CN111733436A - Silver-iodine surface modified titanium alloy implant and preparation method thereof - Google Patents
Silver-iodine surface modified titanium alloy implant and preparation method thereof Download PDFInfo
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Abstract
The invention provides an antibacterial silver-iodine surface modified titanium alloy implant and a preparation method thereof, wherein a coating containing silver and iodine is fixed on a titanium alloy by a micro-arc oxidation reaction and an electrochemical method, and the silver ions and the iodine ions are mutually combined so as to further enhance the combination capability of the titanium alloy and obtain stable antibacterial performance; the material prepared by the process has a relatively obvious broad-spectrum antibacterial effect, the antibacterial active ingredients are silver, iodine and silver iodide, and compared with a single silver or iodine surface modification scheme, the combined use of the silver and iodine elements can enhance the antibacterial effect, reduce the use amount of the silver and iodine elements and also reduce the toxic and side effects caused by overhigh local concentration of the silver or iodine to a certain extent; the invention is applied to the surgical operation using the titanium alloy implant at present, and reduces the related infection of the implant and the corresponding complication which appear after the operation.
Description
Technical Field
The invention relates to a silver-iodine surface modified titanium alloy implant with excellent antibacterial performance and a preparation method thereof.
Background
Due to the characteristics of high strength, corrosion resistance and the like, the titanium alloy material is widely applied to the fields of artificial joints, fracture internal fixation devices, spine fixation and fusion materials, oral repair and the like at present, but related infection caused by internal implants also becomes a problem which is relatively troublesome clinically at present. For such infections, treatment regimens with systemic antibiotics are currently mainly adopted clinically. However, such treatment schemes have the defects of long treatment course, poor effect, easy double infection, easy organ injury and the like.
The excellent antibacterial property of silver has been known and utilized for a long time, and has high efficiency, broad-spectrum antibacterial property and good drug resistance. Nano silver is a nano-scale silver elementary substance particle. It has stronger antibacterial performance than common silver, and is applied to antibacterial medicines and medical appliances, antibacterial plastics and rubber products, antibacterial textiles and clothes, shoes and socks, antibacterial coatings, ceramics and glass, tableware, milk bottles and the like at present. Nano silver is currently considered as a safe material.
Iodine has broad-spectrum antibacterial activity. It can be combined with the cell wall, cell membrane and protein on cytoplasm of microorgans such as yeast, mould, protozoan and virus to modify them, so as to obtain the antibacterial effect. Polyvinylpyrrolidone iodine (PVP-I) is currently the only iodophor accepted by the national drug code in china, the uk, the usa, japan, etc. and approved for use in medical hygiene and in human disinfection. It has the characteristics of no toxicity, no irritation, safe use, good stability and the like.
The micro-arc oxidation method is also called as a plasma electrolytic oxidation method and is a novel surface modification method. The literature proves that the titanium dioxide coating is prepared on the titanium substrate by utilizing the micro-arc oxidation technology, and the titanium dioxide coating can induce the growth of hydroxyapatite on the surface of the material and has good cell adhesion property. In the preparation method, the surface area of the base material is increased through micro-arc oxidation so as to be beneficial to deposition of elements such as Ag, I and the like, and the base material has certain biological activity.
Disclosure of Invention
The invention provides a silver-iodine surface-modified titanium alloy implant with antibacterial performance and a preparation method thereof, aiming at the problem of implant infection caused by the use of a titanium alloy medical material in the orthopedic field.
The invention uses an electrochemical method to carry out silver-iodine modification on the surface of the micro-arc titanium oxide alloy, and mainly comprises three steps of titanium alloy surface roughening, silver surface modification and iodine surface modification.
The technical scheme of the invention is as follows:
a titanium alloy implant with a silver-iodine surface modification is prepared by the following method:
(1) surface roughening of titanium alloys
After the surface of the titanium alloy substrate is pretreated, the titanium alloy substrate is immersed into an electrolytic bath solution for electrochemical treatment to form a surface porous film structure;
specifically, the surface pretreatment method comprises the following steps: polishing, sand blasting and impurity removing are carried out on the material, and the impurity removing comprises the following steps: washing with acetone (more than or equal to 99.5%), ethylene glycol (more than or equal to 99.5%) and ultrapure water in sequence, then acid washing, and finally ultrasonic cleaning; the acid cleaning adopts HF and HNO3、H3PO4The acid washing time of the mixed acid solution is 5-25 min; the ultrasonic cleaning comprises the following steps: cleaning the material in ultrapure water for 5minPer time, 3 times of circulation;
the electrochemical treatment is anodic oxidation or micro-arc oxidation; the electrolytic cell solution comprises: 1-20g/L of calcium acetate, 1-20g/L of monocalcium phosphate, 10-20g/L of ethylene diamine tetraacetic acid disodium salt, 1-20g/L of calcium glycerophosphate and deionized water as a solvent; in the electrochemical reaction process, a titanium alloy base material is placed on a titanium alloy hook or a mesh basket to serve as an anode, a pure titanium plate serves as a cathode, the distance between the anode and the cathode is 10-30cm, the voltage is controlled to be 200-700V during the reaction period, the frequency is 100-500HZ, the duty ratio is 10-30%, the temperature is 20-40 ℃, and the reaction time is 2-15 min;
the thickness of the obtained porous film is 5-20 μm;
(2) silver modification on surface of titanium alloy material
Placing the titanium alloy material with the roughened surface in a silver nitrate aqueous solution for electrochemical treatment to obtain a titanium alloy material with a silver-modified surface;
the concentration of the silver nitrate aqueous solution is 0.005-0.02 g/L;
the electrochemical treatment method comprises the following steps: taking a silver nitrate aqueous solution as an electrolyte, placing the material on a titanium alloy hook or a mesh basket as a cathode under the environment of normal temperature (20-30 ℃) and 3-10V constant pressure, taking a titanium alloy plate as an anode, and reacting for 10-60s, wherein the distance between the cathode and the anode is 10-18 cm; after each time of the operation, the material is soaked in pure water for 1min, and the operation is circulated for 3 times;
(3) iodine modification on surface of titanium alloy material
Placing the material subjected to surface silver modification in an iodine-containing solution, performing surface iodine modification by an electrochemical method, and then cleaning and drying to obtain the titanium alloy implant subjected to surface silver iodine modification;
the iodine-containing solution is a mixed aqueous solution of an iodine compound and beta-cyclodextrin, wherein the concentration of the iodine compound is 2-6g/L, and the concentration of the beta-cyclodextrin is 1-8 g/L; the mass ratio of the iodine compound to the polyvinylpyrrolidone iodine complex powder is (1-5): 1;
the electrochemical method comprises the following steps: using iodine-containing solution as electrolyte, placing the material on a titanium alloy hook or a mesh basket as an anode under the conditions of normal temperature and constant pressure of 30-90V, using a pure titanium plate as a cathode, wherein the distance between the cathode and the anode is 10-20cm, and the reaction time is 10-70 min;
the drying temperature is 30-40 ℃, the drying time is 3-6h, and light shielding is required.
The effective antibacterial components of the titanium alloy implant with the silver-iodine surface modified are silver and iodine substances, and the iodine substances comprise iodine simple substance, silver iodide and polyvinylpyrrolidone iodine. The thickness of the silver-iodine antibacterial coating on the surface of the titanium alloy implant is 10-20 mu m, the silver content on the surface is 0.03-0.2 wt%, and the iodine content on the surface is 0.5-2 wt%.
The application of the silver-iodine surface modified titanium alloy implant comprises but is not limited to internal and external fixation of orthopedics and the range of the implant, and the titanium alloy implant has obvious bacteriostatic action on common infectious strains of surgical operations, such as staphylococcus aureus, escherichia coli and the like.
The antibacterial material prepared by the invention has good biological safety and antibacterial activity. Wherein the CCK-8 experimental results suggest that the three batches of materials subjected to the repeated tests have no obvious difference in cell proliferation activity in the group, i.e. the experimental group has no obvious cytotoxicity (as shown in fig. 2, the experimental group is a titanium alloy containing silver and iodine elements on the surface, the control group is a common titanium alloy, and the shown result is the result of 24h in vitro culture of human-derived mesenchymal stem cells on the surface of the material); in vitro antibacterial experiments show that the modified material has a relatively obvious antibacterial effect on staphylococcus aureus (as shown in figure 3, the main experimental process comprises the steps of dripping standard staphylococcus aureus liquid with the concentration of 2-5 multiplied by 105/ml in a logarithmic phase on the surface of a disc-shaped material with the diameter of 2cm after sterilization, culturing for 3 hours under the condition of 37 ℃ and proper humidity, eluting surface bacteria by 3ml of sterile SBF liquid, uniformly oscillating and diluting eluent into a plurality of concentration gradients, coating 100ul of each group on a culture plate, and culturing for 16 hours in a constant temperature box at 23 ℃ under the conditions that the experimental group is a titanium alloy with the surface containing silver and iodine elements and the comparison group is a common titanium alloy).
The invention has the advantages that:
the invention utilizes the compound with nano silver, iodine and iodine to have strong antibacterial performance, achieves the purpose of endowing the material with strong antibacterial performance by constructing the silver-iodine modified surface layer on the iodine-carrying titanium alloy part, and avoids the toxic and side effects of cells caused by excessive use of a single element by combined use of two elements of silver and iodine. The method has the advantages of simple process, proper reaction conditions, high efficiency and short production period, and the obtained titanium alloy implant has very obvious antibacterial effect.
Drawings
FIG. 1: and (3) performing surface electron microscope characterization and element EDS analysis on the titanium alloy modified by the silver and iodine surface.
FIG. 2: material CCK8 experimental results.
FIG. 3: the detection result of the antibacterial performance of the material is as follows: a is a comparison group, common titanium alloy; b is the experimental group, silver iodine coated titanium alloy.
FIG. 4: after the three materials are placed in a light environment for 1 day and 3 days, the surface bacteriostasis effect detection is carried out: the reference group is a common titanium alloy sample sheet; group A is sample wafer for direct anodic oxidation iodine-carrying treatment; group B is the silver iodine surface modified coupon prepared according to example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1
1. The material (supplied by Zhejiang Uhui medical instruments Co., Ltd.) was polished and sandblasted. The surface roughness Ra value of the treated material is in the range of 0-0.4 microns. Pretreating with acetone (not less than 99.5%), ethylene glycol (not less than 99.5%), ultrapure water, etc., and adding HF (not less than 40%, 20ml/L) and HNO3(65.0～68.0％，80ml/L)、H3PO4Acid washing in solution system (85%, 15ml/L) for 15min, finally ultrasonic cleaning for 3 times, and blow drying.
2. And (3) carrying out micro-arc oxidation on the material subjected to the step (1), wherein the reaction solution system is as follows: calcium acetate (AR,10g/L), monocalcium phosphate (AR,10g/L), ethylenediaminetetraacetic acid disodium salt (AR, 15g/L), calcium glycerophosphate (AR,10g/L), the material being immobilized on the anode side, the distance between the anode side and the cathode side being 25cm, the reaction conditions being: the voltage is 300V, the frequency is 100HZ, the duty ratio is 10 percent, the water temperature is 30 ℃, and the reaction time is 5 min; and finally, placing the sample subjected to the oxidation operation in an aqueous solution for ultrasonic immersion cleaning for 3min, and circulating for 3 times.
3. And (3) carrying out short-time, low-voltage and multi-time silver plating treatment and immersion cleaning on the material which is subjected to the step (2), wherein the process is as follows: placing the material in silver nitrate solution with concentration of 0.005g/L, fixing the prepared material on the cathode side, reacting for 45s under the condition of constant pressure of 3V and spacing between cathode and anode of 15cm, soaking and washing in pure water for 1min after each reaction, circulating for 3 times, and drying.
4. The material completing step 3 was placed in a mixed solution system of an iodine compound [ wherein potassium iodide powder 3g (Aladdin CAS #7681-11-0), povidone iodine 3g (Ron's reagent CAS #25655-41-8) ] at a concentration of 6g/L and beta-cyclodextrin at a concentration of 5 g/L. Fixing the material on the anode side, keeping the distance between the cathode and the anode at 20cm, reacting at constant pressure of 60V for 45min, washing, drying at 30-40 deg.C in dark for 6h, and sterilizing by irradiation.
5. the invention relates to an antibacterial test of an iodine-carrying titanium alloy implant, which is characterized in that staphylococcus aureus (ATCC25923) is used as test bacteria, common titanium sheets with the side length of 10mm and the height of 2mm and iodine-carrying titanium sheets with silver-iodine modified surface layers are selected, two groups of titanium sheets are sterilized and then are placed in a 24-hole plate, each group is provided with 3 multiple holes, and staphylococcus aureus (ATCC25923) bacterium liquid (about 2-5 × 10) is added6CFU/ml) was inoculated in a volume of 100. mu.l per well to each of the above groups of titanium plates, and the plates were subjected to static culture at 37 ℃ for 18 hours in a constant humidity environment. Bacteria adhered to the surface of the titanium sheet are eluted by sterile PBS, the eluent is diluted to a proper concentration in an equal proportion, and then an agarose gel culture dish is coated, and the bacteria colony is counted and photographed after being cultured for 24 hours at 37 ℃ in an incubator (the result is shown in figure 3).
6. the sample biocompatibility test of the experiment is to adopt CCK-8(Cell Counting Kit-8) method to measure the index of Cell proliferation capacity to judge Cell culture, wherein rat-derived mesenchymal stem cells are taken for culture, cells in logarithmic growth phase are digested by trypsin, and the cells are counted under a microscope to be prepared into 5 multiplied by 104Individual cells/ml of cell suspension. Taking 1ml to 12-hole plates respectively,each group of cells was seeded in 3 identical wells per plate for repeat experiments, 5 × 104Cells/well, incubated overnight at 37 ℃; placing sterilized circular common titanium plate with diameter of 20mm and silver-iodine-containing modified surface titanium plate into the well plates of control group and experimental group respectively, and adding 1ml DMEM (minimum Eagle's medium) complete culture medium into each well; after 24h of culture, CCK-8 and serum-free essential medium were mixed at a volume ratio of 1:10, 500ul per well, 5% CO at 37 ℃2Incubating for 2h in an incubator; 100ul of the supernatant was added to a 96-well plate per well, absorbance at 450nm was measured by a microplate reader, and the value of each plate was recorded (results are shown in FIG. 2).
7. Coating antibacterial effect contrast experiment: dividing the titanium alloy sample into a control group, an A group and a B group; wherein the control group sample is not subjected to operations except impurity removal and disinfection; the group A samples are prepared into iodine-carrying titanium alloy sample wafers according to the prior art (the preparation process refers to Chinese patent document CN 102416202A); and preparing the group B samples according to the steps 1-4 to obtain the silver-iodine surface layer modified titanium alloy sample. Placing the samples of the control group, the group A and the group B in natural light at room temperature of 20-30 deg.C for 24h and 72h, and performing antibacterial detection on the obtained sample according to step 5 to obtain the results shown in FIG. 4. From the results, the silver-iodine modified titanium alloy sample has more advantages in bacteriostasis effect and lasting action time than the iodine-carrying titanium alloy sample prepared by the prior art, which is probably the result of the combined action of two elements of silver and iodine.
Claims (6)
1. The titanium alloy implant with the silver-iodine surface modified is characterized by being prepared by the following method:
(1) surface roughening of titanium alloys
After the surface of the titanium alloy substrate is pretreated, the titanium alloy substrate is immersed into an electrolytic bath solution for electrochemical treatment to form a surface porous film structure;
the electrolytic cell solution comprises: 1-20g/L of calcium acetate, 1-20g/L of monocalcium phosphate, 10-20g/L of ethylene diamine tetraacetic acid disodium salt, 1-20g/L of calcium glycerophosphate and deionized water as a solvent;
the electrochemical treatment is anodic oxidation or micro-arc oxidation;
(2) silver modification on surface of titanium alloy material
Placing the titanium alloy material with the roughened surface in a silver nitrate aqueous solution for electrochemical treatment to obtain a titanium alloy material with a silver-modified surface;
the concentration of the silver nitrate aqueous solution is 0.005-0.02 g/L;
(3) iodine modification on surface of titanium alloy material
Placing the material subjected to surface silver modification in an iodine-containing solution, performing surface iodine modification by an electrochemical method, and then cleaning and drying to obtain the titanium alloy implant subjected to surface silver iodine modification;
the iodine-containing solution is a mixed aqueous solution of an iodine compound and beta-cyclodextrin, wherein the concentration of the iodine compound is 2-6g/L, and the concentration of the beta-cyclodextrin is 1-8 g/L; the mass ratio of the iodine compound to the polyvinylpyrrolidone iodine complex powder is (1-5): 1.
2. The silver-iodine surface-modified titanium alloy implant according to claim 1, wherein in the electrochemical reaction process in the step (1), the titanium alloy substrate is placed on a titanium alloy hook or a mesh basket to serve as an anode, a pure titanium plate is used as a cathode, the distance between the anode and the cathode is 10-30cm, the voltage is controlled to be 200-700V during the reaction, the frequency is 100-500HZ, the duty ratio is 10% -30%, the temperature is 20-40 ℃, and the reaction time is 2-15 min.
3. The silver-iodine surface-modified titanium alloy implant according to claim 1, wherein in the step (2), the electrochemical treatment method comprises: taking silver nitrate aqueous solution as electrolyte, placing the material on a titanium alloy hook or a mesh basket as a cathode under the environment of normal temperature and constant voltage of 3-10V, taking a titanium alloy plate as an anode, and reacting for 10-60s, wherein the distance between the cathode and the anode is 10-18 cm; after each completion of the operation, the material was immersed in pure water for 1min, and the operation was repeated 3 times.
4. The silver-iodine surface-modified titanium alloy implant according to claim 1, wherein in the step (3), the electrochemical method comprises: using iodine-containing solution as electrolyte, placing the material on a titanium alloy hook or a mesh basket as an anode under the conditions of normal temperature and constant pressure of 30-90V, using a pure titanium plate as a cathode, wherein the distance between the cathode and the anode is 10-20cm, and the reaction time is 10-70 min.
5. The silver-iodine surface-modified titanium alloy implant according to claim 1, wherein in the step (3), the drying temperature is 30-40 ℃, the drying time is 3-6h, and light shielding is required.
6. The use of the silver-iodine surface-modified titanium alloy implant according to claim 1 for preparing orthopedic internal and external fixation and implants.
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