CN115721777A - Polydopamine adhered CuS/CaCO 3 Titanium alloy screw with nano composite material as antibacterial coating - Google Patents
Polydopamine adhered CuS/CaCO 3 Titanium alloy screw with nano composite material as antibacterial coating Download PDFInfo
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Abstract
The invention relates to a polydopamine adhered CuS/CaCO 3 A titanium alloy screw with a nano composite material as an antibacterial coating belongs to the technical field of medical materials. The composite material takes waste eggshells as raw materials to prepare CuS/CaCO with antibacterial effect 3 Then using polydopamine as adhesive to make CuS/CaCO 3 And the titanium alloy screw are tightly adhered together. The composite material has excellent antibacterial performance and adhesiveness, and the hydrophilic surface of the titanium alloy can promote osteogenic growth, differentiation and maturation of cells; at the same time has advantagesExceptional cell safety. The coating provided by the invention takes the biomass material eggshell as a main body, so that the waste resources can be recycled to the greatest extent, and the coating is rich in material source, high in safety, simple in preparation process, low in cost and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of medical materials, and particularly relates to polydopamine-adhered CuS/CaCO 3 Titanium alloy screw with nano composite material as antibacterial coating and its preparation.
Background
Eggshells, one of the wastes of daily life, produce a large amount of eggshells every day, and statistically, the number of eggs produced and consumed globally is huge (about 1.275 trillion) according to the report in 2014. If the egg shell is not properly treated, a new pollution is caused to the environment, and researchers pay attention to how to reasonably recycle the egg shell. In fact, the main component of the eggshell powder is calcium carbonate, and meanwhile, the eggshell powder has the characteristics of good adsorbability, porous structure and the like. It can also degrade slowly to release Ca 2+ And Ca 2+ It is one of the components required for human bone growth, and is involved in the proliferation and differentiation of osteoclasts and osteoblasts, and regulates the osteogenesis process, thereby promoting the formation of new bone.
Copper sulfide is an antibacterial material widely used so far, and has an excellent antibacterial effect against both gram-positive bacilli typified by staphylococcus aureus and gram-negative bacilli typified by escherichia coli. This is extremely beneficial to eradicate stubborn bacteria in a patient's wound, and is beneficial to create a sterile environment.
The invention provides a composite antibacterial coating which is prepared by compounding calcium carbonate/copper sulfide and titanium alloy screws by using polydopamineThe layer screw is used for preparing calcium carbonate by using the eggshell, so that not only is the waste recycled, but also various trace elements such as zinc, copper, iron, selenium and the like in the eggshell are reserved, and the trace elements required by a human body are supplemented to a certain extent; meanwhile, the adsorption effect of the copper sulfide is utilized to load copper sulfide for antibiosis. Then the adhesion of polydopamine is utilized to lead the CuS/CaCO 3 The nano composite material and the titanium alloy screw are tightly bonded. The polydopamine adhered CuS/CaCO prepared by the invention 3 The titanium alloy screw with the nano composite material as the antibacterial coating provides a feasible and effective new material for the technical field of medical materials, and is beneficial to the development of the bone transplantation field.
Disclosure of Invention
The invention aims to provide an antibacterial screw which has good cell safety, proper osteoinductivity and excellent antibacterial property and comprises a product obtained by using waste eggshells, copper sulfide and polydopamine as raw materials and adopting a chemical impregnation mode and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
polydopamine adhered CuS/CaCO 3 The preparation method of the titanium alloy screw with the nano composite material as the antibacterial coating comprises the following steps:
(1) Taking waste egg shells as raw materials, washing the waste egg shells by deionized water, calcining the waste egg shells, performing wet ball milling by a ball mill, taking out the waste egg shells, drying and grinding the waste egg shells to obtain nano-scale egg shell powder;
(2) Dispersing eggshell powder into Cu (NO) 3 ) 2 ·3H 2 Soaking in O solution for several hours, and adding Na 2 S·9H 2 Stirring the O solution for several hours, separating the product, washing with deionized water for several times, separating solid and liquid, drying, and grinding to obtain CuS/CaCO 3 A nanocomposite;
(3) Respectively soaking the titanium alloy screws in acetone, ethanol and ultrapure water, performing ultrasonic cleaning treatment, and then placing the titanium alloy screws into an autoclave for sterilization; dissolving dopamine hydrochloride in a Tris-HCl buffer solution, then putting a screw sample into the solution for soaking, putting the solution in a constant-temperature shaking table for uniformly mixing for several hours, taking out the solution, and keeping the solution in a dark place for several hours to finally obtain a polydopamine coated screw;
(4) Then the polydopamine coating screw rod and CuS/CaCO are put into 3 Mixing the nano composite materials, and fully shaking in a constant-temperature shaking table to obtain the polydopamine-adhered CuS/CaCO 3 The titanium alloy screw with the nanometer composite material as the antibacterial coating.
Furthermore, the drying conditions in the step (1) are all 50-70 ℃, and the drying time is 4-6 h.
Further, the calcining conditions in the step (1) are as follows: 600. calcining at 6-8h deg.C at a temperature rise rate of 5 deg.C/min.
Further, the soaking time in the step (2) is 2-4 h.
Further, in the step (2), the stirring speed is 1000r/min, and the stirring time is 12-16h.
Further, the pH value of the Tris-HCl buffer solution in the step (3) is 8-9.
Further, the light-shielding preservation time in the step (3) is 12-18 h.
Further, in the step (4), the shaking table speed is 180 r/min, and the shaking time is 18-24 h.
Further, the polydopamine adhered CuS/CaCO 3 The application of the titanium alloy screw with the nano composite material as the antibacterial coating in preparing the bone repair material.
The invention has the beneficial effects that:
the invention takes the waste eggshells as the raw material to prepare the CuS/CaCO with the antibacterial effect 3 Then using polydopamine as adhesive to make CuS/CaCO 3 And the titanium alloy screw are tightly adhered together. The composite material has excellent antibacterial performance and adhesiveness, and the hydrophilic surface of the titanium alloy can promote osteogenic growth, differentiation and maturation of cells; and has excellent cell safety. The coating provided by the invention takes the biomass material eggshell as a main body, so that the waste resources can be recycled to the greatest extent, and the coating is rich in material source, high in safety, simple in preparation process, low in cost and environment-friendly.
Drawings
Fig. 1 is a comparison of the antibacterial effect of a conventional titanium alloy screw and a PCC screw.
Fig. 2 is a diagram showing the effect of simulating the friction motion in the human body by using a common titanium alloy screw and a PCC screw.
FIG. 3 is CuS/CaCO 3 Cytotoxicity assay plots of nanocomposites.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The orthopedic antibacterial screw is characterized in that waste egg shells are used as raw materials to prepare calcium carbonate, copper sulfide is used as an antibacterial agent, and polydopamine is used for adhering the calcium carbonate to the screw. Wherein, the eggshell is used as raw material, and calcium carbonate is obtained by selecting, cleaning and drying the eggshell, and then calcining the eggshell at high temperature, and is used for promoting the regeneration of bone tissue and playing a role in loading. Dopamine can be self-polymerized into polydopamine in a weakly alkaline environment, a polydopamine layer can be formed on the surface of the titanium alloy screw, and then CuS/CaCO is adhered by the polydopamine layer 3 The nanocomposite is tightly bonded to the screw surface.
The invention relates to polydopamine-adhered CuS/CaCO 3 The preparation method of the titanium alloy screw taking the nano composite material as the antibacterial coating specifically comprises the following steps:
(1) Egg shell pretreatment: collecting waste egg shell, repeatedly cleaning the collected egg shell, soaking at room temperature for 1-2 hr, and removing shell membrane from the egg shell with tweezers.
(2) Preparation of calcium carbonate: and (2) taking the eggshell obtained in the step (1), putting the eggshell into an oven to be dried for 2-4h at 50-70 ℃, taking out the eggshell, grinding the eggshell for 6-10h in a ball mill, sieving the ground eggshell by a 200-mesh sieve, then putting the ground eggshell into a muffle furnace, setting the calcination condition to be 500-600 ℃, and setting the temperature rise speed to be 5 ℃/min, and calcining the eggshell for 6-8h to obtain the calcium carbonate.
（3）CuS/CaCO 3 Preparation of the nanocomposite: placing the calcium carbonate obtained in the step (2) in Cu (NO) 3 ) 2 Soaking in the solution for a period of time to make copper ions successfully adsorbed on calcium carbonate. After 3h, na was added to the solution 2 S solution is stirred for 12 hours, then solid-liquid separation is carried out, precipitate is taken out, dried and ground to obtain CuS/CaCO 3 A nanocomposite material.
(4) Preparing a titanium alloy screw: cleaning titanium alloy screws with acetone, ethanol and ultrapure water in sequence to remove residues such as oil stains and stains, and then sterilizing in a sterilizing pot for 30min.
(5) Preparing a polydopamine screw: preparing a Tris-HCl solution with the pH value equal to 8.5, then placing dopamine hydrochloride into the solution, simultaneously placing the screw obtained in the step (4) into the solution, then placing the solution into a constant-temperature shaking table, shaking for 0.5h, taking out the solution, and standing for 16h in a dark place to obtain the polydopamine coating screw.
(6) The CuS/CaCO obtained in the step (3) 3 Mixing the nano composite material with the polydopamine coating screw obtained in the step (5), and then placing the mixture in a constant-temperature shaking table to shake and shake for 12 hours to finally obtain the polydopamine adhered CuS/CaCO 3 The titanium alloy screw with the nanometer composite material as the antibacterial coating.
Example 1
Polydopamine adhered CuS/CaCO 3 The titanium alloy screw with the nano composite material as the antibacterial coating comprises the following raw materials, by mass, 40 g of egg shells, 0.15M of copper nitrate solution and 36 g of Na 2 S·9H 2 O,1 g dopamine hydrochloride, 200 ml Tris-HCl buffer (pH = 8.5).
The processing method of the calcium carbonate comprises the following steps:
(1) Repeatedly cleaning the collected eggshells, soaking for 1h at room temperature, cleaning, tearing off shell membranes, drying in an oven at 60 ℃ for 3h, taking out, grinding in a ball mill for 8h, and sieving with a 200-mesh sieve;
(2) And (2) placing the egg shell powder obtained in the step (1) of 35 g in a muffle furnace, setting the calcining condition to be 600 ℃, heating up at the speed of 5 ℃/min, and calcining 6h to obtain the calcium carbonate powder.
CuS/CaCO 3 The preparation of the nanocomposite material comprises the following steps;
(3) Placing the 30 g calcium carbonate obtained in the step (2) in Cu (NO) 3 ) 2 3h is soaked in the solution, so that copper ions are successfully adsorbed on calcium carbonate. 3h, na was added to the solution 2 S solution, continuously stirring for 12h, then carrying out solid-liquid separation for a plurality of times, drying and grinding the precipitate to obtain CuS/CaCO 3 A nanocomposite material.
(4) Preparing 200 ml of Tris-HCl solution with the pH value equal to 8.5, then placing dopamine hydrochloride into the solution, simultaneously placing a titanium alloy screw into the solution, placing the titanium alloy screw into a constant temperature shaking table, shaking for 0.5h, taking out, and standing for 16h in a dark place to obtain the polydopamine coated screw.
(5) Mixing CuS/CaCO 3 Mixing the nano composite material with the polydopamine coating screw, and then placing the mixture in a constant-temperature shaking table to shake for 12 hours to finally obtain the polydopamine adhered CuS/CaCO 3 Titanium alloy screw (PCC screw) with nano composite material as antibacterial coating.
Example 2
(1) And (3) pouring the nutrient agar into a culture dish, taking holes after cooling and solidification, and respectively taking out the round holes and the holes with the sizes of the screw samples so as to respectively carry out two groups of antibacterial experiments.
(2) Mixing CuS/CaCO 3 The nanometer composite material and the PCC screw are arranged in the hole and respectively use CaCO 3 And a common titanium alloy screw is used as a control group, and then the control group is placed in an incubator to be incubated for 18h, and an antibacterial result is observed. The results are shown in FIG. 1.
Example 3
(1) Two appropriate screw holes are drilled on bought pig thighbones by screws, repeated screwing experiments are carried out by using common titanium alloy screws and PCC screws respectively, the friction process of the movement of the screws in a human body is simulated, and the screwing times and phenomena are recorded.
(2) The ordinary titanium alloy screw and the PCC screw are respectively used for 10, 30 and 50 times of insertion and extraction of the pig femur, and the times and the phenomena are recorded by taking pictures. The results are shown in FIG. 2.
Example 4
(1) Plating the cells in a 96-well plate at about 1000-10000 cells per well, then subjecting to 37 deg.C and 5% CO 2 Culturing 24h in a concentrated incubator to stabilize cells while adding CuS/CaCO 3 The nanocomposite and the cell culture medium were co-cultured in an incubator at 37 ℃ for 24 hours to prepare a cell extract.
(2) After 24 hours of cell plating, replacing cell culture media of a blank group and a control group, simultaneously replacing the cell culture media of an experimental group with 100 mu l of cell extracting solution, wherein the concentrations are respectively 50, 125, 250, 500 and 1000 mu g/ml, each group is provided with 5 multiple holes, and then placing the groups in a cell culture box for culture.
(3) After 24h of culture, 10 mul of CCK-8 reagent is added into each hole, placed in an incubator for reaction for 1.5h, then placed in an enzyme-labeling instrument, read under absorbance of 450nm, and the activity of each group of cells is calculated. The results are shown in FIG. 3.
FIG. 1: a. b is CuS/CaCO 3 Nanocomposite and CaCO 3 Respectively shows the antibacterial effect on staphylococcus aureus and escherichia coli; c. d is a graph of the antibacterial effect of the PCC screw and the common titanium alloy screw on staphylococcus aureus and escherichia coli respectively. The two groups of experimental groups of the antibacterial experiments can see obvious inhibition zones, and the size of the inhibition zone is 0.3-1.2cm. CuS/CaCO 3 The nanocomposite shows excellent antibacterial activity, which will contribute to sterilization of the wound site and repair of the wound.
FIG. 2: a1-d1 are effect graphs of simulating 0, 10, 30 and 50 times of in-vivo movement friction of a common titanium alloy screw; a2-d2 are graphs of the effect of simulating 0, 10, 30 and 50 times of in-vivo movement friction of the PCC screw.
After the common titanium alloy screw is repeatedly inserted into the femur of the pig for 10 times, the common titanium alloy screw is found to be adhered to the bone marrow of the pig, and after the common titanium alloy screw is repeatedly inserted, the bone marrow on the screw falls off due to friction. After the PCC screw is inserted for 10 times, the PCC coating on the head of the screw slightly falls off, but the PCC material on the tail part still adheres to the screw, and CuS/CaCO is arranged on the screw thread 3 The adhesion of (2). After 50 times of insertion, the bone marrow on the common screw is almost completely removed without adhesion. And the surface coating of the PCC screw is not changed much for the 10 th time, and the subsequent shedding is less. The experiment simulates that the screw is arranged on the human bodyThe inner motion friction process proves that the surface coating of the PCC screw still has good adhesive force under the action of motion friction external force.
FIG. 3 shows CuS/CaCO 3 Graph of cytotoxicity results of nanocomposites. By calculating the cell activity of each group, it can be seen that when the concentration of the leaching liquor is up to 1000 mug/ml, good cell activity still exists, the cell activity of each group in the experimental group is higher than 75% of that of the control group, and each group does not show cytotoxicity, which proves that the cell activity of CuS/CaCO 3 The nano composite material has excellent cell safety, which is favorable for the proliferation and differentiation of wound bone cells.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. Polydopamine adhered CuS/CaCO 3 The preparation method of the titanium alloy screw taking the nano composite material as the antibacterial coating is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking waste egg shells as raw materials, washing the waste egg shells by deionized water, calcining the waste egg shells, performing wet ball milling by a ball mill, taking out the waste egg shells, drying and grinding the waste egg shells to obtain nano-scale egg shell powder;
(2) Dispersing eggshell powder into Cu (NO) 3 ) 2 ·3H 2 Soaking in O solution for several hours, and adding Na 2 S·9H 2 Stirring O solution for several hours, separating the product, washing with deionized water for several times, separating solid and liquid, drying, grinding to obtain CuS/CaCO 3 A nanocomposite;
(3) Respectively soaking the titanium alloy screws in acetone, ethanol and ultrapure water, performing ultrasonic cleaning treatment, and then placing the titanium alloy screws into an autoclave for sterilization; dissolving dopamine hydrochloride in Tris-HCl buffer solution, then putting a screw sample into the solution for soaking, putting the solution in a constant-temperature shaking table for uniformly mixing for several hours, taking out the solution, and keeping the solution in a dark place for several hours to finally obtain a polydopamine coated screw;
(4) Then the polydopamine coating screw rod and CuS/CaCO are put into 3 The nano-composite material is mixed inFully shaking in a constant temperature shaking table to finally obtain the polydopamine adhered CuS/CaCO 3 The titanium alloy screw with the nanometer composite material as the antibacterial coating.
2. The method of claim 1, wherein: the drying conditions in the step (1) are all 50-70 ℃, and the drying time is 4-6 h.
3. The method of claim 1, wherein: the calcining conditions in the step (1) are as follows: 600. calcining at 6-8h deg.C at a temperature rise rate of 5 deg.C/min.
4. The method of claim 1, wherein: the soaking time in the step (2) is 2-4 h.
5. The method of claim 1, wherein: in the step (2), the stirring speed is 1000r/min, and the stirring time is 12-16h.
6. The method of claim 1, wherein: the pH value of the Tris-HCl buffer solution in the step (3) is 8-9.
7. The method of claim 1, wherein: the light-shielding preservation time in the step (3) is 12-18 h.
8. The production method according to claim 1, characterized in that: in the step (4), the shaking table speed is 180 r/min, and the shaking time is 18-24 h.
9. Polydopamine-adhered CuS/CaCO produced by the production method according to any one of claims 1 to 8 3 The application of the titanium alloy screw with the nano composite material as the antibacterial coating in preparing the bone repair material.
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