CN118141989A - Aramid fiber magnesium alloy composite material for promoting cell proliferation and preparation method thereof - Google Patents
Aramid fiber magnesium alloy composite material for promoting cell proliferation and preparation method thereof Download PDFInfo
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- CN118141989A CN118141989A CN202410585481.0A CN202410585481A CN118141989A CN 118141989 A CN118141989 A CN 118141989A CN 202410585481 A CN202410585481 A CN 202410585481A CN 118141989 A CN118141989 A CN 118141989A
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- 230000001737 promoting effect Effects 0.000 title claims abstract description 57
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Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the technical field of aramid fiber magnesium alloy composite materials, in particular to an aramid fiber magnesium alloy composite material for promoting cell proliferation and a preparation method thereof, wherein the aramid fiber magnesium alloy composite material comprises a medical magnesium alloy substrate, an aramid fiber nanofiber layer and an antibacterial proliferation-promoting hydrogel layer, and the aramid fiber nanofiber layer is positioned between the medical magnesium alloy substrate and the antibacterial proliferation-promoting hydrogel layer; the antibacterial proliferation promoting hydrogel layer comprises aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative, wherein the L-chiral amino acid derivative contains hydroxyl and ether bonds, and the antibacterial agent is one or more of gentamicin, azithromycin and rhein. The aramid fiber magnesium alloy composite material has higher strength, can promote the adhesion and proliferation of cells, can compensate the strength loss of magnesium alloy during degradation, and ensures the effective healing of bone tissues.
Description
Technical Field
The invention relates to an aramid fiber magnesium alloy composite material for promoting cell proliferation and a preparation method thereof, belonging to the technical field of aramid fiber magnesium alloy composite materials.
Background
The biological alloy medical material has excellent strength, toughness and fatigue resistance, and has great advantages in the fields of orthopedic implant materials and dental implant materials. Compared with other inert alloys, the magnesium alloy has degradability, does not need secondary operation, and effectively relieves the pain of patients; and the magnesium alloy is equivalent to the bone density of a human body, so that stress shielding is reduced, stress transfer is hindered, and adjacent tissues are damaged. However, magnesium alloy has poor corrosion resistance, and degradation of magnesium alloy can lead to failure of supporting effect of stent material after implantation into human body, and influence tissue healing. Therefore, how to improve the corrosion resistance and biocompatibility of the magnesium alloy, slow down the strength loss when the magnesium alloy is degraded, accelerate the proliferation of cells and tissues on the surface of the material, and become a key factor for improving the development of the magnesium alloy composite material.
Inspired by the three-dimensional network fiber structure of the natural extracellular matrix (ECM), many biomimetic materials were developed to accelerate cell attachment and proliferation on the surface of the material. Common biomimetic extracellular matrix (ECM) materials are electrospun fibers (polycaprolactone fibers, polylactic acid fibers, chitosan fibers, etc.) and hydrogel materials. For example, chinese patent application CN106063949a discloses a high-strength degradable endosteal fixation composite material, using polylactic acid and magnesium alloy; chinese patent CN111419479B discloses a composite scaffold for repairing hip joint cartilage and its preparation method, which uses hydrogel material. However, at present, both materials have certain problems, such as lower strength, and cannot compensate for strength loss when magnesium alloy is degraded; the bonding force with the matrix is poor, and stripping is easy to occur; the chiral structure of the extracellular matrix cannot be simulated, which is unfavorable for cell adhesion and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the aramid fiber magnesium alloy composite material for promoting cell proliferation and the preparation method thereof, wherein the aramid fiber magnesium alloy composite material has higher strength, can promote cell adhesion and proliferation, can compensate strength loss during magnesium alloy degradation, and can ensure effective healing of bone tissues.
The technical scheme for solving the technical problems is as follows: the aramid fiber magnesium alloy composite material for promoting cell proliferation comprises a medical magnesium alloy substrate, an aramid fiber nanofiber layer and an antibacterial proliferation promoting hydrogel layer, wherein the aramid fiber nanofiber layer is positioned between the medical magnesium alloy substrate and the antibacterial proliferation promoting hydrogel layer;
the antibacterial proliferation promoting hydrogel layer comprises aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative, wherein the L-chiral amino acid derivative contains hydroxyl and ether bonds.
Further, the diameter of the aramid nanofiber in the aramid nanofiber layer and the aramid nanofiber in the antibacterial proliferation-promoting hydrogel layer is 30-100nm, and the length of the aramid nanofiber is 10-30 mu m.
Further, the antibacterial agent is one or more of gentamicin, azithromycin and rhein.
Further, the L-chiral amino acid derivative is one or more of an L-alanine derivative, an L-tryptophan derivative and an L-phenylalanine derivative;
the structural formula of the L-alanine derivative is as follows:
；
The structural formula of the L-phenylalanine derivative is as follows:
；
the structural formula of the L-tryptophan derivative is as follows:
。
further, in the antibacterial proliferation promoting hydrogel layer, the weight ratio of the aramid nanofiber to the antibacterial agent to the L-chiral amino acid derivative is 1: (0.5-1): (2-5).
The invention also discloses a preparation method of the aramid fiber magnesium alloy composite material for promoting cell proliferation, which comprises the following steps:
s1, firstly, performing corrosion resistance treatment on a medical magnesium alloy substrate;
s2, uniformly coating the aramid nanofiber on the medical magnesium alloy substrate subjected to the corrosion resistance treatment, and then drying to form an aramid nanofiber layer on the medical magnesium alloy substrate;
S3, preparing the aramid nanofiber, the antibacterial agent, the L-chiral amino acid derivative and deionized water into hydrogel, uniformly coating the hydrogel on the aramid nanofiber layer to form an antibacterial proliferation-promoting hydrogel layer, and then drying to obtain the aramid magnesium alloy composite material.
Further, in step S1, the method of the corrosion resistance treatment is any one of plasma spraying, electrochemical deposition and micro-arc oxidation.
Further, in step S2, the preparation method of the aramid nanofiber includes: adding para-aramid short fibers into a protonation solvent of dimethyl sulfoxide, then adding potassium hydroxide, stirring until the solution becomes a reddish brown viscous solution, obtaining an aramid nanofiber solution, then adding deionized water, uniformly mixing, carrying out solid-liquid separation, and washing to remove the potassium hydroxide and the protonation solvent to obtain the aramid nanofiber;
The volume ratio of the dimethyl sulfoxide to the protonated solvent is 50 (1-2), the concentration of the potassium hydroxide in the protonated solvent of the dimethyl sulfoxide is 0.0095-0.0196 g/mL, and the mass ratio of the para-aramid staple fiber to the potassium hydroxide is 1: (0.5-1).
Further, in step S3, the preparation method of the hydrogel includes: adding aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative into deionized water, uniformly stirring and heating to completely dissolve the molecules, and then slowly cooling to room temperature to obtain the hydrogel, wherein the cooling speed of the slow cooling is 0.5-1 ℃/min.
Further, the thickness of the aramid nanofiber layer is 100-500 microns, and the thickness of the antibacterial proliferation-promoting hydrogel layer is 500-800 microns.
The beneficial effects of the invention are as follows:
The three components of the aramid nanofiber, the antibacterial agent and the L-chiral amino acid derivative in the hydrogel can form a three-dimensional chiral cross-linked extracellular matrix-like structure through non-covalent bond action (hydrogen bond, pi-pi accumulation, van der Waals force and the like) so as to promote cell proliferation; in addition, the aramid nanofiber in the hydrogel can be crosslinked with the hydrogen bond of the aramid nanofiber layer, so that the interlayer binding force is improved. In the aramid fiber magnesium alloy composite material, a firm assembly structure is realized through non-covalent bond interaction between a magnesium alloy matrix, aramid fiber nanofiber and hydrogel, and the nanostructure and chiral units simulate a three-dimensional chiral cross-woven network structure of an extracellular matrix together to cooperatively promote adhesion and proliferation of cells. The extracellular matrix (ECM) is formed by the interlacing of various chiral proteins and fibers. The porous three-dimensional chiral network structure can provide proper microenvironment for cells, promote the adhesion and migration of the cells and perform intercellular signal transmission. The aramid nanofiber layer presents a porous, interconnected and permeable three-dimensional cross structure, so that a space is provided for cells and nutrient substances to enter, and the L-chiral gel of the antibacterial proliferation-promoting hydrogel layer has stronger cell affinity, and is beneficial to further proliferation of cells. Therefore, in the aramid fiber magnesium alloy composite material, the three-dimensional structure of the aramid fiber nanofiber and the chiral hydrogel are cooperated, and meanwhile, the composite material is endowed with a crossed nano-network structure and a chiral spiral structure, so that the double effects are achieved, and the cell adhesion and proliferation are promoted.
According to the aramid fiber magnesium alloy composite material, the strength of the magnesium alloy can be effectively improved through the synergistic effect of the aramid fiber nanofiber and the chiral hydrogel, and the strength loss during degradation of the magnesium alloy is compensated; the adhesion and proliferation of cells can be improved by the cooperation of the nanofiber and the chiral spiral structure, and the high-strength high-modulus aramid nanofiber can effectively compensate the strength loss during magnesium alloy degradation and ensure the effective healing of bone tissues.
The Aramid Nanofiber (ANF) used in the aramid magnesium alloy composite material is a one-dimensional nanofiber prepared by deprotonating poly-paraphenylene terephthalamide (PPTA) fibers. The aramid nanofiber not only maintains the characteristics of high strength, high modulus, high specific surface area and high thermochemical stability of the aramid fiber, but also remarkably improves the inertia of the surface of the aramid fiber, the high strength and high modulus of the aramid nanofiber can effectively compensate the strength loss during magnesium alloy degradation, the effective healing of bone tissues is ensured, and meanwhile, the aramid nanofiber has biocompatibility and biocompatibility, can be discharged through metabolism and can not damage organisms.
The hydrogel contains an antibacterial agent, so that the antibacterial activity of the material can be ensured, the antibacterial rate of the aramid fiber magnesium alloy composite material on staphylococcus aureus and escherichia coli can reach 97% or higher, the healing environment can be purified, and secondary injuries such as wound pollution caused by bacteria can be reduced. The protein and DNA in the living body are L-chirality, and the L-chiral amino acid derivative can make the biological cells more easy to proliferate in the living body-like environment. In addition, the L-chiral amino acid derivative contains a large number of hydroxyl groups and ether bonds, so that the formation of hydrogel is facilitated, the non-covalent bond acting force such as intermolecular hydrogen bonds is stronger, and the application performance of the aramid fiber magnesium alloy composite material is finally improved. The preparation method can prepare the aramid fiber magnesium alloy composite material with antibacterial property, proliferation promoting property and high strength.
According to the preparation method of the aramid magnesium alloy composite material, the firm combination of the matrix, the nano layer and the gel layer is realized by a non-covalent bond assembly method, the process is simple, and complicated processing is avoided.
Drawings
FIG. 1 is a schematic diagram of a preparation process of an aramid fiber magnesium alloy composite material;
FIG. 2 is a graph showing the comparison of the results of cell proliferation tests of the unmodified magnesium alloy and aramid magnesium alloy composite material of example 1;
FIG. 3 is a graph showing the comparison of the results of cell proliferation tests of the unmodified magnesium alloy and aramid magnesium alloy composites of example 2;
FIG. 4 is a graph showing the comparison of the results of cell proliferation tests of the unmodified magnesium alloy and aramid magnesium alloy composites of example 3.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The aramid fiber magnesium alloy composite material for promoting cell proliferation comprises a medical magnesium alloy substrate, an aramid fiber nanofiber layer and an antibacterial proliferation promoting hydrogel layer, wherein the aramid fiber nanofiber layer is positioned between the medical magnesium alloy substrate and the antibacterial proliferation promoting hydrogel layer;
the antibacterial proliferation promoting hydrogel layer comprises aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative, wherein the L-chiral amino acid derivative contains hydroxyl and ether bonds.
Specifically, the diameter of the aramid nanofiber in the aramid nanofiber layer and the aramid nanofiber in the antibacterial proliferation-promoting hydrogel layer is 30-100nm, and the length of the aramid nanofiber is 10-30 mu m.
Specifically, the antibacterial agent is one or more of gentamicin, azithromycin and rhein.
Specifically, the L-chiral amino acid derivative is one or more of an L-alanine derivative, an L-tryptophan derivative and an L-phenylalanine derivative;
the structural formula of the L-alanine derivative is as follows:
；
The structural formula of the L-phenylalanine derivative is as follows:
；
the structural formula of the L-tryptophan derivative is as follows:
。
Specifically, in the antibacterial proliferation promoting hydrogel layer, the weight ratio of the aramid nanofiber to the antibacterial agent to the L-chiral amino acid derivative is 1: (0.5-1): (2-5).
As shown in fig. 1, a preparation method of an aramid fiber magnesium alloy composite material for promoting cell proliferation comprises the following steps:
s1, firstly, performing corrosion resistance treatment on a medical magnesium alloy substrate;
s2, uniformly coating the aramid nanofiber on the medical magnesium alloy substrate subjected to the corrosion resistance treatment, and then drying to form an aramid nanofiber layer on the medical magnesium alloy substrate;
S3, preparing the aramid nanofiber, the antibacterial agent, the L-chiral amino acid derivative and deionized water into hydrogel, uniformly coating the hydrogel on the aramid nanofiber layer to form an antibacterial proliferation-promoting hydrogel layer, and then drying to obtain the aramid magnesium alloy composite material.
Specifically, in step S1, the method of the corrosion resistance treatment is any one of plasma spraying, electrochemical deposition and micro-arc oxidation.
Specifically, in step S2, the preparation method of the aramid nanofiber includes: adding para-aramid short fibers into a protonation solvent of dimethyl sulfoxide, then adding potassium hydroxide, stirring until the solution becomes a reddish brown viscous solution, obtaining an aramid nanofiber solution, then adding deionized water, uniformly mixing, carrying out solid-liquid separation, and washing to remove the potassium hydroxide and the protonation solvent to obtain the aramid nanofiber;
The volume ratio of the dimethyl sulfoxide to the protonated solvent is 50 (1-2), the concentration of the potassium hydroxide in the protonated solvent of the dimethyl sulfoxide is 0.0095-0.0196 g/mL, and the mass ratio of the para-aramid staple fiber to the potassium hydroxide is 1: (0.5-1).
The protonated solvent is one or more of methanol, ethanol and water.
Specifically, the mass fraction of the aramid nanofibers in the aramid nanofiber solution is 0.5% -4%; more specifically, in the embodiment of the invention, the mass fraction of the aramid nanofiber in the aramid nanofiber solution is 1.8% -2.0%.
Specifically, in step S3, the preparation method of the hydrogel includes: adding aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative into deionized water, uniformly stirring and heating to completely dissolve the molecules, and then slowly cooling to room temperature to obtain the hydrogel, wherein the cooling speed of the slow cooling is 0.5-1 ℃/min.
Specifically, the total concentration of the hydrogel can be 10-30 mg/mL; more specifically, the total concentration of the hydrogel in the embodiment of the invention is 9-11 mg/mL.
Specifically, in the preparation process of the hydrogel, the heating and dissolving temperature is more than 80 ℃, namely, the heating temperature is 80-100 ℃.
The para-aramid short fiber used in the embodiment of the invention has the length of 1-2 cm, the strength of 20.5cN/dtex and the elongation of 3.5-4.5%.
Specifically, the thickness of the aramid nanofiber layer is 100-500 microns, and the thickness of the antibacterial proliferation-promoting hydrogel layer is 500-800 microns.
Specifically, the preparation method of the L-chiral amino acid derivative in the embodiment of the invention comprises the following steps: terephthaloyl chloride (15 mmol) was previously dissolved in 20mL of methylene chloride, methyl ester hydrochloride (30 mmol) of L-amino acid and triethylamine (60 mmol) were previously dissolved with 100mL of methylene chloride with stirring, and then terephthaloyl chloride solution was slowly added dropwise to methyl ester hydrochloride solution of L-amino acid and stirring was continued at room temperature for 48 hours. The suspension after the reaction was subjected to rotary evaporation and washing and drying with ethanol several times, 6mmol of the obtained substance was added to 20mL of methanol solution, 10mL of 2mol/L aqueous sodium hydroxide solution was added, stirring was continued for 24 hours, pH of the solution was adjusted to about 3 with hydrochloric acid (3M) and precipitation was accompanied, and the precipitate was washed and dried for use. Adding the obtained precipitate into excessive diethylene glycol, adding hydrochloric acid to catalyze the reaction to accelerate, and washing and drying the precipitate separated out by the rapid cooling of a reaction bottle for multiple times after the reaction is carried out for 6 hours to obtain the L-chiral amino acid derivative.
The methyl ester hydrochloride of the L-amino acid is L-alanine methyl ester hydrochloride, L-tryptophan methyl ester hydrochloride or L-phenylalanine methyl ester hydrochloride.
Example 1
The preparation of the aramid fiber magnesium alloy composite material for promoting cell proliferation specifically comprises the following steps:
(1) The medical magnesium alloy with the thickness of 10 multiplied by 5mm is polished by sand paper, repeatedly cleaned by deionized water and alcohol and then dried, and the oxide layer and dirt on the surface are removed. Placing the medical magnesium alloy into an autoclave containing an Al (NO 3)3·9H2 O aqueous solution) with the pH value of 12, carrying out hydrothermal reaction for 15 hours at the temperature of 100 ℃, taking out a sample, repeatedly cleaning and drying to obtain the medical magnesium alloy substrate after corrosion resistance treatment.
(2) Adding 1g of para-aramid short fiber into a conical flask, adding 50ml of dimethyl sulfoxide, adding 1g of potassium hydroxide (KOH), stirring uniformly, adding 1ml of deionized water, stirring at 25 ℃ for 7 days until the solution turns into a reddish brown viscous solution, adding the reddish brown solution into the deionized water, stirring at 10000rpm for 1 hour at a high speed, carrying out suction filtration and washing, uniformly coating the obtained aramid nanofiber on a medical magnesium alloy substrate subjected to corrosion resistance treatment, and drying at 80 ℃ in an oven to obtain an aramid nanofiber layer, wherein the thickness of the aramid nanofiber layer is 300-350 microns.
(3) Adding 2mg of aramid nanofiber, 1mg of gentamicin and 7mg of L-propylamino acid derivative into 1mL of deionized water, uniformly stirring and heating to 85 ℃ to completely dissolve various components, and slowly cooling at a cooling speed of 1 ℃/min to obtain hydrogel. The hydrogel is coated on the surface of the aramid nanofiber layer for multiple times and dried at 60 ℃, and the cell proliferation promoting aramid magnesium alloy composite material can be finally prepared after the moisture in the hydrogel is removed, wherein the thickness of the antibacterial proliferation promoting hydrogel layer is 500-600 microns.
1. Cell proliferation assay test was performed:
Cell resuscitation: taking 1mL of frozen CHO cells, rapidly shaking in a water bath at 37 ℃ for thawing, adding 4mL of Dynamic culture solution, uniformly mixing, centrifuging for 4 minutes at 200RPM to remove supernatant, supplementing 1-2mL of culture medium, and repeatedly blowing to resuspend the cells; inoculating 1mL of the cell suspension and 9mL of the culture medium into a shake flask, and culturing overnight; cell number and cell viability were tested using Vi-cell from 200. Mu.L of the cell fluid until the cell number reached 1X 10 5/mL, with the viability remaining at 98%.
Cell proliferation assay: the above cell culture was centrifuged at 200rpm for 4 minutes, the supernatant was removed, and added to 1mL of the culture medium to be resuspended and then divided into two parts, and 9.5mL of the culture medium was added to each of the above cell solutions, to which the medical magnesium alloy (i.e., unmodified magnesium alloy) and aramid magnesium alloy composite material of this example were added, respectively, and the cell numbers were measured at 4 hours, 12 hours, 24 hours, and 36 hours, respectively, to thereby obtain the results shown in table 1 and fig. 2 below.
TABLE 1 results of cell proliferation test of unmodified magnesium alloy and aramid magnesium alloy composite material of example 1
2. Antibacterial condition test
The testing method comprises the following steps: antibacterial tests were performed with reference to AATCCTEST METHOD 100 (bacterial count assay) standards.
The antibacterial rate of the aramid fiber magnesium alloy composite material prepared by the embodiment on staphylococcus aureus and escherichia coli can reach 97.2 percent.
Example 2
The preparation of the aramid fiber magnesium alloy composite material for promoting cell proliferation specifically comprises the following steps:
(1) The medical magnesium alloy with the thickness of 8 multiplied by 2mm is polished by sand paper, repeatedly cleaned by deionized water and alcohol and then dried, and the oxide layer and dirt on the surface are removed. And placing the medical magnesium alloy in a nitrogen or argon atmosphere, and carrying out plasma spraying at a current of 70A and a rotation speed of 35r/min by adopting a voltage of 500V to obtain the medical magnesium alloy substrate after corrosion resistance treatment.
(2) Adding 1g of para-aramid short fiber into a conical flask, adding 50ml of dimethyl sulfoxide, adding 0.5g of potassium hydroxide (KOH), stirring uniformly, adding 1ml of methanol, stirring at 25 ℃ for 7 days until the solution turns into a reddish brown viscous solution, adding the reddish brown solution into deionized water, stirring at a high speed of 30000rpm for 0.5 hour, carrying out suction filtration and washing to obtain aramid nanofiber, uniformly coating the obtained aramid nanofiber on the surface of a medical magnesium alloy substrate subjected to corrosion resistance treatment, and drying at 80 ℃ in an oven to obtain an aramid nanofiber layer, wherein the thickness of the aramid nanofiber layer is 200-280 microns.
(3) Adding 3mg of aramid nanofiber, 2mg of rhein and 6mg of L-phenylpropanoid acid derivative into 1mL of deionized water, uniformly stirring, heating to 90 ℃ to completely dissolve various components, and slowly cooling at a cooling speed of 0.5 ℃/min to obtain hydrogel. The hydrogel is coated on the surface of the aramid nanofiber layer for multiple times and dried at 60 ℃, and the cell proliferation promoting aramid magnesium alloy composite material can be finally prepared after the moisture in the hydrogel is removed, wherein the thickness of the antibacterial proliferation promoting hydrogel layer is 650-750 microns.
1. Cell proliferation assay test was performed:
Cell resuscitation: taking 1mL of frozen CHO cells, rapidly shaking in a water bath at 37 ℃ for thawing, adding 4mL of Dynamic culture solution, uniformly mixing, centrifuging for 4 minutes at 200RPM to remove supernatant, supplementing 1-2mL of culture medium, and repeatedly blowing to resuspend the cells; inoculating 1mL of the cell suspension and 9mL of the culture medium into a shake flask, and culturing overnight; cell number and cell viability were tested using Vi-cell from 200. Mu.L of the cell fluid until the cell number reached 1X 10 5/mL, with the viability remaining at 98%.
Cell proliferation assay: the above cell culture was centrifuged at 200rpm for 4 minutes, the supernatant was removed, and added to 1mL of the culture medium to be resuspended and then divided into two parts, and 9.5mL of the culture medium was added to each of the above cell solutions, to which the medical magnesium alloy (i.e., unmodified magnesium alloy) and aramid magnesium alloy composite material of this example were added, respectively, and the cell numbers were measured at 4 hours, 12 hours, 24 hours, and 36 hours, respectively, to thereby obtain the results shown in table 2 and fig. 3 below.
TABLE 2 results of cell proliferation test of unmodified magnesium alloy and aramid magnesium alloy composite material of example 2
2. Antibacterial condition test
The testing method comprises the following steps: as in example 1.
The antibacterial rate of the aramid fiber magnesium alloy composite material prepared by the embodiment on staphylococcus aureus and escherichia coli can reach 97.0%.
Example 3
The preparation of the aramid fiber magnesium alloy composite material for promoting cell proliferation specifically comprises the following steps:
(1) The medical magnesium alloy with the thickness of 10 multiplied by 1mm is polished by sand paper, repeatedly cleaned by deionized water and alcohol and then dried, and the oxide layer and dirt on the surface are removed. The pretreated medical magnesium alloy is used as a cathode, a platinum electrode is used as an anode, the electrolyte is prepared from a PEI/PSS mixture of nano TiO 2 containing nano TiO 2, the current used for preparing the coating is 0.3A, and finally the medical magnesium alloy substrate after corrosion resistance treatment is obtained.
(2) Adding 2g of para-aramid short fibers into a conical flask, adding 100ml of dimethyl sulfoxide, adding 2g of potassium hydroxide (KOH), stirring uniformly, adding 2ml of methanol, stirring at 25 ℃ for 7 days until the solution turns into a reddish brown viscous solution, adding the reddish brown solution into deionized water, stirring at 20000rpm for 1 hour at high speed, carrying out suction filtration and washing to obtain aramid nanofibers, uniformly coating the obtained aramid nanofibers on the surface of a magnesium alloy, and drying at 80 ℃ in an oven, wherein the thickness of the aramid nanofiber layer is 350-450 micrometers.
(3) Adding 2mg of aramid nanofiber, 2mg of rhein and 6mg of L-color amino acid derivative into 1mL of deionized water, uniformly stirring, heating to 95 ℃ to completely dissolve various components, and slowly cooling at a cooling speed of 1 ℃/min to obtain the hydrogel. The hydrogel is coated on the surface of the aramid nanofiber layer for multiple times and dried at 60 ℃, and the cell proliferation promoting aramid magnesium alloy composite material can be finally prepared after the moisture in the hydrogel is removed, wherein the thickness of the antibacterial proliferation promoting hydrogel layer is 650-750 microns.
1. Cell proliferation assay test was performed:
Cell resuscitation: taking 1mL of frozen CHO cells, rapidly shaking in a water bath at 37 ℃ for thawing, adding 4mL of Dynamic culture solution, uniformly mixing, centrifuging for 4 minutes at 200RPM to remove supernatant, supplementing 1-2mL of culture medium, and repeatedly blowing to resuspend the cells; inoculating 1mL of the cell suspension and 9mL of the culture medium into a shake flask, and culturing overnight; cell number and cell viability were tested using Vi-cell from 200. Mu.L of the cell fluid until the cell number reached 1X 10 5/mL, with the viability remaining at 98%.
Cell proliferation assay: the above cell culture was centrifuged at 200rpm for 4 minutes, the supernatant was removed, and added to 1mL of the culture medium to be resuspended and then divided into two parts, and 9.5mL of the culture medium was added to each of the above cell solutions, to which the medical magnesium alloy (i.e., unmodified magnesium alloy) and aramid magnesium alloy composite material of this example were added, respectively, and the cell numbers were measured at 4 hours, 12 hours, 24 hours, and 36 hours, respectively, to thereby obtain the results shown in table 3 and fig. 4 below.
TABLE 3 results of cell proliferation test of unmodified magnesium alloy and aramid magnesium alloy composite material of example 3
2. Antibacterial condition test
The testing method comprises the following steps: as in example 1.
The antibacterial rate of the aramid fiber magnesium alloy composite material prepared by the embodiment on staphylococcus aureus and escherichia coli can reach 97.0%.
Comparative example 1
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: the aramid nanofibers are not added into the hydrogel in the step (3).
Because of the non-covalent bond interaction such as amide hydrogen bond and pi-pi accumulation and the like between the aramid nanofiber and the nanofiber layer in the hydrogel, an interlayer bridge connection effect is achieved, the interface combination between the aramid nanofiber layer and the antibacterial proliferation-promoting hydrogel layer is poor due to the fact that the aramid nanofiber is not added into the hydrogel, in an antibacterial test, interlayer shedding of the aramid nanofiber layer and the antibacterial proliferation-promoting hydrogel layer occurs, bacteria easily pass through the shed antibacterial layer, are directly attached to the aramid nanofiber layer, and finally bacteria proliferation is achieved. The antibacterial result shows that: the antibacterial rate of the composite material without adding aramid nanofibers into the hydrogel is only 79%. Similarly, the shedding of the aramid nanofiber layer and the antibacterial pro-proliferative hydrogel layer also resulted in a decrease in the pro-cell proliferation effect (as shown in table 4), since the synergistic effect of pro-cell proliferation was lost, and only a single assembly layer was relied upon for pro-cell proliferation.
TABLE 4 comparative example 1 and aramid magnesium alloy composite cell proliferation test results
Comparative example 2
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: the hydrogel in the step (3) is cooled in a quenching way, the cooling speed reaches more than 10 ℃/min, the hydrogel is directly separated in phase, and assembly separation occurs (namely, three components cannot be uniformly precipitated out of gel to form a co-assembly). This operation directly leads to failure of assembly, resulting in a decrease in antibacterial performance, wherein the antibacterial rate against staphylococcus aureus and escherichia coli can be only 87%, because the antibacterial agent cannot be uniformly dispersed in the hydrogel, resulting in an increase in local bacterial infection. The cell proliferation promoting effect was also decreased (as shown in table 5), because of the decreased ability to adhere cells due to the uneven dispersion of the L chiral amino acid derivative.
TABLE 5 results of cell proliferation test of aramid magnesium alloy composite and comparative example 2
Comparative example 3
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: the antibacterial proliferation promoting hydrogel layer is directly coated on the medical magnesium alloy substrate after the corrosion resistance treatment without the intermediate aramid nanofiber layer.
Compared with the aramid nanofiber antibacterial hydrogel composite layer, the aramid nanofiber layer is not added, so that the antibacterial performance is not obviously affected, and the antibacterial performance can reach 97%, because the original antibacterial agent is not changed due to the fact that the aramid nanofiber layer is not added, and therefore the antibacterial effect is not affected. But the cell proliferation effect is obviously reduced, because the aramid nanofiber layer can provide a porous, interconnected and permeable three-dimensional cross structure, a space is provided for the cells and nutrient substances to enter, a proper microenvironment is provided for the cells, the adhesion and migration of the cells are promoted, and the signal transmission among the cells is carried out, so that the effect and the effect of promoting the cell proliferation are finally achieved, and the effect of cell proliferation is reduced due to the lack of the aramid nanofiber layer (shown in a table 6).
TABLE 6 results of cell proliferation test of aramid magnesium alloy composite and comparative example 3
Comparative example 4
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: in the preparation process of the aramid nanofiber in the step (2), the adding amount of potassium hydroxide is reduced, the adding amount of potassium hydroxide in the comparative example 4 is 0.3g, the diameter of the prepared aramid nanofiber is generally more than 800nm, the length of the prepared aramid nanofiber is also more than 100 mu m, the size of the prepared aramid nanofiber is larger, the specific surface area is small, the interface contact is poor, and the subsequent uniform assembly is not facilitated. The antibacterial performance of the aramid magnesium alloy composite material prepared from the large-size aramid nanofiber is slightly reduced by 91 percent, and the effect of promoting cell proliferation is also reduced (shown in table 7).
TABLE 7 aramid magnesium alloy composite and comparative example 4 cell proliferation test results
Comparative example 5
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: in the preparation process of the aramid nanofiber in the step (2), the stirring time is shortened, the next operation is carried out without changing into a reddish brown viscous solution, which means that the aramid staple fiber is still in a macroscopic fiber state and is not converted into a nanofiber, and the macroscopic staple fiber at the moment is not in a nanoscale in length and diameter and has strong surface inertia, so that the subsequent assembly work cannot be carried out.
Comparative example 6
The aramid fiber magnesium alloy composite material is prepared by adopting the same method as in the embodiment 1, except that: and (3) replacing the L-phenylpropanoid derivative in the step (3) with L-phenylpropanoid.
Compared with the L-phenylpropanoid derivatives, the L-phenylpropanoid has fewer non-covalent bond sites, and cannot be assembled together with the L-chiral amino acid and the antibacterial agent through intermolecular non-covalent bond interaction to form a uniform assembly, so that the antibacterial effect of the composite material on cell proliferation and antibacterial effect can be influenced (as shown in table 8), and the antibacterial rate of the composite material on staphylococcus aureus and escherichia coli can reach 93%.
TABLE 8 aramid magnesium alloy composite and comparative example 6 cell proliferation test results
From the experimental data results of examples 1-3, it can be seen that: the aramid fiber magnesium alloy composite material takes magnesium alloy as a substrate; the transition layer is an aramid nanofiber layer and has the functions of enhancing magnesium alloy and promoting cell proliferation; the outer layer is an antibacterial proliferation promoting hydrogel layer, and the L chiral structure can further increase cell adhesion proliferation and has antibacterial activity. In the preparation process, the magnesium alloy substrate is subjected to corrosion resistance treatment, the prepared para-aramid nanofiber is uniformly coated on the metal surface to form an entangled nanofiber network structure, and finally the antibacterial proliferation-promoting hydrogel is coated on the surface of the alloy/nanofiber layer, so that the aramid magnesium alloy composite material integrating corrosion resistance, antibacterial property and cell proliferation promotion is prepared through interlayer non-covalent bond interaction. The invention can avoid complicated processing procedures, provides the aramid magnesium alloy medical composite material for promoting cell proliferation through an assembly method and a preparation method thereof, and realizes a firm assembly structure through non-covalent bond interaction between a matrix, nanofiber and hydrogel. The nanostructure and chiral unit simulate the three-dimensional chiral cross-woven network structure of the extracellular matrix together, and cooperatively promote the adhesion and proliferation of cells. In addition, the high-strength high-modulus aramid nanofiber can effectively compensate for the strength loss during magnesium alloy degradation, and ensure the effective healing of bone tissues.
From comparison of the experimental results of example 1 and comparative example 1, it can be seen that: if the aramid nanofiber is not added into the hydrogel, the interface combination between the aramid nanofiber layer and the antibacterial proliferation-promoting hydrogel layer is poor, so that the subsequent two assembly layers are broken or destroyed, and the antibacterial and cell proliferation-promoting effects are further affected.
From comparison of the experimental results of example 1 and comparative example 2, it can be seen that: the preparation process of the hydrogel adopts a quenching mode to cool, so that the phase separation of the hydrogel can be directly caused, the components of the hydrogel after the phase separation cannot be uniformly dispersed, and the antibacterial and cell proliferation promoting effects are reduced. This is due to the uneven distribution of L chiral amino acid derivatives, antimicrobial agents, aramid nanofibers, leading to increased local bacterial proliferation without sufficient antimicrobial agents, and also to local cell lack of attachment points, and failure to follow-up proliferation.
From comparison of the experimental results of example 1 and comparative example 3, it can be seen that: if the intermediate aramid nanofiber layer is lacking, the antibacterial proliferation promoting hydrogel layer is directly coated on the medical magnesium alloy substrate after corrosion resistance treatment, the antibacterial performance of the composite material is not obviously affected, but the cell proliferation effect is obviously reduced. The intermediate aramid nanofiber layer does not have an antibacterial effect, so that the antibacterial performance of the whole material is not obviously affected, but the aramid nanofiber layer can provide a porous, interconnected and permeable three-dimensional cross structure, a space is provided for the cells and nutrient substances to enter, a proper microenvironment is provided for the cells, the adhesion and migration of the cells are promoted, the signal transmission among the cells is carried out, and finally, the effect and the effect of promoting the proliferation of the cells are achieved, so that the effect of cell proliferation is reduced due to the lack of the aramid nanofiber layer.
From comparison of the experimental results of example 1 and comparative example 4, it can be seen that: in the preparation process of the aramid nanofiber, the addition amount of potassium hydroxide is reduced, so that the antibacterial and cell proliferation promoting effects of the composite material are reduced. The method is characterized in that the deprotonation process of the aramid short fiber is affected by reducing the content of sodium hydroxide, so that the formed aramid nanofiber is large in diameter and length, small in specific surface area and poor in interface contact, and subsequent uniform assembly is not facilitated.
From comparison of the experimental results of example 1 and comparative example 5, it can be seen that: in the preparation process of the aramid nanofiber, the stirring time is shortened, the aramid staple fiber is still in a macroscopic fiber state because the aramid nanofiber is not changed into a reddish brown viscous solution, the macroscopic fiber is high in surface inertia and few in active sites, the aramid nanofiber cannot be coated on the surface of a magnesium alloy in a nanofiber layer structure, the hydrogel cannot be formed, the composite material is completely invalid, and the effects of resisting bacteria and promoting cell proliferation are completely absent.
From comparison of the experimental results of example 1 and comparative example 6, it can be seen that: the replacement of the L-phenylpropanoid derivatives with L-phenylpropanoid results in a decrease in the cell proliferation and antibacterial effect of the composite material. This is because the L-phenylpropanoid has fewer active sites than the L-phenylpropanoid derivatives, lacks functional groups such as hydroxyl groups and ether linkages which can participate in formation of intermolecular hydrogen bonds, and therefore has weak intermolecular noncovalent bonding forces, and cannot be co-assembled with the L-chiral amino acid and the antibacterial agent to form a uniform assembly, thereby affecting the cell proliferation promoting and antibacterial effects of the composite material.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. The aramid fiber magnesium alloy composite material for promoting cell proliferation is characterized by comprising a medical magnesium alloy substrate, an aramid fiber nanofiber layer and an antibacterial proliferation promoting hydrogel layer, wherein the aramid fiber nanofiber layer is positioned between the medical magnesium alloy substrate and the antibacterial proliferation promoting hydrogel layer;
the antibacterial proliferation promoting hydrogel layer comprises aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative, wherein the L-chiral amino acid derivative contains hydroxyl and ether bonds.
2. The cell proliferation promoting aramid magnesium alloy composite material according to claim 1, wherein the aramid nanofiber layer and the antibacterial proliferation promoting hydrogel layer have the diameter of 30-100nm and the length of 10-30 μm.
3. The aramid magnesium alloy composite material for promoting cell proliferation according to claim 1, wherein the antibacterial agent is one or more of gentamicin, azithromycin and rhein.
4. The aramid magnesium alloy composite material for promoting cell proliferation according to claim 1, wherein the L-chiral amino acid derivative is one or more of L-alanine derivative, L-tryptophan derivative and L-phenylalanine derivative;
the structural formula of the L-alanine derivative is as follows:
；
The structural formula of the L-phenylalanine derivative is as follows:
；
the structural formula of the L-tryptophan derivative is as follows:
。
5. The cell proliferation promoting aramid magnesium alloy composite material according to any one of claims 1 to 4, wherein in the antibacterial proliferation promoting hydrogel layer, the weight ratio of the aramid nanofiber, the antibacterial agent and the L-chiral amino acid derivative is 1: (0.5-1): (2-5).
6. A method for preparing an aramid magnesium alloy composite material for promoting cell proliferation according to any one of claims 1 to 5, which is characterized in that the method comprises the following steps:
s1, firstly, performing corrosion resistance treatment on a medical magnesium alloy substrate;
s2, uniformly coating the aramid nanofiber on the medical magnesium alloy substrate subjected to the corrosion resistance treatment, and then drying to form an aramid nanofiber layer on the medical magnesium alloy substrate;
S3, preparing the aramid nanofiber, the antibacterial agent, the L-chiral amino acid derivative and deionized water into hydrogel, uniformly coating the hydrogel on the aramid nanofiber layer to form an antibacterial proliferation-promoting hydrogel layer, and then drying to obtain the aramid magnesium alloy composite material.
7. The method for preparing a cell proliferation promoting aramid magnesium alloy composite material according to claim 6, wherein in the step S1, the corrosion resistance treatment method is any one of plasma spraying, electrochemical deposition and micro-arc oxidation.
8. The method for preparing an aramid fiber magnesium alloy composite material for promoting cell proliferation according to claim 6, wherein in the step S2, the method for preparing the aramid fiber is as follows: adding para-aramid short fibers into a protonation solvent of dimethyl sulfoxide, then adding potassium hydroxide, stirring until the solution becomes a reddish brown viscous solution, obtaining an aramid nanofiber solution, then adding deionized water, uniformly mixing, carrying out solid-liquid separation, and washing to remove the potassium hydroxide and the protonation solvent to obtain the aramid nanofiber;
The volume ratio of the dimethyl sulfoxide to the protonated solvent is 50 (1-2), the concentration of the potassium hydroxide in the protonated solvent of the dimethyl sulfoxide is 0.0095-0.0196 g/mL, and the mass ratio of the para-aramid staple fiber to the potassium hydroxide is 1: (0.5-1).
9. The method for preparing an aramid fiber magnesium alloy composite material for promoting cell proliferation according to claim 6, wherein in the step S3, the method for preparing the hydrogel is as follows: adding aramid nanofibers, an antibacterial agent and an L-chiral amino acid derivative into deionized water, uniformly stirring and heating to completely dissolve the molecules, and then slowly cooling to room temperature to obtain the hydrogel, wherein the cooling speed of the slow cooling is 0.5-1 ℃/min.
10. The method for preparing a cell proliferation promoting aramid magnesium alloy composite material according to claim 6, wherein the thickness of the aramid nanofiber layer is 100-500 microns, and the thickness of the antibacterial proliferation promoting hydrogel layer is 500-800 microns.
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| CN104587515A (en) * | 2013-11-01 | 2015-05-06 | 上海交通大学医学院附属第九人民医院 | Medical wound dressing with anti-infection function |
| WO2020079330A1 (en) * | 2018-10-16 | 2020-04-23 | Van Cleef Jean Francois | Composite protecting device that fits closely onto a wound |
| CN114507910A (en) * | 2022-02-22 | 2022-05-17 | 西安工程大学 | Nano-aramid fiber reinforced regenerated cellulose fiber material, preparation method and application |
| CN115073774A (en) * | 2021-03-12 | 2022-09-20 | 南雄中科院孵化器运营有限公司 | Preparation method and application of aramid fiber reinforced PVA hydrogel |
| CN115154642A (en) * | 2022-07-05 | 2022-10-11 | 福州大学 | Bionic asymmetric sponge dressing and preparation method thereof |
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| CN104587515A (en) * | 2013-11-01 | 2015-05-06 | 上海交通大学医学院附属第九人民医院 | Medical wound dressing with anti-infection function |
| WO2020079330A1 (en) * | 2018-10-16 | 2020-04-23 | Van Cleef Jean Francois | Composite protecting device that fits closely onto a wound |
| CN115073774A (en) * | 2021-03-12 | 2022-09-20 | 南雄中科院孵化器运营有限公司 | Preparation method and application of aramid fiber reinforced PVA hydrogel |
| CN114507910A (en) * | 2022-02-22 | 2022-05-17 | 西安工程大学 | Nano-aramid fiber reinforced regenerated cellulose fiber material, preparation method and application |
| CN115154642A (en) * | 2022-07-05 | 2022-10-11 | 福州大学 | Bionic asymmetric sponge dressing and preparation method thereof |
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