CN117797330A - Preparation method of antibacterial and anticoagulant coating with high bonding strength on zinc alloy surface - Google Patents
Preparation method of antibacterial and anticoagulant coating with high bonding strength on zinc alloy surface Download PDFInfo
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- CN117797330A CN117797330A CN202410207034.1A CN202410207034A CN117797330A CN 117797330 A CN117797330 A CN 117797330A CN 202410207034 A CN202410207034 A CN 202410207034A CN 117797330 A CN117797330 A CN 117797330A
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 149
- 238000000576 coating method Methods 0.000 title claims abstract description 104
- 239000011248 coating agent Substances 0.000 title claims abstract description 97
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 239000003146 anticoagulant agent Substances 0.000 title claims abstract description 27
- 229940127219 anticoagulant drug Drugs 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 26
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims abstract description 25
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- 238000004132 cross linking Methods 0.000 claims abstract description 4
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- 239000000956 alloy Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- 239000000126 substance Substances 0.000 claims description 8
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- 238000005234 chemical deposition Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
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- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims 1
- -1 1-ethyl- (3-dimethylaminopropyl) carbonyl Ethylenediamine Chemical compound 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 2
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- 108090000190 Thrombin Proteins 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- 210000000329 smooth muscle myocyte Anatomy 0.000 description 2
- 229960004072 thrombin Drugs 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 description 1
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- 238000006845 Michael addition reaction Methods 0.000 description 1
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- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
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- 230000001028 anti-proliverative effect Effects 0.000 description 1
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
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- WJSSIRUDIALLQN-UHFFFAOYSA-K dizinc;phosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])([O-])=O WJSSIRUDIALLQN-UHFFFAOYSA-K 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to the field of biomedical material surface modification, and provides a preparation method of an antibacterial anticoagulant coating with high bonding strength on a zinc alloy surface. The method firstly carries out normal pressure plasma treatment on the surface of the zinc alloy to improve the surface roughness of the zinc alloy. And then constructing a composite coating consisting of three components a, b and c on the surface of the treated zinc alloy. Wherein the layer a is a zinc phosphate (ZnP) coating which can inhibit Zn in the degradation process of the zinc alloy 2+ The biocompatibility and the antibacterial property of the zinc alloy are improved; the layer b is an organic coating based on Catechol (CA) and Polyethyleneimine (PEI) crosslinking, and mainly serves to connect the layer a and the layer c; layer c is composed of Heparin (Hep) drug coatingThe zinc alloy matrix is endowed with the required anticoagulation function. The multifunctional composite coating obtained by the method provided by the invention consists of three components of ZnP, CA/PEI and Hep, can effectively protect a zinc alloy substrate, and has a good application prospect in the field of coating materials for zinc alloy brackets.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a preparation method of an antibacterial anticoagulant coating with high bonding strength on a zinc alloy surface.
Background
The increasing prevalence of cardiovascular disease is one of the major problems threatening human health. Vascular stent intervention is the primary treatment modality for cardiovascular disease. In clinic, the use of permanent stents is dominant, but permanent stents are not absorbed by the human body after being placed in the body, and besides the need for patients to take antiplatelet drugs for a long period of time to prevent thrombosis, other potential risks may exist, such as chronic damage to the inner wall of the vessel, intimal hyperplasia, and restenosis of the vessel caused later. Thus, conventional metallic stents remain a challenge in clinical applications.
Biodegradable stents are the latest generation of stents and are characterized in that the biodegradable stents can be absorbed by the human body after being implanted into the human body, and degradation products do not cause serious host reaction so as to avoid risks and wounds caused by secondary operations. Among biodegradable metals, zinc and its alloys are considered as a very promising biodegradable orthopedic and cardiovascular implant material. Zinc ion is one of the most abundant trace metal elements in organisms, is closely related to the realization of biological functions of human bodies, and plays an important role in the activities and functions of various enzymes and cell metabolism; secondly, the corrosion potential of zinc is between that of magnesium and iron, and zinc alloy corrode at a rate of tens of micrometers per year, which is much lower than that of magnesium and magnesium alloy by about hundreds of micrometers per year; in addition, zinc-based implants have ideal degradation behavior in animals, slow followed by fast, with moderate overall degradation rates. The zinc and zinc alloy have good biological safety and application prospect as degradable medical metal materials.
With the intensive research and application of zinc alloy in degradable medical materials, the zinc alloy is used as a material with high biological activity, and Zn of the zinc alloy is used as a material with high biological activity 2+ Is a key factor in causing toxicity of Zn implants. A number of studies have shown that Zn for endothelial cells, smooth muscle cells and osteoblasts 2+ Exhibits a dual effect. In general, zn is present in a low concentration 2+ Can improve cell activity, promote cell proliferation, adhesion and migration, and has too high concentration of Zn 2+ It exhibits strong cytotoxicity in vitro. Zn released excessively during degradation of zinc-based alloy 2+ Is the main cause of serious cytotoxicity and poor biocompatibility, and is a technical bottleneck problem which limits the further application of the composition. How to control Zn in the degradation process of zinc matrix in vivo 2+ The excessive release behavior of (c) is a critical technical problem to be solved.
The material surface modification treatment provides a possible solution technical means. The preparation of the coating with biological function on the surface of the degradable zinc alloy can effectively solve Zn 2+ And the problem of excessive release, and simultaneously, the biocompatibility and the antibacterial property of the zinc alloy are further improved. Recent studies in the patent demonstrate that ZnP coatings are often used to improve the corrosion resistance of metals, and methods of preparing such coatings on zinc and zinc alloy surfaces have demonstrated some success. Patent CN 113529062A discloses a method for preparing ZnP chemical conversion film on zinc alloy surface, the ZnP coating has obvious protective effect on Zn alloy, can regulate corrosion rate of matrix, and can prevent rapid dissolution of matrix and excessive release of ions. However, the single ZnP coating has voids and cracks that are not strongly bonded to the zinc alloy substrate, which can lead to penetration of the solution into the substrate. At present, a method for preparing an antibacterial and anticoagulant composite coating with high bonding strength on the surface of a zinc alloy is not reported yet.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an antibacterial anticoagulant coating with high bonding strength on the surface of a zinc alloy aiming at the defects of the prior art. The coating layer is composed of a composite coating of ZnP, CA/PEI and Hep. The composite coating inhibits Zn 2+ Excessive release improves the biocompatibility and antibacterial property of the zinc alloy matrix, endows the zinc alloy with anticoagulation function and improves the clinical application effect. The invention mainly solves two technical problems, namely, the invention adopts normal pressure plasma treatment to increase the roughness of the zinc alloy surface and improve the firmness of ZnP coating cladding in order to solve the defect that the ZnP coating and the alloy substrate have weak binding force; secondly, the problem of single function of the ZnP coating is solved, a CA/PEI conversion coating is prepared on the ZnP surface, heparin molecules are grafted on the CA/PEI coating through amidation reaction, and the heparin grafted by the method can be firmly fixed on the ZnP coating surface and is not easy to fall off, so that the anticoagulation function of the coating is exerted.
The invention aims at realizing the following technical scheme:
(1) Firstly, carrying out pretreatment on the surface of a degradable zinc alloy material, and then carrying out normal-pressure plasma treatment on the surface of the zinc alloy to improve the binding force between ZnP and the zinc alloy;
(2) Preparing a ZnP conversion film on the surface of the zinc alloy by utilizing a chemical liquid phase deposition method;
(3) Grafting a CA/PEI coating on the surface of the zinc alloy containing the ZnP coating prepared in the step 2) based on crosslinking between CA and PEI molecules and chelation with Zn ions, wherein the CA represents catechol and the PEI represents polyethyleneimine;
the phenolic hydroxyl group on CA can be oxidized into a quinone group, and reacts with amine on PEI through Schiff base reaction and Michael addition to form a copolymer of CA and PEI, and then the copolymer is chelated with zinc ions to form a compact CA/PEI organic coating on the surface of zinc alloy. Wherein the amine moiety of PEI is consumed by catechol/quinone, thereby reducing cytotoxicity;
(4) And (3) further fixing heparin molecules on the zinc alloy material containing ZnP and the CA/PEI coating prepared in the step (3) by utilizing amidation reaction to obtain the degradable zinc alloy biomedical material with the high-bonding-strength antibacterial and anticoagulant coating.
The pretreatment step comprises polishing, ultrasonic cleaning, drying and the like, and further the cleaning solution is acetone, absolute ethyl alcohol and ultrapure water, and the ultrasonic cleaning time is 3-5 min.
Further, the atmospheric pressure plasma treatment employs ionized CO 2 、N 2 Or an open-air jet in the air is processed under the working conditions that the nozzle height is 0.2-0.8 cm, the gas flow is 30-80 SLPM, the interval is 0.04-0.09 cm, and the scanning speed is 100-800 cm/min.
The ZnP coating adopted by the invention can release a proper amount of zinc ions with biological activity, and has promotion effect on endothelial cells and smooth muscle cells.
Further, the preparation steps of the ZnP coating in the step 2) are specifically as follows: preparing a phosphating solution, fully dissolving the phosphating solution by ultrasonic treatment, and regulating the PH of the solution to be 2-3 by using a NaOH solution with the concentration of 5 mol/L. Placing the zinc alloy obtained in the step 1) into phosphating solution for constant temperature soaking, respectively ultrasonically cleaning the soaked zinc alloy with absolute ethyl alcohol and ultrapure water for 2-3 times, and placing the zinc alloy into an oven for drying until the surface has no water, thus obtaining the degradable zinc alloy material with the surface coated with ZnP.
Further, the main component of the phosphating solution in the step 2) is ZnP, and the substance for providing phosphate ions is H 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the The substance providing zinc ions is a zinc alloy matrix.
Further, the phosphating solution in the step 2) contains an accelerator, wherein the accelerator is Ca (NO 3 ) 2 ·4H 2 O、NaClO 3 、C 6 H 8 O 7 ·H 2 O、NaNO 3 Several of them;
further, the constant-temperature soaking temperature in the step 2) is 25 ℃, the soaking time is 30-60 minutes, and the pH of the phosphating solution is 2.0-3.0. When the temperature is too low, the zinc-phosphorus salt nucleation and the growth reaction rate are too slow; when the temperature is too high, the zinc corrosion reaction rate is too high, which is unfavorable for the growth and deposition of the coating, and the long-time high temperature also easily affects the mechanical strength of the zinc matrix; when the soaking time is too short, the coating is carried out in an island-shaped growth mode and does not cover the whole surface of the matrix completely, when the soaking time is too long, the reaction is balanced, and the thickness and the components of the coating are not changed basically; when the pH value of the solution is too low, zinc and phosphorus mainly exist in the solution in the form of respective ions, which is unfavorable for reaction nucleation and growth, and when the pH value of the solution is too high, zinc ions reach a saturated state, and are easy to form precipitation and separation in the forms of zinc hydroxide and zinc oxide.
Further, the preparation steps of the CA/PEI coating in the step 3) are specifically as follows: preparing Tris buffer solution containing CA and PEI, regulating pH value of the solution to 8.5, soaking zinc alloy sample with ZnP coating layer in the above liquid at constant temperature, ultrasonically cleaning the soaked sample with ultrapure water, and treating with N 2 And is dried and stored in a vacuum oven.
Further, the concentration of CA is 1-3 mg mL -1 PEI concentration is 2-6 mg mL -1 Further, the soaking time is 10-14 h.
Further, the preparation steps of the heparin coating in the step 4) are specifically as follows: a mixed solution containing heparin, a catalyst and ethanesulfonic acid (MES) was prepared, and a Zn-CA/PEI sample was immersed in the above mixed solution at 37℃for 3 h times, and then washed with distilled water for 3 times.
Further, the catalyst comprises one of EDC, HOBT or DMAP, and the concentration of heparin in the soaking solution is 3-5 mg/mL.
The preparation method of the antibacterial and anticoagulant coating with high bonding strength on the zinc alloy surface has the advantages that firstly, the zinc alloy surface is treated by adopting normal pressure plasma, the roughness of the alloy substrate surface is improved, and strong bonding force is provided for the adhesion of the surface ZnP coating; the zinc salt coating mainly exists in a form of which the solubility product is far smaller than ZnP of other zinc salts, can be used as an effective corrosion barrier layer, obviously reduces the initial release of zinc ions, improves the antibacterial performance of medical zinc base, and provides active sites for the surface of the zinc base through the crosslinking between CA and PEI molecules and the chelation with Zn ions, so that further grafted heparin medicine molecules can be firmly combined on the prepared ZnP coating, the problem that medicines are easy to fall off in vivo is solved, and the anticoagulation function is provided for the zinc base medical material.
The preparation method can be completed at normal temperature, and has the advantages of simple process, low cost, uniform and complete film layer, and fine and compact crystal grains.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a process flow diagram of the preparation of an antibacterial anticoagulant coating with high bonding strength on the surface of a zinc alloy.
FIG. 2 is an electron microscope scan of samples of uncoated zinc alloy substrates and samples of zinc phosphate alloys on the surface of the samples of examples 1-6 of the present invention.
FIG. 3 is a plot of the Taphil polarization curves for an uncoated zinc alloy substrate sample, a ZnP-zinc alloy sample, and a ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
FIG. 4 is a graph of the results of biocompatibility of the uncoated zinc alloy substrate sample, the ZnP-zinc alloy sample, the ZnP-CA/PEI-and the ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
FIG. 5 is a graph of the antimicrobial results of an uncoated zinc alloy substrate sample, a ZnP-zinc alloy sample, a ZnP-CA/PEI-and ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
FIG. 6 is a graph showing anticoagulation results of the samples in example 1 and comparative example 3 according to the invention.
Detailed Description
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
In the following examples, a process flow diagram of the preparation of the high bonding strength antibacterial anticoagulant coating on the surface of the zinc alloy provided by the invention is shown in fig. 1. The process flow is described below in connection with specific embodiments.
Example 1
The preparation method of the antibacterial anticoagulant coating with high bonding strength on the surface of the extruded Zn alloy material comprises the following specific steps:
1) Firstly, preparing a 13X 1.5mm round sheet-shaped sample of the extruded Zn alloy, sequentially polishing by using 200# water sand paper, 600# water sand paper and 1200# water sand paper, sequentially ultrasonically cleaning each sample for 4 min by using acetone, absolute ethyl alcohol and ultrapure water, drying, and treating the front and back surfaces of the sample by using an ultraviolet ozone cleaning instrument for 10 min.
2) Performing normal pressure plasma treatment on the sample in the step 1) by adopting a plasma laser, wherein the selected gas is ionized CO 2 The working conditions are as follows: nozzle height 0.5 cm, gas flow 50 SLPM, pitch 0.06 cm, scan rate 500 cm/min.
3) Preparing phosphating solution, namely measuring H 3 PO 4 13.3 ml, HNO 3 37.5 ml，Ca(NO 3 ) 2 ·4H 2 O 4.72 g，NaClO 3 2.13 g，C 6 H 8 O 7 ·H 2 O3.85 g, 1L of ultrapure water was added for dissolution, and 5mol/L NaOH was added to adjust the ph=2.5.
4) Placing the Zn alloy sample obtained in the step 2) into the phosphating solution, standing for 45 min at room temperature, respectively washing the soaked sample with ultrapure water and absolute ethyl alcohol for 3 times, each time for 3-5 min, and drying to obtain the Zn alloy sample with the surface coated ZnP coating.
5) Surface coating ZnP samples in the presence of CA (2 mg mL -1 ) And PEI (4 mg mL) -1 ) Is immersed in Tris buffer solution (ph=8.5) at 22 ℃ for 12 hours. Ultrasonic cleaning ZnP-CA/PEI zinc alloy sample with distilled water, then washing in N 2 And is stored in a vacuum oven.
6) The concentrations of heparin, EDC and ethanesulfonic acid (MES) in the mixed solution were 4 mg mL each -1 、1 mg mL -1 And 9.8 mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The coated ZnP-CA/PEI sample is soaked in the mixed solution at 37 ℃ for 3 h, and then washed with ultrapure water for 3 times, thus obtaining the zinc alloy sample with the surface coated with ZnP-CA/PEI-HeP.
Example 2
The preparation method of the antibacterial anticoagulant coating with high bonding strength on the surface of the extruded Zn alloy material comprises the following specific steps:
1) Firstly, preparing an extruded Zn alloy into a 13X 1.5mm round sheet sample, sequentially polishing the sheet sample by using 200# water sand paper, 600# water sand paper and 1200# water sand paper, sequentially ultrasonically cleaning the sheet sample by using acetone, absolute ethyl alcohol and ultrapure water for 3 min respectively, drying the sheet sample, and treating the front and back surfaces of the sheet sample by using an ultraviolet ozone cleaning instrument for 10 min respectively.
2) Performing normal pressure plasma treatment on the sample in the step 1) by adopting a plasma laser, wherein the selected gas is ionized CO 2 The working conditions are as follows: nozzle height 0.2 cm, gas flow 30 SLPM, pitch 0.04 cm, scan rate 100 cm/min.
3) Preparing phosphating solution, namely measuring H 3 PO 4 6.65 ml, HNO 3 18.75 ml，Ca(NO 3 ) 2 ·4H 2 O 2.36 g，NaClO 3 1.07 g，C 6 H 8 O 7 ·H 2 O1.93 g, 1L of ultrapure water was added for dissolution, and then 5mol/L NaOH solution was added for ph=2.
4) Placing the Zn alloy sample obtained in the step 2) into the phosphating solution, standing for 30min at room temperature, respectively washing the soaked sample with ultrapure water and absolute ethyl alcohol for 3 times, each time for 3-5 min, and drying to obtain the Zn alloy sample with the surface coated ZnP coating.
5) Surface coated ZnP samples were prepared in a solution containing CA (1 mg mL -1 ) And PEI (2 mg mL) -1 ) Is immersed in Tris buffer solution (ph=8.5) at 22 ℃ for 10 hours. The coated ZnP-CA/PEI sample was sonicated with distilled water and then washed in N 2 And is stored in a vacuum oven.
6) The concentrations of heparin, EDC and ethanesulfonic acid (MES) in the mixed solution were 4 mg mL each -1 、1 mg mL -1 And 9.8 mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The coated ZnP-CA/PEI sample is soaked in the mixed solution at 37 ℃ for 3 h, and then washed with ultrapure water for 3 times, thus obtaining the zinc alloy sample with the surface coated with ZnP-CA/PEI-HeP.
Example 3
The preparation method of the antibacterial anticoagulant coating with high bonding strength on the surface of the extruded Zn alloy material comprises the following specific steps:
1) Firstly, preparing an extruded Zn alloy into a 13X 1.5mm round sheet sample, sequentially polishing the round sheet sample by using 200# water sand paper, 600# water sand paper and 1200# water sand paper, sequentially ultrasonically cleaning the round sheet sample by using acetone, absolute ethyl alcohol and ultrapure water for 5min respectively, drying the round sheet sample, and treating the front and back surfaces of the round sheet sample by using an ultraviolet ozone cleaning instrument for 10 min respectively.
2) Performing normal pressure plasma treatment on the sample in the step 1) by adopting a plasma laser, wherein the selected gas is ionized CO 2 The working conditions are as follows: nozzle height 0.8 cm, gas flow 80 SLPM, pitch 0.09 cm, scan rate 800 cm/min.
3) Preparing phosphating solution, namely measuring H 3 PO 4 19.95 ml, HNO 3 56.25 ml，Ca(NO 3 ) 2 ·4H 2 O 7.08 g，NaClO 3 3.21g，C 6 H 8 O 7 ·H 2 O5.79 g, 1L of ultrapure water was added for dissolution, and 5mol/L NaOH was added to adjust the ph=3 of the solution.
4) Placing the Zn alloy sample obtained in the step 2) into the phosphating solution, standing for 60 min at room temperature, respectively washing the soaked sample with ultrapure water and absolute ethyl alcohol for 3 times, each time for 3-5 min, and drying to obtain the Zn alloy sample with the surface coated ZnP coating.
5) Surface coated ZnP samples were prepared in a solution containing CA (3 mg mL -1 ) And PEI (6 mg mL) -1 ) Is immersed in Tris buffer solution (ph=8.5) at 22 ℃ for 14 hours. The coated ZnP-CA/PEI sample was sonicated with distilled water and then washed in N 2 And is stored in a vacuum oven.
6) The concentrations of heparin, EDC and ethanesulfonic acid (MES) in the mixed solution were 4 mg mL each -1 、1 mg mL -1 And 9.8 mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the Immersing ZnP-CA/PEI sample in the mixed solution at 37 ℃ for 3 h, and then flushing with ultrapure water for 3 times to obtain the zinc alloy sample with the surface coated with ZnP-CA/PEI-HeP.
Example 4
The same as in example 1, except that the gas selected for the normal pressure plasma treatment of the sample by the plasma laser was ionized N 2 The working conditions are as follows: nozzle height 0.4 cm, gas flow 45 SLPM, pitch 0.06 cm, scan rate 300 cm/min.
Example 5
The other points are the same as in example 1, except that: step 6) the concentration of heparin in the mixed solution is 3 mg mL -1 The corresponding EDC was 0.75 mg mL -1 Ethanesulfonic acid (MES) was 7.35 mg mL -1 。
Example 6
The other points are the same as in example 1, except that: step 6) the concentration of heparin in the mixed solution is 5 mg mL -1 The corresponding EDC was 1.25 mg mL -1 Ethanesulfonic acid (MES) was 12.25 mg mL -1 。
The antibacterial and anticoagulant coating with high bonding strength is prepared on the surface of the zinc alloy by adopting the method, and the zinc alloy is a binary and multi-element zinc alloy of Zn-Cu system, zn-Mg system, zn-Sr system, zn-Mn system, zn-Li system, zn-Ag system, zn-Fe system or Zn-Re system.
Comparative example 1
Other conditions were identical to example 1 except that no atmospheric plasma treatment was performed on the pretreated zinc alloy samples in step 2).
Comparative example 2
Other conditions were identical to example 1 except that the sample without surface coating ZnP in step 5) was prepared with a CA/PEI organic coating and the heparin drug coating in step 6) was chemically deposited onto the ZnP coating by chemical deposition, comprising the following steps: heparin concentration was set to 4 mg mL -1 Is a solution of (a); znP-CA/PEI sample is soaked in heparin solution at 37 ℃ for 3 h, and then washed with ultrapure water for 3 times, thus obtaining the zinc alloy sample with the surface coated with ZnP-HeP.
Comparative example 3
Other conditions were identical to example 1 except that no heparin drug coating was prepared in step 6), and that only ZnP-CA/PEI-coating was prepared on the zinc alloy substrate.
Comparative example 4
Otherwise identical to example 1, except that step 2) employs ionized CO 2 The working conditions for normal pressure plasma treatment of the sample are as follows: nozzle height 0.1 cm, gas flow 20 SLPM, pitch 0.02 cm, scan rate 80 cm/min.
Comparative example 5
The procedure is otherwise as in example 1, except that the phosphating solution of step 3) is prepared by taking H 3 PO 4 3.3 ml, HNO 3 9.4 ml，Ca(NO 3 ) 2 ·4H 2 O 1.18 g，NaClO 3 0.53 g，C 6 H 8 O 7 ·H 2 O0.97, g, 1L of ultrapure water was added for dissolution, and then 5mol/L NaOH solution was added for ph=2.5.
Comparative example 6
The procedure is otherwise as in example 1, except that the CA concentration in step 5) is 0.5 mg mL -1 PEI concentration of 1 mg mL -1 The soaking time was 8 hours.
Scanning electron microscope analysis
The microscopic morphology of the uncoated zinc alloy substrate material samples of examples 1 to 6 and the surface zinc phosphate zinc alloy samples of examples 1 to 6 were analyzed by using a scanning electron microscope.
FIG. 2 is a scanning electron microscope image (FIG. 2B) of an uncoated zinc alloy substrate material sample (FIG. 2A) and a surface preparation ZnP coated zinc alloy sample employed in example 1 of the present invention.
As can be seen from fig. 2, under the given conditions, zinc element contained in the zinc alloy can be converted into ZnP to cover the surface of the alloy, the film layer is compact and complete, the crystal grains are of micron-sized structures and grow in an island shape and spread around in a chrysanthemum shape, and the phenomenon shows that the preparation of the chemical conversion film on the surface ZnP of the zinc alloy matrix can be realized in a short time.
Analysis of binding force Strength
The coating bond force, which is the sum of the physical and chemical forces between the coating and the substrate, is related to the protective capability of the coating to the substrate, and table 1 reveals the coating bond force ratings of examples 1-6 and comparative examples 1-6 according to ASTM3359-02 standard painted-tape peel test:
TABLE 1 sample binding force class distribution table
As can be seen from Table 1, the coating bonds of examples 1 to 6, comparative example 3 and comparative example 6 are all 5 grades, which indicates that the sample coating has no obvious cracks or drops during the test; comparative example 1 did not subject the sample to atmospheric plasma treatment, resulting in an untight bond between the ZnP coating and the zinc alloy matrix and therefore a weak bond; in the comparative example 2, the organic coating of CA/PEI is not prepared, so that the heparin drug coating is only combined on the surface of the ZnP coating by a chemical deposition method, and therefore heparin molecules are easy to fall off and have weak binding force; comparative example 4 changed the working conditions during normal pressure plasma treatment, and the surface of the zinc alloy did not reach the expected roughness due to the small gas flow, too slow scanning rate, etc., resulting in the weakening of the binding force between the coating and the zinc alloy substrate; comparative example 5 changes the concentration of the active ingredient in the phosphating solution, resulting in the existence of voids and cracks in the prepared ZnP coating, and thus resulting in reduced coating binding force; the results show that the normal pressure plasma treatment of the zinc alloy substrate and the preparation of the CA/PEI organic coating can obviously enhance the firmness of the composite coating and the zinc alloy metal substrate and improve the bonding force of the coating.
Electrochemical test analysis
FIG. 3 is a plot of Taphillips polarization curve versus an uncoated zinc alloy substrate sample, a ZnP-zinc alloy sample, a ZnP-CA/PEI-zinc alloy sample, and a ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
As can be seen from fig. 3, the corrosion potentials of the ZnP-zinc alloy sample, znP-CA/PEI-zinc alloy sample and ZnP-CA/PEI-Hep-zinc alloy sample all showed positive movement compared to the uncoated zinc alloy substrate sample, indicating that the coating can effectively improve the corrosion resistance of the zinc alloy substrate; wherein, the self-corrosion potential of the ZnP-CA/PEI-Hep-zinc alloy sample is closest to the positive electrode, which indicates that the corrosion resistance of the coating is the best.
Biocompatibility test analysis
FIG. 4 is a graph of the results of biocompatibility testing of the uncoated zinc alloy substrate sample, the ZnP-zinc alloy sample, the ZnP-CA/PEI-zinc alloy sample, and the ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
As can be seen from fig. 4, the cell activities of the uncoated zinc alloy substrate sample, the ZnP-zinc alloy sample, the ZnP-CA/PEI-zinc alloy sample and the ZnP-CA/PEI-Hep-zinc alloy sample are 19.28%, 28.88%, 32.46% and 40.12%, respectively, which indicates that the coating can effectively improve the biocompatibility of the zinc alloy substrate; compared with an uncoated zinc alloy substrate sample, the cell activity of the ZnP-CA/PEI-Hep-zinc alloy sample is doubled, which shows that the ZnP-CA/PEI-Hep-coating can greatly improve the biocompatibility of the zinc alloy substrate.
Antimicrobial test analysis
FIG. 5 is a graph of the antimicrobial test results of the uncoated zinc alloy substrate sample, the ZnP-zinc alloy sample, the ZnP-CA/PEI-zinc alloy sample, and the ZnP-CA/PEI-Hep-zinc alloy sample of example 1 of the present invention.
As can be seen from fig. 5, the antibacterial rates of the uncoated zinc alloy substrate sample, the ZnP-zinc alloy sample, the ZnP-CA/PEI-zinc alloy sample and the ZnP-CA/PEI-Hep-zinc alloy sample are 68.97%, 77.72%, 76.23% and 78.18%, respectively, which indicates that the coating can effectively improve the antibacterial property of the zinc alloy substrate.
Anticoagulation effect test analysis
1) Heparin has a well-known anticoagulant function and has a remarkable antiproliferative effect on Vascular Smooth Muscle Cells (VSMCs), so that the heparin drug coating is introduced into the zinc alloy to endow the zinc alloy with the anticoagulant function; FIG. 6 shows graphs of the results of the example 1 and comparative example 3 samples co-cultured with VSMCs for 1 day and 3 days. Example 1 comparative example 3 differs in the presence or absence of a heparin drug coating, and as can be seen from fig. 6, the introduction of the heparin coating can significantly inhibit the proliferation of VSMCs, imparting anticoagulant function to the zinc alloy.
2) Activated Partial Thrombin Time (APTT) test (clotting time for detecting biomolecules): the Activated Partial Thrombin Time (APTT) of each fresh serum sample was first tested using a fully automatic coagulometer and recorded as the original value, and then the APTT was again tested after incubating the serum on the coatings prepared in each example and comparative example for 30min, with the pretreated zinc alloy matrix as the blank. The test results are shown in table 2:
table 2 APTT test results
As shown in Table 2, the APTT values of the coatings prepared in the examples 1-6 of the invention after the serum is incubated are obviously prolonged compared with the initial values, and the prolonged time is more than 30s (more than 10s are clinically significant), which indicates that the composite coating has good anticoagulation effect, and the coatings prepared in the examples 1-6 of the invention have certain anticoagulation performance.
In conclusion, the preparation method of the multifunctional composite coating can form a coating with degradation inhibition function on the surface of the zinc alloy, reduce the degradation rate of the zinc alloy, inhibit excessive release of zinc ions and endow the zinc alloy material with the comprehensive functions of anticoagulation, anti-inflammation, endothelialization, low toxicity and high biocompatibility. The multifunctional composite coating constructed on the surface of the zinc alloy material can obviously improve the service length and quality of the zinc alloy, and has good application prospect in the fields of coating and finishing materials of zinc alloy brackets.
Claims (9)
1. The preparation method of the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy is characterized by comprising the following steps of:
(1) Pretreating the degradable zinc alloy material, and carrying out normal-pressure plasma treatment on the treated zinc alloy surface to improve the binding force between the ZnP coating and the substrate;
(2) Preparing a ZnP conversion film on the surface of the zinc alloy by utilizing a chemical liquid phase deposition method;
(3) Grafting a CA/PEI coating on the surface of the zinc alloy containing the ZnP coating prepared in the step 2) based on crosslinking between CA and PEI molecules and chelation with Zn ions, wherein the CA represents catechol; the PEI represents polyethylenimine;
(4) And (3) further fixing heparin molecules on the zinc alloy material containing the ZnP and CA/PEI coatings prepared in the step (3) by utilizing amidation reaction to obtain the degradable zinc alloy biomedical material with the antibacterial and anticoagulant coatings ZnP-CA/PEI-HeP.
2. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the pretreatment step in the step 1) comprises the steps of polishing, ultrasonic cleaning, drying and the like.
3. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the normal pressure plasma treatment in the step 1) adopts ionized CO 2 、N 2 Or one of the open air jet flows in the air is treated, and further, the gas flow is 30-80 SLPM, and the scanning speed is 100-800 cm/min.
4. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the preparation steps of the ZnP coating in the step 2) are specifically as follows: preparing phosphating solution, soaking the zinc alloy obtained in the step 1) in the phosphating solution at constant temperature, respectively ultrasonically cleaning the soaked zinc alloy with absolute ethyl alcohol and ultrapure water for 2-3 times, and placing the cleaned zinc alloy into an oven for drying until the surface has no water, thus obtaining the degradable zinc alloy material with the surface coated with ZnP.
5. The method for preparing a high-bonding-strength antibacterial anticoagulant coating on a zinc alloy surface according to claim 4, wherein the phosphating solution contains an accelerator, and the accelerator is Ca (NO 3 ) 2 ·4H 2 O、NaClO 3 、C 6 H 8 O 7 ·H 2 O、NaNO 3 Several of them; further, the concentration of each substance in the phosphating solution is: phosphoric acid 0.1-0.3 mol/L, nitric acid 0.3-0.9 mol/L, and accelerator 0.01-0.03 mol/L; further, the pH value of the phosphating solution is 2.0-3.0.
6. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 4, wherein the constant-temperature soaking time in the phosphating solution is 30-60 min.
7. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the CA/PEI coating in the step 3) adopts a chemical deposition method, and the concentration of CA is 1-3 mg mL -1 PEI concentration is 2-6 mg mL -1 Further, the soaking time is 10-14 h.
8. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the amidation reaction in the step 4) is one of 1-ethyl- (3-dimethylaminopropyl) carbonyl Ethylenediamine (EDC), 4-Dimethylaminopyridine (DMAP) and 1-Hydroxybenzotriazole (HOBT).
9. The method for preparing the antibacterial and anticoagulant coating with high bonding strength on the surface of the zinc alloy according to claim 1, wherein the concentration of heparin in the soaking solution is 3-5 mg/mL in the step 4).
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| KR20130011354A (en) * | 2011-07-21 | 2013-01-30 | 연세대학교 산학협력단 | Bio-inspired multilayer hydrogel coating with adhesive polymer-catechol conjugates |
| CN108721704A (en) * | 2018-07-05 | 2018-11-02 | 四川大学 | It is a kind of to have both anticalciumization and the difunctional long-acting slow-release angiocarpy coating material and preparation method thereof of anti-proliferate |
| CN109939272A (en) * | 2019-03-21 | 2019-06-28 | 西南交通大学 | A kind of anticoagulant material and preparation method thereof |
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| KR20130011354A (en) * | 2011-07-21 | 2013-01-30 | 연세대학교 산학협력단 | Bio-inspired multilayer hydrogel coating with adhesive polymer-catechol conjugates |
| CN108721704A (en) * | 2018-07-05 | 2018-11-02 | 四川大学 | It is a kind of to have both anticalciumization and the difunctional long-acting slow-release angiocarpy coating material and preparation method thereof of anti-proliferate |
| CN109939272A (en) * | 2019-03-21 | 2019-06-28 | 西南交通大学 | A kind of anticoagulant material and preparation method thereof |
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