CN116236623A - Space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material and preparation method and application thereof - Google Patents
Space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material and preparation method and application thereof Download PDFInfo
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- CN116236623A CN116236623A CN202310210621.1A CN202310210621A CN116236623A CN 116236623 A CN116236623 A CN 116236623A CN 202310210621 A CN202310210621 A CN 202310210621A CN 116236623 A CN116236623 A CN 116236623A
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 118
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 33
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 201000009859 Osteochondrosis Diseases 0.000 title claims abstract description 24
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 37
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002344 surface layer Substances 0.000 claims abstract description 17
- 238000000016 photochemical curing Methods 0.000 claims abstract description 12
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical group C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 7
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- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 10
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 9
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- 229910000882 Ca alloy Inorganic materials 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
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- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims description 3
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- OOIBFPKQHULHSQ-UHFFFAOYSA-N (3-hydroxy-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2(O)CC1(OC(=O)C(=C)C)C3 OOIBFPKQHULHSQ-UHFFFAOYSA-N 0.000 description 13
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Abstract
The invention discloses a space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material and a preparation method and application thereof, and belongs to the technical field of biomedicine. The magnesium alloy composite hydrogel stent material sequentially comprises a basal layer, an intermediate layer and a surface layer from inside to outside, wherein the basal layer is DCPD modified porous magnesium alloy; the intermediate layer and the surface layer are formed by curing a photo-curing hydrogel, wherein the photo-curing hydrogel is a methacryloyl modified hydrogel, and the photo-curing hydrogel used for the surface layer contains zinc ions. The invention endows the common material with new functions, good performance and simple preparation mode, can be widely applied to the integrated repair of infectious osteochondral defects, and realizes the controllable regulation of antibiosis and repair promotion.
Description
Technical Field
The invention belongs to the technical field of biomedicine, and particularly relates to a space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material, and a preparation method and application thereof.
Background
With the development of society, open fracture caused by high-energy wound is increasing, and the probability of infectious osteochondral defect is increasing, and although anti-infection and operation treatment are greatly developed for a long time, the treatment effect is not ideal because of the infection and bone defect double lesions of patients.
Magnesium alloys, which are biodegradable metals, have good biocompatibility and an ideal young's modulus close to natural bone, are widely recognized as potential revolutionary biomaterials for orthopedics. The porous magnesium alloy not only can meet the bearing requirement of materials, but also can provide three-dimensional growth space and channel for cells, thereby being capable of being integrated with human bones as soon as possible. However, it is difficult for a single magnesium alloy scaffold to simultaneously perform antibacterial and repair functions on infectious osteochondral defects.
The zinc ion is used as a trace element necessary for human body, plays an important role in regulating cell growth and differentiation, immune system and nervous system functions, has good biocompatibility and has a good antibacterial effect. However, there are two different physiological and pathological processes of infection and defect in the infectious osteochondral defect, and there is a sequence of anti-infection and osteochondral repair in the treatment stage, so that the existing built-in object cannot achieve the integrative repair of osteochondral and the controllable regulation of anti-infection and repair promotion. Therefore, how to construct an implant that can promote the integrated repair of osteochondral and to achieve the controlled regulation of antibacterial and repair-promoting actions is a problem currently in the prime of solution.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the technical problems, the invention provides the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel bracket material, and the preparation method and application thereof, which endow the common material with new functions, good performance and simple preparation mode, and can be widely applied to the integrated repair of infectious osteochondral defects to realize the controllable adjustment of antibiosis and repair promotion.
The technical scheme is as follows: the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material sequentially comprises a basal layer, an intermediate layer and a surface layer from inside to outside, wherein the basal layer is DCPD modified porous magnesium alloy; the intermediate layer and the surface layer are formed by curing a photo-curing hydrogel, wherein the photo-curing hydrogel is a methacryloyl modified hydrogel, and the photo-curing hydrogel used for the surface layer contains zinc ions.
Preferably, the pores of the magnesium alloy are 500 μm to 1000 μm.
Preferably, the surface layer uses a photocurable hydrogel having a concentration of zinc ions of 1X 10 -5 ~9×10 -3 mol/L。
Preferably, the photocurable hydrogel is selected from the group consisting of methacryloylated hyaluronic acid, methacryloylated gelatin, methacryloylated sodium alginate, methacryloylated chitosan, methacryloylated dextran, methacryloylated chondroitin sulfate, and methacryloylated silk fibroin.
Preferably, the light-cured hydrogel used in the intermediate layer is 10g/L of a methacryloylated hyaluronic acid solution.
Preferably, the surface layer uses a photo-setting hydrogel of 50g/L of a solution of methacryloylated gelatin.
The preparation method of the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material comprises the following steps:
firstly, preparing porous magnesium alloy by using magnesium alloy as a raw material and NaCl particles as pore-forming agents through a negative pressure seepage casting method, and electrodepositing a DCPD coating to obtain a substrate layer;
step two, performing methacryloylation modification on the hydrogel, adding the hydrogel into a photoinitiator without zinc ions to obtain a hydrogel solution without zinc ions, immersing a substrate layer in the hydrogel solution without zinc ions, and performing ultraviolet light curing to form an intermediate layer;
and thirdly, performing methacryloylation modification on the hydrogel, adding the hydrogel into a photoinitiator containing zinc ions to obtain a hydrogel solution containing zinc ions, immersing the intermediate layer in the hydrogel solution containing zinc ions, and performing ultraviolet light curing to form a surface layer to obtain the composite hydrogel scaffold material.
Preferably, the preparation method of the porous magnesium alloy in the first step comprises the following steps: magnesium alloy with the purity of 99.95% and magnesium-calcium alloy with the purity of Mg-30wt.% Ca are used as raw materials, spherical NaCl particles with different diameters after pretreatment are used as pore formers, the smelted raw materials are poured into gaps of the pore formers under negative pressure environment, after cooling and demoulding, the NaCl particles are removed by ultrasonic cleaning in alkali liquor, and then the porous magnesium alloy is obtained by drying.
Further, the pretreatment method of the NaCl particles is as follows: and (3) placing NaCl particles into a heat treatment furnace, heating once at 50 ℃ and preserving heat for 30min, heating to 400 ℃ in a gradient way, cooling, sieving and vacuum sealing for standby after the treatment is finished.
Further, the smelting method of the raw materials comprises the following steps: placing magnesium alloy with purity of 99.95% into a mold with temperature of 400-450 ℃, and introducing CO with volume fraction of 96% after the temperature reaches 450 DEG C 2 And 4% SF 6 As a protective gas, heating to 660 ℃ and preserving heat; after the magnesium alloy with the purity of 99.95% is completely melted, wrapping the magnesium-calcium alloy with Mg-30wt.% Ca by using aluminum foil, adding the wrapped magnesium-calcium alloy, stirring, skimming, standing after the magnesium alloy is completely melted, and heating to 760 ℃ for standby.
Further, the cleaning process is specifically as follows: firstly, carrying out ultrasonic cleaning and oil removal by using absolute ethyl alcohol, then carrying out ultrasonic cleaning by using sodium hydroxide solution to remove NaCl particles, then carrying out ultrasonic activation on the surface of the porous magnesium alloy by using nitrate alcohol, and finally carrying out ultrasonic cleaning by using double distilled water.
Further, the concentration of the sodium hydroxide solution is 24g/L, and the pH is more than 13.
Further, the volume fraction of nitric acid in the alcohol nitrate was 4%.
Preferably, the preparation method of the DCPD coating in the step one is as follows: weighing sodium phosphite powder, dissolving the sodium phosphite powder in double distilled water according to the mass fraction of 3.1%, adding calcium nitrate into the double distilled water according to the mass fraction of 5.3%, and adjusting the pH value to 3.5 to obtain a deposition solution; adding the porous magnesium alloy into the deposition solution, reacting for 3 hours at 45 ℃, taking out, ultrasonically cleaning, drying and vacuum sealing.
Preferably, the method for the methacryloylation modification of the hydrogel in the second and third steps comprises the following steps: the hydrogel is dissolved in double distilled water according to the ratio of 0.02g/mL, then reacts with 20 times of excessive methacrylic anhydride, the pH value is adjusted to 8, then the hydrogel is placed at the temperature of 5 ℃ for incubation for 24 hours, the incubated solution is used for precipitating methacrylic acid and methacrylic anhydride, and finally the precipitate is freeze-dried to obtain the methacryloyl modified hydrogel.
Preferably, the photoinitiator in the second and third steps is a solution of phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate.
The application of the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material in preparing bone implants or spinal column orthopedic medical devices.
The beneficial effects are that: the invention provides a controllable slow-release porous magnesium alloy material prepared by a modification mode of pore adjustment and coating coverage, wherein a compact and slowly-degraded polymer hydrogel intermediate layer is coated on the outer layer of the modified porous magnesium alloy, so that the contact water molecules of the magnesium alloy are reduced, the degradation rate of the magnesium alloy is further reduced, the concentration and the molecular weight of the polymer hydrogel can be regulated, the contact water molecules of the magnesium alloy can be regulated, and the controllable regulation of the degradation rate of the magnesium alloy is realized, wherein the pores of the magnesium alloy can be 550 mu m, 750 mu m and 950 mu m.
The invention also provides an enhanced material antibacterial mode. The magnesium ion released after the magnesium alloy is degraded has a certain antibacterial property, but the infection focus of the infectious osteochondral defect can not be effectively controlled. When the outer hydrogel is rapidly degraded, zinc ions can be locally accumulated, so that the early sterilization effect can be achieved, and after preliminary effective sterilization, slowly degraded magnesium ions penetrate into a local microenvironment to achieve a continuous antibacterial effect.
The invention also creates a space-time adjustment system. According to the manufacturing sequence, the porous magnesium alloy surface covered by the coating is covered with the slowly degraded polymer hydrogel, and then the outermost layer is covered with a layer of rapidly degraded hydrogel containing zinc ions, so as to form the composite stent. The stent system can realize the sequential release of ions through two hydrogels with differential degradation characteristics on the outer layer of the alloy, and can realize the control of the slow release rate and the local ion concentration by regulating the concentration and the molecular weight of the hydrogels; in addition, by compounding ions with different types, numbers and the like at different parts of the hydrogel, the slow-release spatial regulation of the composite stent can be realized.
Drawings
FIG. 1 is a schematic illustration of a method of preparing a space-time adjustable, infectious osteochondral defect magnesium alloy composite hydrogel scaffold of the present invention;
FIG. 2 is a general view and a scanning electron microscope view of the magnesium alloy of the present invention;
FIG. 3 is a scanning electron microscope image of two hydrogels of the present invention;
FIG. 4 is a schematic view of a magnesium alloy composite hydrogel scaffold prepared in example 1 of the present invention;
FIG. 5 is a schematic view of the antibacterial action of example 1 of the present invention;
FIG. 6 is a graph showing the time variation of ion concentration at different concentrations of zinc ion doping amount in example 1 of the present invention;
fig. 7 is a schematic application diagram of embodiment 1 of the present invention.
Description of the embodiments
The invention is further described below with reference to the drawings and specific embodiments.
Example 1
The preparation method of the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material comprises the following steps:
(1) Preparation of basal layer (magnesium scaffold)
The preparation method comprises the following steps: commercial magnesium alloy magnesium ingots with the raw material purity of 99.95% and Mg-30wt.% Ca magnesium-calcium intermediate alloy are used, and the pore-forming agent is spherical industrial NaCl particles with the particle diameters of about 550 mu m, 750 mu m and 950 mu m.
Pretreatment of pore-forming particles: since the industrial NaCl particles contain a certain spinel, explosion can occur under high-temperature heating, and the explosion risk also exists when the industrial NaCl particles are contacted with the magnesium melt. Therefore, the NaCl particles need to be pretreated before smelting. And (3) placing NaCl particles in a heat treatment furnace, heating the NaCl particles from 100 ℃ to 400 ℃ in a gradient way, heating the NaCl particles once every 50 ℃ and preserving the temperature for 30 minutes each time, taking the NaCl particles out after the treatment is finished, sieving the NaCl particles again after cooling, and sealing the NaCl particles in vacuum as soon as possible for standby.
Smelting: the pretreated three-particle-size NaCl particles are respectively poured into three molds and compacted, the molds are placed in a heating furnace, and the preheating temperature is set to be 400 ℃. Heating the die to 400 ℃, placing the cleaned graphite crucible into a resistance furnace, placing a pre-weighed raw material magnesium ingot into the crucible, setting the initial furnace temperature to be 450 ℃, and introducing 96% CO into a hearth of the resistance furnace after the temperature reaches 2 And 4% SF 6 The shielding gas is mixed to prevent combustion of the magnesium melt. At the same time, the temperature of the die is raised to 660 ℃ for heat preservation. After the magnesium ingot is completely melted, wrapping the prepared magnesium-calcium intermediate alloy with aluminum foil, putting the wrapped magnesium-calcium intermediate alloy into a crucible, fully stirring the magnesium-calcium intermediate alloy after the magnesium ingot is completely melted, skimming slag, standing the magnesium-calcium intermediate alloy, and heating the furnace to 760 ℃ for standby.
Pouring: taking out the mould from the heating furnace by using holding pliers, fixing the mould on a flange plate of a negative pressure seepage device, simultaneously pouring the magnesium melt into the mould from an upper opening of the mould, and opening a vacuum valve to ensure that the magnesium melt is uniformly distributed in gaps among NaCl pore-forming particles under a negative pressure environment. And after the die is naturally cooled, demolding to obtain the composite body of the magnesium alloy and NaCl particles.
And (3) alkaline washing to remove the NaCl prefabricated template: cutting the Mg-NaCl composite obtained by smelting into a circular sheet with phi=10 mm, d=2 mm and a circular bar with phi=10 mm, d=10 mm by using a wire electric discharge machine, degreasing by using absolute ethyl alcohol in an ultrasonic cleaner, removing NaCl particles by ultrasonic cleaning in a NaOH solution (24 g/L, pH > 13), finally activating the surface of the foam magnesium bracket by using 4vol.% nitric acid alcohol for 30 seconds, and drying after double-distilled water ultrasonic cleaning to obtain the porous magnesium alloy.
Coating coverage: weigh a certain weight of sodium phosphite (Na 2 HPO 4 ) Dissolving the powder in double distilled water according to the mass fraction of 3.1%, preparing a solution, and then according to the following steps5.3% by mass of a certain weight of calcium nitrate (Ca (NO 3 ) 2 ) Adding the mixture into the solution, uniformly mixing, regulating the pH value to 3.5 to obtain a deposition solution, putting the deposition solution into the prepared porous magnesium alloy, reacting for 3 hours at 45 ℃, taking out a sample, putting the sample into acetone, ultrasonically cleaning the sample for 10 minutes, ultrasonically cleaning the sample by double distilled water, drying the sample, and sealing the sample in vacuum.
(2) Raw material preparation of intermediate layer and surface layer (modification of hydrogel and ion loading)
Photo-curing modification: in this example, methacryloylated hyaluronic acid and methacryloylated gelatin are taken as examples, respectively, and those skilled in the art can freely match with methacryloylated sodium alginate, methacryloylated chitosan, methacryloylated dextran, methacryloylated chondroitin sulfate and methacryloylated silk fibroin.
Photo-curing modification of hyaluronic acid: a weight of Hyaluronic Acid (HA) powder was weighed, dissolved in double distilled water at a weight-to-volume ratio of 2% w/v, reacted with 20-fold excess Methacrylic Anhydride (MA) in solution, adjusted to PH 8 with 5mol/L sodium hydroxide (NaOH), and then incubated at 5 ℃ for 24 hours. The incubated solution was then precipitated with 95% ethanol and repeatedly operated to wash away more methacrylic acid and methacrylic anhydride, after which the obtained precipitate was freeze-dried to obtain methacrylated hyaluronic acid (HAMA).
Photo-curing modification of gelatin: a certain weight of gelatin (Gel) powder was weighed, dissolved in double distilled water at a weight-to-volume ratio of 2% w/v, reacted with 20-fold excess Methacrylic Anhydride (MA) in solution, adjusted to PH 8 with 5mol/L sodium hydroxide (NaOH), and then the solution was incubated at 5 ℃ for 24 hours. The incubated solution was then precipitated with 95% ethanol and repeatedly operated to wash away more methacrylic acid and methacrylic anhydride, after which the obtained precipitate was freeze-dried to obtain methacryloylated hyaluronic acid (GelMA).
Configuration and ion loading of the photoinitiator: weigh a certain weight of sulfuric acidZinc (ZnSO) 4 ) Powder according to 5X 10 -3 mol/L、5×10 -4 mol/L、5×10 -5 The concentration of mol/L is dissolved in double distilled water to prepare a solution. Using phenyl (2, 4, 6-trimethylbenzoyl) phosphate lithium salt (Lap) as a photoinitiator, 0.025g of Lap was separately weighed and dissolved in 10ml of the above solution to prepare a zinc ion-loaded photoinitiator. To be free of ZnSO 4 Is used for preparing the photoinitiator special for dissolving HAMA.
Configuration of the photocurable hydrogel: weighing 0.1g of HAMA in 10mL of ZnSO-free solution 4 Is stored in a dark place. Weighing 0.5g of GelMA in 10mL containing ZnSO 4 Is stored in a dark place. Both hydrogels were in liquid form.
(3) Preparation of intermediate and surface layers (composite scaffolds)
HAMA hydrogel cover: 200 mu L of the above non-ZnSO-containing solution was taken 4 Injecting the HAMA hydrogel solution into a small hole of a 48-hole plate, and irradiating with ultraviolet rays with the wavelength of 360nm for 5 seconds to enable the hydrogel to be in a semi-coagulated state; the porous magnesium alloy with 1 DCPD coating is horizontally placed on semi-solidified HAMA hydrogel, forceps are used for lightly pressing down to enable the porous magnesium alloy bracket to be wrapped in the hydrogel, ultraviolet rays with the wavelength of 360nm are irradiated for 30 seconds, and the HAMA hydrogel is thoroughly solidified to form an intermediate layer.
Removal of HAMA hydrogel scaffold: 1mL of absolute ethyl alcohol is dripped on the covered hydrogel, then a metal rod with a flat thickness of about 1mm is used for being tightly attached to the inner wall of the small hole and inserted between the hydrogel and the inner wall, and the hydrogel and the inner wall of the small hole are slowly slid for a circle to be filled with the absolute ethyl alcohol. The bottom of the hydrogel is tilted slightly by a metal rod to erect the hydrogel, the hydrogel is taken out by tweezers and put into a clean small culture dish, the ethanol remained on the surface is washed by PBS solution, and the surface moisture is naturally dried.
Covering of GelMA hydrogel: 200 mu L of the above-mentioned material containing ZnSO 4 The GelMA hydrogel is flatly paved at the bottom of a small hole of a 24-hole plate, and ultraviolet rays with the wavelength of 360nm are irradiated for 5 seconds, so that the hydrogel is in a semi-solidification state; placing the HAMA covered magnesium alloy scaffold prepared in the previous step in the center of semi-solidified GelMA hydrogel, and addingAnd (3) covering the HAMA hydrogel bracket by 500 mu L of GelMA hydrogel, and radiating with ultraviolet rays with the wavelength of 360nm for 45 seconds to thoroughly solidify the GelMA hydrogel to form a surface layer, thereby obtaining the magnesium alloy composite hydrogel bracket.
Taking out the magnesium alloy composite hydrogel scaffold: 1ml of absolute ethyl alcohol is dripped on the magnesium alloy composite hydrogel bracket, then a metal rod with a flat thickness of about 1mm is used for being tightly attached to the inner wall of the small hole and inserted between the hydrogel and the inner wall, and the metal rod slowly slides for a circle to enable the absolute ethyl alcohol to be filled between the hydrogel and the inner wall of the hole. The bottom of the hydrogel is lifted up by a metal rod to stand up, the hydrogel is taken out by forceps and put into a clean small culture dish, and the ethanol remained on the surface is washed by PBS solution and soaked in the required solution for use.
The invention provides a method for preparing a controllable slow-release porous magnesium alloy material by modifying pore adjustment and coating coverage, which is shown in figure 1; the modified porous magnesium alloy is coated with a compact and slowly degraded polymer hydrogel intermediate layer, so that the contact of the magnesium alloy with water molecules is reduced, the degradation rate of the magnesium alloy is further reduced, the concentration and the molecular weight of the polymer hydrogel are regulated, and the quantity of the contact of the magnesium alloy with water molecules is regulated, so that the degradation rate of the magnesium alloy is regulated, wherein the pores of the magnesium alloy can be 550 mu m, 750 mu m and 950 mu m.
The invention also provides an enhanced material antibacterial mode. The magnesium ion released after the magnesium alloy is degraded has a certain antibacterial property, but the infection focus of the infectious osteochondral defect can not be effectively controlled. When the outer hydrogel is rapidly degraded, zinc ions can be locally accumulated, so that the early sterilization effect can be achieved, and after preliminary effective sterilization, slowly degraded magnesium ions penetrate into a local microenvironment to achieve a continuous antibacterial effect.
The invention also creates a space-time adjustment system. According to the above manufacturing sequence, a slowly degradable polymer hydrogel is covered on the surface of the porous magnesium alloy covered by the coating, and then a layer of rapidly degradable hydrogel containing zinc ions is covered on the outermost layer, so as to form the composite stent, as shown in fig. 3. The stent system can realize the sequential release of ions through two hydrogels with differential degradation characteristics on the outer layer of the alloy, and can realize the control of the slow release rate and the local ion concentration by regulating the concentration and the molecular weight of the hydrogels; in addition, by compounding ions with different types, numbers and the like at different parts of the hydrogel, the slow-release spatial regulation of the composite stent can be realized.
FIG. 4 is an example of a scaffold prepared schematically according to FIG. 3, with two layers of hydrogels (HAMA and GelMA) coated on the outer layer and DCPD magnesium alloy scaffold (750 μm pores) on the inner layer. Fig. 2 shows the microscopic structure of the scanning electron microscope of the two hydrogels at the outer layer, and it can be seen from the figure that the HAMA hydrogel has a denser structure, so that the degradation rate is slower than that of the GelMA hydrogel, and the differential degradation effect is formed, so that zinc ions are released at first, and magnesium ions are released by the delay of wrapping the magnesium alloy by the HAMA. FIG. 5 shows the antibacterial property of the active ingredients constituting the composite scaffold, and it can be seen from the results that the composition contains 10 -3 、10 -4 、10 -5 The antibacterial effect of the hydrogel of mol/L zinc ions is gradually decreased, and meanwhile, the magnesium alloy has certain antibacterial property, so that the antibacterial effect is stronger after the composite stent is formed. Fig. 6 shows the concentration of released zinc ions at different time points when the hydrogel doped with zinc ions at three different concentrations is degraded in a simulated body fluid, so that it can be seen that the ion release rates of the three zinc ion hydrogels at different concentrations are different, but the trend is that the hydrogel is quick and slow.
The space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material prepared by the invention can be used for preparing bone implants or spinal column orthopedic medical devices, and is shown in fig. 7.
Claims (10)
1. The space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material is characterized by sequentially comprising a basal layer, an intermediate layer and a surface layer from inside to outside, wherein the basal layer is DCPD modified porous magnesium alloy; the intermediate layer and the surface layer are formed by curing a photo-curing hydrogel, wherein the photo-curing hydrogel is a methacryloyl modified hydrogel, and the photo-curing hydrogel used for the surface layer contains zinc ions.
2. The space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel scaffold material of claim 1, wherein the pores of the magnesium alloy are 500-1000 μm.
3. The space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel scaffold material according to claim 1, wherein the surface layer uses a photo-setting hydrogel having a concentration of zinc ions of 1 x 10 -5 ~9×10 -3 mol/L。
4. The space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel scaffold material according to claim 1, wherein the photo-cured hydrogel is selected from the group consisting of methacryloylated hyaluronic acid, methacryloylated gelatin, methacryloylated sodium alginate, methacryloylated chitosan, methacryloylated dextran, methacryloylated chondroitin sulfate and methacryloylated silk fibroin.
5. The method for preparing the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel stent material as claimed in claim 1, which is characterized by comprising the following steps:
firstly, preparing porous magnesium alloy by using magnesium alloy as a raw material and NaCl particles as pore-forming agents through a negative pressure seepage casting method, and electrodepositing a DCPD coating to obtain a substrate layer;
step two, performing methacryloylation modification on the hydrogel, adding the hydrogel into a photoinitiator without zinc ions to obtain a hydrogel solution without zinc ions, immersing a substrate layer in the hydrogel solution without zinc ions, and performing ultraviolet light curing to form an intermediate layer;
and thirdly, performing methacryloylation modification on the hydrogel, adding the hydrogel into a photoinitiator containing zinc ions to obtain a hydrogel solution containing zinc ions, immersing the intermediate layer in the hydrogel solution containing zinc ions, and performing ultraviolet light curing to form a surface layer to obtain the composite hydrogel scaffold material.
6. The method according to claim 5, wherein the method for preparing the porous magnesium alloy in the first step comprises the following steps: the preparation method of the porous magnesium alloy in the first step comprises the following steps: magnesium alloy with the purity of 99.95% and magnesium-calcium alloy with the purity of Mg-30wt.% Ca are used as raw materials, spherical NaCl particles with different diameters after pretreatment are used as pore formers, the smelted raw materials are poured into gaps of the pore formers under negative pressure environment, after cooling and demoulding, the NaCl particles are removed by ultrasonic cleaning in alkali liquor, and then the porous magnesium alloy is obtained by drying.
7. The method of claim 5, wherein the DCPD coating in step one is prepared by the following steps: weighing sodium phosphite powder, dissolving the sodium phosphite powder in double distilled water according to the mass fraction of 3.1%, adding calcium nitrate into the double distilled water according to the mass fraction of 5.3%, and adjusting the pH value to 3.5 to obtain a deposition solution; adding the porous magnesium alloy into the deposition solution, reacting for 3 hours at 45 ℃, taking out, ultrasonically cleaning, drying and vacuum sealing.
8. The preparation method according to claim 5, wherein the method for the modification of the hydrogel by methacryloylation in the second and third steps comprises the following steps: the hydrogel is dissolved in double distilled water according to the ratio of 0.02g/mL, then reacts with 20 times of excessive methacrylic anhydride, the pH value is adjusted to 8, then the hydrogel is placed at the temperature of 5 ℃ for incubation for 24 hours, the incubated solution is used for precipitating methacrylic acid and methacrylic anhydride, and finally the precipitate is freeze-dried to obtain the methacryloyl modified hydrogel.
9. The method according to claim 5, wherein the photoinitiator in the second and third steps is a solution of phenyl (2, 4, 6-trimethylbenzoyl) phosphate lithium salt.
10. Use of the space-time adjustable infectious osteochondral defect magnesium alloy composite hydrogel scaffold material according to claim 1 for preparing bone implants or spinal orthopedic medical devices.
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