CN111773432A - Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and preparation and application thereof - Google Patents

Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and preparation and application thereof Download PDF

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CN111773432A
CN111773432A CN201910270874.1A CN201910270874A CN111773432A CN 111773432 A CN111773432 A CN 111773432A CN 201910270874 A CN201910270874 A CN 201910270874A CN 111773432 A CN111773432 A CN 111773432A
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magnesium
based amorphous
calcium
calcium phosphate
calcium silicate
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谭丽丽
杨柯
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Institute of Metal Research of CAS
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/06—Flowable or injectable implant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high bioactivity, which comprises the following components in part by weight: solid phase material obtained by uniformly mixing composite calcium phosphate salt/calcium silicate salt and magnesium-based amorphous powder/fiber, and solidified liquid obtained by dissolving hydrogen phosphate in water. The invention also discloses a preparation method and application of the injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement and the solid filling block: uniformly mixing the curing liquid and the solid-phase substance, and blending to form a paste to obtain the injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement with high bioactivity, which is used for preparing injectable products for repairing bone tissue wounds; the bone cement is cured and dried in vitro to form a block-shaped filler for filling open bone defects. The invention has low cost of raw materials and simple preparation method, and the obtained magnesium-based amorphous-calcium phosphate/calcium silicate composite filler has high bioactivity, can form a porous structure in vivo and is beneficial to tissue repair.

Description

Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and preparation and application thereof
Technical Field
The invention belongs to the technical field of preparation of medical bone filling materials, and particularly provides a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high bioactivity, and a preparation method and application thereof.
Background
Bone defects caused by bone tumors, limb spinal deformity correction, severe bone trauma, osteoporosis, osteonecrosis and the like in clinic need to be reconstructed and treated by a bone grafting method. However, the limited availability of autogenous bone increases surgical trauma and the risk of immunological reactions and disease transmission in allogeneic bone limits its clinical use. Artificial bone implant materials have been the focus of bone tissue research, and applications that can replace autologous or allogeneic bone are desired. High porosity, degradability, high initial mechanical properties and good biological activity are essential conditions that bone repair materials must meet.
Calcium sulfate has been used in bone replacement materials for over 100 years and has proven to be safe and biocompatible. In 1980, Coetzee et al used calcium sulfate for 110 cases of defective skull and facial bone, and he concluded that calcium sulfate is an excellent substitute for bone graft, even comparable to bone graft itself. Calcium sulphate has then been criticized for its degradation before the new bone has not been fully inserted, and as a result calcium sulphate is used as a bone filling material, its degradation rate is too fast, and therefore calcium phosphate is used as a filler for bone defects and injectable calcium phosphate cements have been developed. Calcium Phosphate Cement (CPC), also known as Hydroxyapatite (HAC), is a self-setting non-ceramic hydroxyapatite artificial bone material first developed by Brown and Chow. The material has good biocompatibility, osteoconductivity, biosafety, arbitrary shaping and isothermality in the curing process, is a novel bone tissue repair and substitute material, receives wide attention of numerous scholars at home and abroad, and becomes one of the hot spots of research and application in the field of clinical tissue repair. CPC is prepared by mixing solid phase and liquid phase raw materials in a certain proportion into paste, implanting into a body, and crystallizing and solidifying in the in vivo environment. The chemical components of the final product after curing are similar to the inorganic components of bone tissues, the crystal phase structure of the final product is also similar to the bone tissues, the final product can be gradually degraded and absorbed after being implanted into bone defects, and calcium and phosphorus released by degradation participate in the formation of the bone tissues in the defect areas. The compression strength of the CPC final product is 36-55 MPa and is between that of cancellous bone and that of cortical bone. The magnitude of compressive strength is closely related to the particle size of the solid phase component used in the solidification process of CPC, the porosity of the final product and HA crystallinity, and the porosity of the final product is directly related to the powder-to-liquid ratio during mixing. The CPC with larger compressive strength is suitable for repairing bone defects of low-load parts, and the CPC with smaller compressive strength is suitable for repairing bone defects or small bone defects of non-load parts and filling root canals. However, the biological activity of CPC still needs to be improved in order to achieve better bone repair effect. Calcium Silicate (CS) -based materials have excellent bioactivity compared to calcium phosphate materials and have received increasing attention in recent years. A large number of researches prove that the CS-based material achieves the effect of quickly forming apatite deposition through the release of Si ions and can promote the formation and reconstruction of bone tissues. The self-setting CS bone cement has the advantage of low self-setting time, and exhibits good bone conductivity and the property of inhibiting inflammation of human dental pulp cells.
However, CPC and CS have several problems in that although they have a certain porosity, since the pore size is in the nanometer or submicron order, they lack macropores for promoting the growth of bone tissue, and not only osteocytes cannot grow in, but also interstitial fluid is difficult to permeate, and it is difficult to exert their osteoconductive effect; moreover, the degradation speed of the calcium silicate bone cement is too low relative to the growth speed of bone tissues, particularly, the degradation and absorption processes of the calcium silicate bone cement in vivo are carried out layer by layer, so that the absorption rate is low, the degradation is slow, and the generation and reconstruction of new bone tissues are hindered; in addition, the exertion of the biological activities of the two has the bone conduction effect, but the biological activities are exerted to a great extent by means of the biological active ions generated by the degradation of self materials, and the low degradation speed of the two makes the exertion of the biological activities insufficient to meet the clinical requirements, and particularly the biological activities are lower in the early stage of implantation.
Disclosure of Invention
In order to overcome the defects of the calcium phosphate/calcium silicate bone cement, the invention provides a preparation method of the calcium phosphate/calcium silicate bone cement and a block filler, which have high biological activity and can be degraded in vivo to form a hole. According to the characteristics that the degradation speed of the magnesium-based amorphous metal material in vivo is higher than that of a calcium phosphate bone cement material, magnesium ions with high biological activity are generated by degradation, and hydrogen is released while degradation, the magnesium-based amorphous metal powder/fiber and the calcium phosphate/calcium silicate powder are compounded, and the characteristic that the calcium phosphate/calcium silicate can be self-cured is utilized to prepare novel bone cement and a massive filling material which have higher biological activity, can be degraded in vivo to form holes, have high later degradation speed and are beneficial to the growth of new bone tissues. In addition, because the degradation speed of the magnesium-based amorphous alloy in vivo is lower than that of crystalline magnesium and the magnesium-based amorphous alloy, the problems of long solidification time and premature collapse in vivo of the composite material caused by high degradation speed of magnesium and the magnesium-based amorphous alloy can be avoided in the preparation process of the composite material.
The technical scheme adopted by the invention is as follows:
a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high bioactivity is characterized in that: the injectable calcium phosphate/calcium silicate filler is added with magnesium-based amorphous powder/fiber to form a composite filler.
As a preferred technical scheme:
the magnesium-based amorphous alloy comprises MgZnCaSr, wherein the Zn content is as follows: 21-40 at.%, the Ca content is: 2-7 at.%, Sr content: 0-5 at.%, balance Mg.
The magnesium-based amorphous powder/fiber content accounts for 1-30 wt.% of the composite filler
The magnesium-based amorphous powder is spherical or irregular, and the particle size is less than 1 mm.
The magnesium-based amorphous fiber has the length of 1-30mm and the width of 0.1-1 mm.
The invention also provides a preparation method of the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler, which is characterized by comprising the following steps:
(1) mixing the calcium phosphate/calcium silicate bone cement solid-phase powder with the magnesium-based amorphous powder/fiber to obtain solid-phase composite powder;
(2) preparing a buffer solution with the equal molar concentration of 0.2-1.0 mol% of sodium dihydrogen phosphate and disodium hydrogen phosphate by using analytically pure or analytically pure sodium dihydrogen phosphate, a disodium hydrogen phosphate reagent and deionized water or distilled water as a curing solution;
(3) and (3) preparing the solid-phase composite powder prepared in the step (1) and the curing liquid prepared in the step (2) according to the solid-liquid ratio of 0.1-3: 1 to prepare composite bone cement slurry, wherein the prepared bone cement slurry can be directly injected into a bone defect part by using an injector for use.
(4) And (4) injecting the bone cement slurry prepared in the step (3) into a mold for curing for 20 minutes to 6 hours, and then drying at 80 to 100 ℃ to prepare a blocky filling material for filling treatment of open bone defects.
The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method can be blended to form paste, and the injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement with high bioactivity can be obtained and used for preparing injectable products for bone tissue wound repair.
The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method can be cured and dried in vitro after being blended to form paste to form a blocky filler for filling open bone defects.
The degradation speed of the calcium phosphate/calcium silicate bone cement is slow, the degradation speed of the magnesium-based amorphous powder/fiber is higher than that of the calcium phosphate/calcium silicate bone cement, magnesium ions with high biological activity generated by degradation can play a role of bone induction, the biological activity of the calcium phosphate/calcium silicate can be further enhanced, particularly in the initial stage of implantation, the calcium phosphate/calcium silicate can not play a role of biological activity due to the slow degradation speed, and the degradation speed of the magnesium-based amorphous powder/fiber is high, so that the bone induction can be effectively played in the initial stage, the early bone healing is promoted, and effective complementation is formed between the degradation speed of the magnesium-based amorphous powder/fiber and the time of the biological;
the vacancy left by the degradation of the magnesium-based amorphous powder/fiber and the hydrogen generated by the degradation can play a pore-forming role, bone cells can grow in the pores, the vascularization of the material is facilitated, and the supply of nutrition to the internal tissues of the material is ensured, so that the growth of new bone tissues and the reconstruction of autologous bones are promoted; meanwhile, the degradation of the magnesium-based amorphous powder/fiber can increase the contact surface area of calcium phosphate/calcium silicate and body fluid, and increase the degradation speed of the implant in the later period.
In addition, because the degradation speed of the magnesium-based amorphous alloy in vivo is lower than that of crystalline magnesium and the magnesium-based amorphous alloy, the problems of long solidification time and premature collapse in vivo of the composite material caused by high degradation speed of magnesium and the magnesium-based amorphous alloy can be avoided in the preparation process of the composite material.
The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler product has the advantages of low cost of raw materials and simple preparation method, has high bioactivity, can form a porous structure in vivo, is beneficial to tissue repair, is mainly used for bone defect repair and bone tissue engineering scaffold materials, and can also be used as a dental repair material. When in use, the prepared slurry can be directly injected into the bone defect part by an injector, or the slurry can be injected into a mould to be solidified and molded and then implanted into the bone defect part.
Drawings
FIG. 1 is a photograph of MgZnCa Mg-based amorphous powder-calcium phosphate composite bone cement.
FIG. 2 shows that after MgZnCa Mg-based amorphous powder-calcium phosphate composite bone cement is cured and soaked in simulated body fluid for 24h, a large number of macroscopic pores appear on the surface.
FIG. 3 is calcium phosphate cement and Mg69Zn26Ca5Macroscopic photographs of the magnesium-based amorphous powder-calcium phosphate composite bone cement before and at 7 and 14 days of immersion in simulated body fluid, wherein the ratio of calcium phosphate bone cement: before soaking (a), soaking for 7 days (b) and soaking for 14 days (c); mg (magnesium)69Zn26Ca5Magnesium-based amorphous powder-calcium phosphate composite bone cement: d) before soaking, 7 days (e) and 14 days (f).
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
α -calcium phosphate powder and Mg69Zn26Ca5Magnesium-based amorphous powder (spherical, particle size of 0.5mm) in which Mg is mixed69Zn26Ca5The magnesium-based amorphous powder accounts for 5 percent by weight(ii) a Preparing buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of the analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 0.3: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use.
In vitro experiments prove that the magnesium-calcium phosphate composite bone cement has good injectability (shown as figure 1) and self-curing performance, and a large number of macroscopic holes (shown as figure 2) appear on the surface after being soaked in simulated body fluid for 24 hours, which indicates that magnesium-based amorphous powder in the composite bone cement begins to degrade at the early stage of soaking, a large number of holes are formed in the bone cement, and favorable conditions can be provided for the ingrowth of surrounding bone tissues. FIG. 3 is a macroscopic photograph of a calcium phosphate cement and a MgZnCa Mg-based amorphous powder-calcium phosphate composite cement before and after 7 and 14 days of immersion in a simulated body fluid. As can be seen from the figure, Mg69Zn26Ca5The magnesium-based amorphous powder-calcium phosphate composite bone cement still maintains an intact structure after being soaked for 14 days, and the calcium phosphate bone cement is collapsed, so that it can be seen that Mg69Zn26Ca5The magnesium-based amorphous powder-calcium phosphate composite bone cement has excellent anti-collapsibility.
Example 2
α -calcium phosphate powder and Mg67Zn28Ca4Sr1Magnesium-based amorphous powder (spherical, particle size of 0.5mm) in which Mg is mixed67Zn28Ca4Sr1The magnesium-based amorphous powder accounts for 5 percent by weight; preparing buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of the analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 0.4: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use. The prepared bone cement slurry is injected into a mold for curing for 2.1 hours, and then is dried at 80-100 ℃ to prepare a massive filling material for filling treatment of open bone defects.
Animal experiments prove that compared with the Mg-free state67Zn28Ca4Sr1α -tricalcium phosphate bulk filler of magnesium-based amorphous powder, Mg67Zn28Ca4Sr1The degradation period of the magnesium-based amorphous-calcium phosphate composite bulk filler is obviously short, and bone tissues grow into the magnesium-calcium phosphate composite bulk filler due to the degradation of magnesium, so that high bioactivity is shown.
Example 3
α -calcium phosphate powder and Mg65Zn30Ca4Sr1Magnesium-based amorphous powder (irregular shape, maximum size of 1mm) in which Mg is mixed65Zn30Ca4Sr1The magnesium-based amorphous powder accounts for 5 percent by weight; preparing buffer solution with equal molar concentration of 1.0 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate by using analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; and (3) preparing the composite bone cement slurry by the prepared solid-phase composite powder and the prepared curing liquid according to the solid-liquid ratio of 1: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use. The prepared bone cement slurry is injected into a mold to be cured for 30 minutes, and then is dried at 80-100 ℃ to prepare a massive filling material for filling treatment of open bone defects.
Animal experiments prove that compared with the Mg-free state65Zn30Ca4Sr1α -tricalcium phosphate bulk filler of magnesium-based amorphous powder, Mg65Zn30Ca4Sr1The magnesium-based amorphous-calcium phosphate composite block filler has obviously accelerated repair speed on cortical bone.
Example 4
Mixing β -tricalcium phosphate (β -TCP) powder with Mg70Zn26Ca2Sr2Magnesium-based amorphous powder (irregular shape, maximum size of 1mm) in which Mg is mixed70Zn26Ca2Sr2The magnesium-based amorphous powder accounts for 10 percent by weight; preparing sodium dihydrogen phosphate and disodium hydrogen phosphate with equal molar concentration of 1.0 by using analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized waterTaking a buffer solution with concentration as a curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 0.7: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use.
Animal experiments prove that compared with the Mg-free state70Zn26Ca2Sr2The β -tricalcium phosphate bone cement of magnesium-based amorphous powder has the advantages that the degradation speed of the bone cement is accelerated after the bone cement is compounded, holes appear, and the repair speed of cortical bone is obviously accelerated.
Example 5
Mixing β -tricalcium phosphate (β -TCP) powder with Mg70Zn26Ca4Mixing magnesium-based amorphous powder (spherical, particle size of 0.3mm), wherein Mg70Zn26Ca4The magnesium-based amorphous powder accounts for 20% by weight; preparing buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of the analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 2.5: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use.
In vitro experiments prove that the Mg70Zn26Ca4The Mg-based amorphous- β -TCP composite bone cement has good injectability and self-curing performance, and a large number of macroscopic holes appear on the surface after the Mg-based amorphous- β -TCP composite bone cement is soaked in simulated body fluid for 24 hours, which shows that Mg in the composite bone cement is in the early stage of soaking70Zn26Ca4The amorphous powder begins to degrade and forms a large number of pores in the bone cement, which may provide favorable conditions for the ingrowth of surrounding bone tissue.
Example 6
Mixing Mg68Zn26Ca1Sr5Amorphous fiber (10 mm long and 0.8mm wide) was mixed with α -tricalcium phosphate powder, in which Mg is present68Zn26Ca1Sr5The amorphous fiber accounts for 20% by weight; preparing buffer with equal molar concentration of 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate by using analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized waterThe solution is used as a curing liquid; and (3) preparing the composite bone cement slurry by the prepared solid-phase composite powder and the prepared curing liquid according to the solid-liquid ratio of 3: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use. The prepared bone cement slurry is injected into a mold for curing for 2 hours, and then is dried at 80-100 ℃ to prepare a massive filling material for filling treatment of open bone defects.
Animal experiments prove that compared with α -tricalcium phosphate blocky filler without MgZnCa amorphous fiber, Mg68Zn26Ca1Sr5The degradation period of the amorphous fiber- α -tricalcium phosphate composite blocky filler is obviously short, and due to the degradation of MgZnCa amorphous fibers, bone tissues grow into Mg68Zn26Ca1Sr5The amorphous fiber- α -tricalcium phosphate composite block filler shows high bioactivity.
Example 7
Mixing Mg67Zn30Ca3Amorphous fiber (15 mm long and 1.0mm wide) was mixed with β -tricalcium phosphate powder, in which Mg is present67Zn30Ca3The weight ratio of the fiber is 30 percent; preparing buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of the analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; and (3) preparing the composite bone cement slurry by the prepared solid-phase composite powder and the prepared curing liquid according to the solid-liquid ratio of 1: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use.
Animal experiments prove that compared with the Mg-free state67Zn30Ca3β -tricalcium phosphate cement of amorphous fibres, Mg67Zn30Ca3The amorphous fiber- β -tricalcium phosphate composite bone cement has obviously accelerated repair speed on cortical bone.
Example 8
Mixing Mg66Zn30Ca2Sr2Amorphous fiber (5 mm long and 0.5mm wide) was mixed with β -tricalcium phosphate powder, in which Mg is present66Zn30Ca2Sr2The amorphous fiber accounts for 30% of the weight ratio; with analytically pure phosphoric acidPreparing a buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of sodium dihydrogen phosphate, a disodium hydrogen phosphate reagent and deionized water as a curing solution; and (3) preparing the composite bone cement slurry by the prepared solid-phase composite powder and the prepared curing liquid according to the solid-liquid ratio of 1: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use. The prepared bone cement slurry is injected into a mold to be cured for 1.2 hours, and then is dried at 80-100 ℃ to prepare a massive filling material for filling treatment of open bone defects.
Animal experiments prove that compared with the Mg-free state66Zn30Ca2Sr2The β -tricalcium phosphate blocky filling material of the amorphous fiber has the advantages that the degradation speed of the blocky filling material is accelerated after the composition, holes appear on the surface, and the repair speed of cortical bone is obviously accelerated.
Example 9
Mixing Mg64Zn30Ca3Sr3Mixing amorphous fiber (7 mm long and 0.5mm wide) with calcium silicate powder, wherein Mg64Zn30Ca3Sr3The amorphous fiber accounts for 5% by weight; preparing buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate equal to that of the analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water as curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 0.5: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use.
Animal experiments prove that compared with the Mg-free state64Zn30Ca3Sr3The amorphous fiber calcium silicate bone cement has the advantages that the degradation speed of the bone cement is accelerated after the composition, holes are formed on the surface, and the repair speed of cortical bone is obviously accelerated.
Example 10
Mixing Mg64Zn30Ca1Sr5Amorphous fiber (length 3mm, width 0.2mm) was mixed with calcium silicate powder, wherein Mg is present64Zn30Ca1Sr5The amorphous fiber accounts for 5% by weight; using analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionizationPreparing a buffer solution with the molar concentration of 0.5 mol of sodium dihydrogen phosphate and the molar concentration of disodium hydrogen phosphate by using water as a curing solution; the prepared solid phase composite powder and the prepared curing liquid are prepared into the composite bone cement slurry according to the solid-liquid ratio of 0.6: 1. The prepared bone cement slurry can be directly injected into the bone defect part by a syringe for use. The prepared bone cement slurry is injected into a mold to be cured for 1.5 hours, and then is dried at 80-100 ℃ to prepare a massive filling material for filling treatment of open bone defects.
Animal experiments prove that compared with the Mg-free state64Zn30Ca1Sr5The amorphous fiber calcium silicate massive filling material is compounded, so that the degradation speed of the massive filling material is accelerated, holes are formed on the surface, and the repair speed of cortical bone is obviously accelerated.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. A magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high bioactivity is characterized in that: the injectable calcium phosphate/calcium silicate filler is added with magnesium-based amorphous powder/fiber to form a composite filler.
2. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous alloy comprises MgZnCaSr, wherein the Zn content is as follows: 21-40 at.%, the Ca content is: 2-7 at.%, Sr content: 0-5 at.%, balance Mg.
3. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous powder/fiber content accounts for 1-30 wt% of the composite filler.
4. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous powder is spherical or irregular, and the particle size is less than 1 mm.
5. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous fiber has the length of 1-30mm and the width of 0.1-1 mm.
6. A method for preparing the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, comprising the steps of:
(1) mixing the calcium phosphate/calcium silicate bone cement solid-phase powder with the magnesium-based amorphous powder/fiber to obtain solid-phase composite powder;
(2) preparing a buffer solution with the equal molar concentration of 0.2-1.0 mol% of sodium dihydrogen phosphate and disodium hydrogen phosphate by using analytically pure or analytically pure sodium dihydrogen phosphate, a disodium hydrogen phosphate reagent and deionized water or distilled water as a curing solution;
(3) and (3) preparing the solid-phase composite powder prepared in the step (1) and the curing liquid prepared in the step (2) according to the solid-liquid ratio of 0.1-3: 1 to prepare the composite bone cement slurry.
7. The method for preparing the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 6, wherein: and (4) injecting the bone cement slurry prepared in the step (3) into a mold, curing for 20 minutes to 6 hours, and then drying at 80 to 100 ℃ to prepare the blocky filling material.
8. Use of a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of claim 6 for the preparation of injectable products for bone tissue wound repair.
9. Use of the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of claim 7 for preparing a filler for open bone defects.
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