8A Active CN114538398B (en) 2022-02-24 2022-02-24 Chiral multilevel structure biological ceramic material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114538398B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106238102A (en) * 2016-08-26 2016-12-21 北京理工大学 There are the preparation method and applications of chirality Salen catalysis ceramic membrane
JP2018008882A (en) * 2016-07-11 2018-01-18 俊則 國府 Biologically Responsive Substance, Method for Producing Functional Ceramics and Chirality Estimation Method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018008882A (en) * 2016-07-11 2018-01-18 俊則 國府 Biologically Responsive Substance, Method for Producing Functional Ceramics and Chirality Estimation Method
CN106238102A (en) * 2016-08-26 2016-12-21 北京理工大学 There are the preparation method and applications of chirality Salen catalysis ceramic membrane

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
GUOBIN ZHANG ET AL.: "Supervariate ceramics: biomineralization mechanism", MATERIALS TODAY ADVANCES, vol. 10, pages 1 - 9 *
HANAN MOUSSA ET AL.: "High strength brushite bioceramics obtained by selective regulation of crystal growth with chiral biomolecules", ACTA BIOMATERIALIA, vol. 106, pages 351 - 359, XP086099063, DOI: 10.1016/j.actbio.2020.01.047 *
STYLIANOS O. SARRIGIANNIDIS ET AL.: "Chiral Tartaric Acid Improves Fracture Toughness of Bioactive Brushite–Collagen Bone Cements", ACS APPLIED BIO MATERIALS, vol. 3, no. 8, pages 5056 - 5066 *
WENGE JIANG ET AL.: "Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate", NATURE COMMUNICATIONS, vol. 8, pages 1 - 13 *
WENGE JIANG ET AL.: "Chiral switching in biomineral suprastructures induced by homochiral l-amino acid", SCIENCE ADVANCES, vol. 4, no. 8, pages 1 - 11 *
WENGE JIANG ET AL.: "Homochirality in biomineral suprastructures induced by assembly of single-enantiomer amino acids from a nonracemic mixture", NATURE COMMUNICATIONS, vol. 10, pages 1 - 9 *

Also Published As

Publication number Publication date
CN114538398B (en) 2024-03-15

Similar Documents

Publication Publication Date Title
CN107161969B (en) A kind of preparation method of nanometer hydroxyapatite/graphene oxide composite material
JP5740314B2 (en) Silicate-substituted hydroxyapatite
CN108404203B (en) Preparation method of reduced graphene oxide/biological glass nanofiber scaffold
Ressler et al. Strontium substituted biomimetic calcium phosphate system derived from cuttlefish bone
Chen et al. Hydroxyapatite coatings with oriented nanoplate and nanorod arrays: Fabrication, morphology, cytocompatibility and osteogenic differentiation
CN104961114B (en) Calcium and magnesium phosphate nano structural material and preparation method thereof
CN101623514A (en) Preparation method for nano hydroxylapatite doped with metal ions
CN104415399A (en) Hydroxyapatite/graphene nano-composite powder and preparation method thereof
CN106186674B (en) A kind of hollow bioactivity glass ball, preparation method and applications
CN108379589B (en) Preparation method of hydroxyapatite/graphene oxide composite material
CN113082290B (en) Zinc oxide coating-hydroxyapatite coating with bioactivity and antibacterial performance, preparation method and application
CN1644561A (en) Method for producing polymeric sol of calcium phosphate compound and method for coating the same on a metal implant
CN103656756B (en) Nano-hydroxyapatite/silk fibroin composite membrane material and preparation method thereof
TW200934461A (en) Calcium silicate-based cements and manufacturing method thereof
TWI388348B (en) Polymer or oligomer-containing calcium silicate bone cement and methods for the preparation
CN114105114B (en) Preparation method and application of chiral mesostructured hydroxyapatite film
Suchanek et al. Assessment of phase stability and in vitro biological properties of hydroxyapatite coatings composed of hexagonal rods
CN114538398B (en) Chiral multilevel structure biological ceramic material and preparation method thereof
WO2015001734A1 (en) Composite material and method for producing composite material
CN112126926B (en) Preparation method for synchronously loading bioactive zinc ions on titanium surface modified nano structure
CN114533950A (en) Biological ceramic-metal assembly for bone defect repair and preparation method thereof
Yokoi The development of novel calcium phosphate–polymer composite biomaterials with macro-to nano-level controlled hierarchical structures
KR20040099964A (en) The biocompatible implant on which is coated with hydroxyapatite/titania double layer
CN1636945A (en) Medical surface bioactive ceramic material and its prepn
CN110141684A (en) A kind of hydro-thermal sterilizing methods of hydroxyapatite coating layer surface in situ synthetic antimicrobial silver orthophosphate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant