CN115814154A - PH response type controlled release bactericidal coating and preparation method and application thereof - Google Patents
PH response type controlled release bactericidal coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a pH response type controlled release bactericidal coating and a preparation method and application thereof, and the invention uses Fe 3+ a/TA complex, or Cu 2+ a/TA complex, or Fe 3+ [ TA ] and Cu 2+ After the alternate deposition of the/TA complex, a pH response type controlled release bactericidal coating is formed; the coating is at physiological pH, fe 3+ the/TA forms a three-complex and at a pH between 3 and 6 (the pH of the infection microenvironment is about 5.5), it will convert to a two-complex due to protonation effect, thus achieving controlled release of TA. In addition, the present invention speculates Cu 2+ The pH-responsive bactericidal effect of/TA also results from TA release due to protonation effects and from Cu 2+ The synergistic effect of (A) and (B). The invention not only improves the antibacterial performance of the implant material, but also solves the problems of lack of controlled release sterilization and storage in the prior artDisadvantages in antibiotic abuse.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a pH response type controlled release bactericidal coating, and a preparation method and application thereof.
Background
A disease in which human tissue or organs leave the normal anatomical site and enter another site through a weakness, defect or aperture formed either congenital or acquired, is known as hernia. Hernia has a serious impact on human life and quality of life. The polypropylene hernia patch is widely applied to tension-free hernia repair because of its characteristics of strong tension resistance, moderate hardness, good biocompatibility and the like. However, polypropylene materials lack antimicrobial properties themselves, which remain in the human body for a long time at risk of bacterial infection. It is well known that the problem of infection of the implanted material has been one of the major factors leading to failure of the surgery.
Surface Modification of implant materials can effectively address the problem of bacterial infection, xiakeer Saitaer et al (SAITAER X, SANBHAL N, QIAO Y, et al. Multidopamine-injected Surface Modification of Polypropylene Hernia Mesh Devices via Cold Oxygen Plasma: antibacterial and Drug Release Properties [ J ]. Coatings,2019,9 (3)) use Oxygen Plasma to activate Polypropylene (PP), and then use dopamine to load the Antibacterial Drug levofloxacin on Polypropylene hernians to achieve the purpose of improving Antibacterial patches. However, there are some problems to be improved with this research: first, the bacterial resistance crisis forces researchers to consider avoiding the use of antibiotics in material modification; secondly, the PP hernia patch prepared by the research shows a sterilization effect in 6 days, the release time of the medicament is 24 hours, the antibacterial performance gradually disappears along with the release of the medicament, namely the antibacterial effect has no long-acting property; finally, the antibacterial performance does not have a controlled release effect, and the medicament is possibly completely released without infection, so that the antibacterial effect cannot be achieved and certain side effects may exist.
In view of the above, it is needed to develop a surface modified coating which is not easy to generate drug resistance, long-acting antibacterial property and response type controlled-release sterilization, and is an implant material such as a polypropylene hernia patch and the like, which is successfully applied to clinical driving protection.
Disclosure of Invention
The invention aims to solve the defects of the existing surface modified implant material, and provides a pH response type controlled release bactericidal coating, and a preparation method and application thereof.
The conception of the invention is as follows:
surface modification for PP implant materials to cope with the current situationThe invention provides a pH response type controlled release bactericidal coating and a preparation method thereof, and solves the problems of the related technology of bacterial infection. The research team of the invention firstly considers that the prepared coating needs to have good adhesive force, thus selecting Tannic Acid (TA), wherein the TA belongs to natural polyphenol compounds and has certain antibacterial performance, and the TA contains abundant catechol or pyrogallol groups (about 25 hydroxyl groups), so the TA can participate in non-covalent interactions such as metal ion chelation, ion pairing, hydrogen bond and the like, and the TA and various substances show very high affinity. Among them, the chelation of TA with various metal ions has attracted the research interest of the research team of the present invention, fe 3+ Can be rapidly complexed with TA (basically completed within 2 min), and complex thereof (Fe) 3+ /TA) pH-responsive due to protonation effects, fe at physiological pH 3+ TA forms a three complex which converts to a double complex at a pH between 3 and 6 and a single complex at a pH less than 3; fe 3+ The pH responsiveness of the/TA complex enables the research team of the invention to speculate that the pH response sterilization effect is achieved, because the pH range of the complex converted into the double complex is just matched with the gastric acid environment (the pH is about 5.5) caused by infection, the complex can just be used for solving the problem of the common iatrogenic infection complications of the implant materials, and meanwhile, the controlled release can be achieved. In addition to that, cu 2+ As a common broad-spectrum antibacterial metal ion, the research team of the invention is based on Fe 3+ pH responsiveness of the/TA Complex, the best guess of Cu 2+ Complex with TA (Cu) 2+ /TA) should also have pH-responsive bactericidal properties and have broad-spectrum bactericidal properties; therefore, the present invention is directed to Cu 2+ The pH responsiveness sterilization effect of the/TA is verified. Further, two complexes (Fe) were also investigated 3+ [ solution ] TA and Cu 2+ /TA) change in its antibacterial properties in the presence of both.
In view of the above, the present invention has been made to separate Fe 3+ Coating deposited with/TA Complex, cu alone 2+ And (3) verifying the antibacterial performance of the/TA complex deposited coating and the alternate deposited coating. Of course, in addition to this, other metal ions which have no significant toxic side effects and which can complex with TA can also be selected and developed for use in the preparation of coatingsPotential, e.g. Zn 2+ 。
In order to achieve the purpose, the technical solution provided by the invention is as follows:
a pH response type controlled release bactericidal coating is characterized in that: comprising a separately deposited N layer of Fe 3+ Tannin Complex layer (Fe) 3+ a/TA complex layer), or a separately deposited M layer of Cu 2+ Tannin complex layer (Cu) 2+ a/TA complex layer) or alternatively deposited S layers of Fe 3+ Tannin complex layer and S layer Cu 2+ A tannin complex layer; wherein, the value ranges of N, M and S are both 1-6.
At physiological pH, fe 3+ the/TA forms a three-complex which converts to a two-complex at a pH between 3 and 6 (the pH of the infection microenvironment is about 5.5) to achieve controlled release of the TA.
Further, with respect to the alternately deposited S layers of Fe 3+ Tannin complex layer and S layer Cu 2+ The tannin complex layers are alternately stacked from bottom to top, and take into account TA and Fe of tannin 3+ Is most strongly complexed, so Fe is added 3+ the/TA is placed in the first deposition.
The preparation method of the pH response type controlled release bactericidal coating is characterized in that:
immersing the implant material subjected to surface activation treatment (deposition should be carried out immediately after the surface activation treatment, the surface activation is mainly because the surface of the implant material is inert, and is convenient for later modification in order to obtain active groups such as hydroxyl groups and the like) in Fe for N times 3 + Tannin mixed solution (i.e. tannin and FeCl) 3 Mixed solution), or M times of immersion in Cu 2+ Tannin mixed solution (i.e. tannin and CuCl) 2 Mixed solution), or alternatively immersed in Fe S times 3+ Tannin mixed solution and Cu 2+ In the tannin mixed solution, finally obtaining a pH response type controlled release bactericidal coating on the surface of the implant material;
wherein, the immersion time is 2-10 min each time (less than 2min, the coating is thinner and even has a porous structure, and the complex is deposited at the lower part of the reaction container when the immersion time is too long, or the coating is too thick and falls off, and the content of metal ions is too much, which may be unfavorable for cell growth), and the complex is rinsed in ultrapure water after being immersed and taken out each time, and then is dried at 40-60 ℃ and then is immersed next time.
Further, tannic acid TA and Fe are considered 3+ The complex is strongest, and the implant material for carrying out surface activation treatment on multiple times of alternate immersion is selected from Fe 3+ Immersing in tannin mixed solution, oven drying, and adding Cu 2+ Immersing in the tannic acid mixed solution, and repeating for S times.
Further, in Fe 3+ Immersing the tannin mixed solution in an oven (such as a blast drying oven) at the drying temperature of 60 ℃ for 2min (the complexation can be completed within 2min, so that the time is greatly saved); in Cu 2+ Immersing in tannin mixed solution for 5min (considering its binding and complexing effects are not good as Fe) 3+ Strong, and suitably prolonged complexing time), a drying temperature of 60 ℃, an oven (for example: an air-blast drying box).
Further, fe 3+ The preparation process of the tannin mixed solution is as follows:
taking equal volume of tannic acid solution and equal volume of FeCl 3 The solution is uniformly mixed (magnetic stirring is adopted, and the rotating speed is 350 r/min), wherein the tannin and FeCl 3 The molar ratio of (a) to (b) is 1: 1 to 3 (preferably 1: 3);
tannic acid solution and FeCl 3 The solutions all use ultrapure water as a solvent, the molar concentration of the tannic acid solution is 10mM, and the pH value is 7.4-7.8 (preferably physiological pH value is 7.4); the pH of the tannic acid solution can be adjusted by using a 1M NaOH solution (the molar concentration is 1M, the pH is well controlled, the concentration of the stock solution is influenced by too low concentration, the adding amount of sodium hydroxide is not well controlled by too high concentration, and the target value to be adjusted is exceeded by a little more, so the NaOH solution with a little higher concentration is also feasible, but the control requirement on the amount is higher);
Cu 2+ the preparation process of the tannin mixed solution is as follows:
taking equal volume of tannic acid solution and equal volume of CuCl 2 The solution is mixed uniformly (magnetic force can be adopted)Stirring uniformly), wherein the tannic acid is mixed with CuCl 2 The molar ratio of (A) to (B) is 1: 1-3;
tannic acid solution and CuCl 2 The solutions all use ultrapure water as a solvent, the molar concentration of the tannic acid solution is 10mM, the pH value is 7.4-7.8, the pH value of the tannic acid solution can be adjusted by using a 1M NaOH solution (the molar concentration is preferably controlled by using 1M, the pH value is influenced by too low concentration, the adding amount of the sodium hydroxide is not well controlled by too high concentration, and the adding amount may exceed a target value to be adjusted, so that the NaOH solution with higher concentration is also feasible, but the control requirement on the amount is higher);
the above tannic acid and FeCl 3 Mixed solution, tannic acid and CuCl 2 The mixed solution is prepared for use at the same time;
further, the surface activation treatment may be performed by using oxygen plasma (air plasma may, of course, not be subjected to plasma treatment due to good adhesion of TA, but may not be subjected to plasma treatment as well), specifically:
ultrasonically cleaning the implant material by adopting acetone, absolute ethyl alcohol and ultrapure water in sequence and drying for later use; and then carrying out oxygen plasma activation treatment by using a plasma treatment instrument for 180-300 s.
Further, the implant material is a metal-based implant material, a ceramic implant material or a polymer implant material, such as a polypropylene hernia patch, although not limited thereto.
The invention also provides application of the pH response type controlled release bactericidal coating in antibacterial modification of an implant material.
A method for carrying out antibacterial modification on an implant material is characterized by comprising the following steps: after the implant material is cut to the desired size, it is modified by the methods described above.
An implant material, characterized in that: the implant material is subjected to antibacterial modification by adopting the method, and then can be used for antibacterial infection treatment.
The principle of the invention is as follows:
the invention is through Fe 3+ /TA complex deposition, or Cu 2+ Deposit of/TA complex, or Fe 3+ Complex of/TA and Cu 2+ After the/TA complex is alternately deposited, a pH response type controlled release bactericidal coating is formed; the coating is at physiological pH, fe 3+ the/TA forms a three-complex and at a pH between 3 and 6 (the pH of the infection microenvironment is about 5.5), it will convert to a two-complex due to protonation effect, thus achieving controlled release of TA. At the same time, cu is presumed 2+ The pH responsiveness of the/TA complex is also derived from protonation response, and the antibacterial property is derived from Cu 2+ And TA synergy. The invention not only improves the antibacterial performance of the implant material (polypropylene hernia patch), but also overcomes the defects of lack of controlled release sterilization and antibiotic abuse in the prior art.
The invention has the advantages that:
1. the invention uses simple soaking method to treat Tannin (TA) and metal ion (Fe) on the implant material with surface activation treatment 2+ And Cu 2+ ) The complex coating is introduced to the surface of the implant material, the whole preparation process is simple, efficient and quick, only 2-10 minutes is needed to complete one-time complex deposition, and the method is favorable for clinical popularization and application;
2. compared with the existing slow-release medicine sterilization technology, the coating has pH response type controlled-release sterilization effect, can achieve high-efficiency utilization of antibacterial components, and is specific to staphylococcus aureus (10) at the pH of 5.5 7 CFU/mL) reaches 100 percent; compared with antibiotic medicines, the antibiotic medicine has less possibility of generating drug resistance, and has obvious application advantage in the large environment of drug-resistant bacteria crisis; in addition, the tannin has good killing effect on methicillin-resistant staphylococcus aureus, namely the complex coating can also kill drug-resistant bacteria MRSA;
3. the tannic acid adopted by the coating has good affinity, so that the complex coating is suitable for various material substrates and can be applied to the surfaces of various matrix implant materials to improve the antibacterial performance of the matrix implant materials;
4. based on Fe 3+ The coating has potential photo-thermal antibacterial effect.
Drawings
FIG. 1 is a schematic flow chart of the preparation of pH-responsive controlled-release bactericidal coating for polypropylene hernia patch by using tannin/metal ion complex according to the present invention;
FIG. 2 is a schematic diagram of pH responsive sterilization of tannin/metal ion complex coatings prepared in accordance with the present invention;
FIG. 3 is the surface water contact angle results for comparative example, example 1, example 2, and example 3;
FIG. 4 is a surface topography plot at different magnifications for samples prepared in comparative example, example 1, example 2, and example 3;
FIG. 5 is an energy spectrum of samples prepared in comparative example, example 1, example 2 and example 3;
FIG. 6 is an X-ray photoelectron spectroscopy (XPS) of a sample prepared by a comparative example;
FIG. 7 is XPS survey spectra and high resolution Cu2p spectra of samples prepared in example 1, example 2 and example 3; a is example 1,b is example 2,c is example 3;
FIG. 8 is the results of plating the samples prepared in comparative example, example 1, example 2 and example 3 for the antibacterial performance against the gram-positive bacterium Staphylococcus aureus (S.aureus) at different pH values;
fig. 9 is a result of sterilization rates against s.aureus for samples prepared in comparative example, example 1, example 2, and example 3 at different pH;
fig. 10 is an SEM topography of the bactericidal effect against s.aureus for samples prepared in comparative example, example 1, example 2 and example 3 at different pH;
FIG. 11 is XPS Cu2p high resolution spectra of example 6;
fig. 12 results of antibacterial performance plating for s.aureus for comparative example, example 1, example 2, example 4, example 5, example 6, and example 7;
fig. 13 is the results of the antibacterial performance of comparative example, example 1, example 2, example 4, example 5, example 6 and example 7 against e.coli;
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
taking a polypropylene hernia patch as an implantation material as an example, the invention provides a method for preparing a pH response type controlled-release bactericidal coating of the polypropylene hernia patch by adopting a tannin/metal ion complex, and the process route is shown in figure 1 and comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples (the required sizes are all) of 4cm multiplied by 4cm, and in order to clean the hernia patch in a short time, sequentially ultrasonically cleaning the hernia patch for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the hernia patch for later use;
oxygen plasma treatment: placing the polypropylene hernia patch with the thickness of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 180-300 s to achieve the purpose of activating the raw material;
preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by magnetic force, and adjusting the pH value of the tannic acid solution to 7.4-7.8 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solutions of tannic acid and FeCl 3 The molar ratio of (A) to (B) is 1: 1-3; pouring the same volume of tannic acid solution into the same volume of FeCl 3 After the solution is quickly and uniformly stirred by magnetic force, the polypropylene hernia patch treated by the oxygen plasma is immersed in Fe 3+ In the tannic acid mixed solution, taking out the mixed solution after 2 to 10min, rinsing the mixed solution in ultrapure water, drying the rinsed solution in a drying oven at the temperature of between 40 and 60 ℃, and repeating the operation (1 to 6 times) to obtain the deposited Fe 3+ a/TA complex coated sample;
preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by magnetic force, and adjusting the pH value of the tannic acid solution to 7.4-7.8 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution of tannic acid with CuCl 2 The molar ratio of (A) to (B) is 1: 1-3; pouring the same volume of tannic acid solution into the same volume of CuCl 2 After the solution is quickly and magnetically stirred uniformly, the polypropylene hernia patch treated by the oxygen plasma is immersed in Cu 2+ In the tannic acid mixed solution, taking out the mixed solution after 2 to 10min, rinsing the mixed solution in ultrapure water, and drying the rinsed solution in a drying oven at the temperature of between 40 and 60 ℃ to obtain the deposited Cu 2+ a/TA complex coated sample;
treating the oxygen plasma according to the method described aboveThe polypropylene hernia patch after being treated is alternately immersed in Fe prepared by the method 3+ Tannin mixed solution and Cu 2+ Respectively depositing Fe in the mixed solution of tannic acid 3+ [ TA ] Complex and Cu 2+ the/TA complex to give Fe deposited finally 3+ Coating of/TA complexes and Cu 2+ the/TA complex coated samples, it is also understood that the procedure is specifically as follows:
1) Pretreatment of
Carrying out surface activation treatment on the implanted material; immediately entering the next step after the surface activation treatment;
2) Deposition of Fe 3+ /TA
Immersing the implant material obtained in the step 1) in Fe 3+ Mixed solution of/TA (i.e. tannic acid and FeCl) 3 Mixed solution) for 2-10 min, taking out, placing in ultrapure water for rinsing, drying, and repeatedly depositing for N times to obtain Fe 3+ The TA complex pH response type controlled release bactericidal coating; wherein, N takes 1 to 6;
alternatively, depositing Cu 2+ /TA
Immersing the implant material obtained in the step 1) in Cu 2+ Mixed solution of/TA (i.e., tannic acid and CuCl) 2 Mixed solution) for 2-10 min, taking out, placing in ultrapure water for rinsing, drying, and repeatedly depositing for M times to obtain Cu 2+ The TA complex pH response type controlled release bactericidal coating; wherein M takes a value of 1-6;
alternatively, fe is deposited alternately 3+ [ TA ] and Cu 2+ /TA
Immersing the implant material obtained in the step 1) in Fe alternately 3+ Mixed solution of/TA and Cu 2+ Repeating S times (i.e. performing S times of cyclic deposition) in the mixed solution of/TA to obtain Fe on the implant material 3+ [ TA ] and Cu 2+ The TA complex pH response type controlled release bactericidal coating; wherein S is 1 to 6.
The time for each immersion is 2-10 min, and after each immersion is finished and taken out, the immersion liquid is firstly placed in ultrapure water for rinsing, and then is dried at the temperature of 40-60 ℃ for next immersion.
The following examples were carried out according to the above procedure:
example 1
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Fe 3+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solution (30 mM); 20mL of tannic acid solution is poured into 20mL of FeCl 3 After the solution is quickly and uniformly stirred by magnetic force, the polypropylene hernia patch (4 cm multiplied by 4 cm) treated by oxygen plasma is immersed in the mixed solution, taken out after 2min, rinsed in ultrapure water and dried in a baking oven at 60 ℃;
Cu 2+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution (30 mM); 20mL of tannic acid solution was poured into 20mL of CuCl 2 After being rapidly and uniformly stirred by magnetic force in the solution, the solution is processed by Fe 3+ Immersing the polypropylene hernia patch (4 cm multiplied by 4 cm) after the deposition of the/TA complex compound in the tannic acid and the CuCl 2 After 5min, the mixture was rinsed in ultrapure water, dried in an oven at 60 ℃ and cut into 1cm by 1cm samples, which were designated as PP-FCT (1).
Comparative example
Cutting the polypropylene hernia patch into a sample of 1cm multiplied by 1cm, sequentially ultrasonically cleaning the sample for 5min by acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the sample, wherein the sample is named as PP.
Example 2
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Fe 3+ deposition of TA on Polypropylene hernia Patches: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solution (30 mM); 20mL of tannic acid solution is poured into 20mL of FeCl 3 After the solution is quickly and magnetically stirred uniformly, the polypropylene hernia patch (4 cm multiplied by 4 cm) treated by oxygen plasma is immersed in the mixed solution, taken out after 2min, rinsed in ultrapure water and dried in a baking oven at 60 ℃;
Cu 2+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution (30 mM); 20mL of tannic acid solution was poured into 20mL of CuCl 2 After being rapidly and uniformly stirred by magnetic force in the solution, the solution is processed by Fe 3+ Immersing the polypropylene hernia patch (4 cm multiplied by 4 cm) after the deposition of the/TA complex compound in the tannic acid and the CuCl 2 After 5min, the mixed solution is taken out and rinsed in ultrapure water, and then dried in an oven at 60 ℃.
Repeating the deposition of Fe 3+ [ TA ] and Cu 2+ After 3 times the/TA complex, the sample was cut to 1cm by 1cm size and designated PP-FCT (3).
Example 3
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Fe 3+ deposition of TA on Polypropylene hernia Patches: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solution (30 mM); 20mL of tannic acid solution is poured into 20mL of FeCl 3 After the solution is quickly and uniformly stirred by magnetic force, the polypropylene hernia patch (4 cm multiplied by 4 cm) treated by oxygen plasma is immersed in the mixed solution, taken out after 2min, rinsed in ultrapure water and dried in a baking oven at 60 ℃;
Cu 2+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution (30 mM); 20mL of the tannic acid solution was poured into 20mL of CuCl 2 After being rapidly and magnetically stirred uniformly in the solution, the solution is subjected to Fe 3+ Immersing the polypropylene hernia patch (4 cm multiplied by 4 cm) after the deposition of the/TA complex compound in the tannin and the CuCl 2 After 5min, the mixed solution was taken out and rinsed in ultrapure water, and then dried in an oven at 60 ℃.
Repeating the deposition of Fe 3+ [ TA ] and Cu 2+ After 5 times the/TA complex, the sample was cut to 1cm by 1cm size and designated PP-FCT (5).
Example 4
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Fe 3+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solution (30 mM); 20mL of tannic acid solution is poured into 20mL of FeCl 3 After the solution is quickly and uniformly stirred by magnetic force, the polypropylene hernia patch (4 cm multiplied by 4 cm) treated by oxygen plasma is immersed in the mixed solution for 2min, taken out and rinsed in ultrapure water, and dried in a 60 ℃ oven, and the sample is named as PP-Fe/TA (1).
Example 5
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Fe 3+ deposition of TA on Polypropylene hernia Patches: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of FeCl using ultrapure water as solvent 3 Solution (30 mM); 20mL of tannic acid solution is poured into 20mL of FeCl 3 After the solution is quickly and uniformly stirred by magnetic force, the polypropylene hernia patch (4 cm multiplied by 4 cm) treated by oxygen plasma is immersed in the mixed solution, taken out after 2min, rinsed in ultrapure water and dried in an oven at 60 ℃.
Repeated deposition of Fe 3+ The sample was designated PP-Fe/TA (3) with 3 times of/TA.
Example 6
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into a sample with the size of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the sample for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the sample for later use;
oxygen plasma treatment: placing a 4 cm-4 cm polypropylene hernia patch in a plasma treatment instrument for treatment for 300s to achieve the purpose of activating a raw material;
Cu 2+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution (30 mM); 20mL of tannic acid solution was poured into 20mL of CuCl 2 Rapidly stirring with magnetic force, and soaking polypropylene hernia patch (4 cm × 4 cm) treated by oxygen plasma in tannin and CuCl 2 After 5min, the mixture was taken out and rinsed in ultrapure water, and then dried in an oven at 60 ℃ to obtain a sample named PP-Cu/TA (1).
Example 7
A method for preparing a pH-responsive controlled-release bactericidal coating of a polypropylene hernia patch by adopting a tannic acid/metal ion complex comprises the following steps:
pretreatment: cutting the polypropylene hernia patch into samples of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the samples for 5min by using acetone, absolute ethyl alcohol and ultrapure water at the frequency of 100Hz, and drying the samples for later use;
oxygen plasma treatment: placing the polypropylene hernia patch of 4cm multiplied by 4cm in a plasma treatment instrument for treating for 300s to achieve the purpose of activating the raw material;
Cu 2+ deposition of TA on Polypropylene hernia Patch: preparing a tannic acid solution (10 mM) by using ultrapure water as a solvent, uniformly stirring by using a magnetic force, and adjusting the pH value of the tannic acid solution to 7.4 by using a 1M NaOH solution; preparation of CuCl with ultrapure water as solvent 2 Solution (30 mM); 20mL of tannic acid solution was poured into 20mL of CuCl 2 Rapidly stirring with magnetic force, and placing the polypropylene hernia patch (4 cm × 4 cm) treated by oxygen plasma in tannin and CuCl 2 After 5min, the mixed solution was taken out and rinsed in ultrapure water, and then dried in an oven at 60 ℃.
Repeatedly depositing Cu 2+ 3 times of TA deposition and the sample was named PP-Cu/TA(3)。
In order to verify the coating and the coating effect, the invention also carried out the following tests:
the change in water contact angle on the surface of each group of samples was characterized by the sessile drop method, and for the convenience of characterization, the same preparation procedure for water contact angle test as that of comparative example, example 1, example 2 and example 3 was performed using polypropylene sheets of 1cm × cm and a thickness of 2 mm. As can be seen from fig. 3, the wettability of the surfaces of examples 1, 2 and 3 is significantly improved compared to that of comparative example 1, and the water contact angles thereof are about 80.83 °, 72.62 ° and 73.17 ° in sequence, which also proves that the coating of the present invention is successfully prepared in the polypropylene hernia patch.
The surface topography of the comparative, example 1, example 2 and example 3 samples was characterized using a very high resolution Field Emission Scanning Electron Microscope (FESEM). As shown in fig. 4, the surfaces of example 1, example 2 and example 3 all exhibited different degrees of coating cracking compared to the comparative examples, demonstrating the successful preparation of the coatings.
The surface element composition of each group of samples is characterized by adopting an energy spectrometer matched with a super-high resolution Field Emission Scanning Electron Microscope (FESEM). As shown in fig. 5, the surfaces of the samples of example 2 and example 3 both contained Fe and Cu elements, as compared to the comparative example, successfully demonstrating the successful preparation of the surface coating. In addition, in example 1, no metal element is detected, which is presumably caused by the detection sensitivity of the instrument, and since the EDS adopts point scanning during material characterization, three-point measurement is carried out, and no Cu is detected; therefore, the invention further adopts XPS with higher sensitivity to detect, successfully detects the Cu element and also proves the successful adhesion of the coating. Generally, EDS has lower sensitivity than XPS, and is not normally detected when the content is relatively low.
The surface chemical compositions of each set of samples were tested using X-ray photoelectron spectroscopy (XPS), with fig. 6 being a full spectrum of the comparative example, and fig. 7 being a full spectrum of examples 1, 2 and 3 and a high resolution spectrum of Cu2 p. From the XPS results, examples 1, 2 and 3 all showed the presence of Cu, and the successful preparation of the coatings was confirmed by the characterization results.
The bactericidal performance of each group of samples under different pH values was tested by a plate coating method, and the selected strains were Staphylococcus aureus (S.aureus) and Escherichia coli (E.coli). As can be seen from fig. 8, the comparative examples have a large amount of bacteria at both pH7.4 and pH5.5, while examples 1, 2 and 3 exhibit good pH-responsive bactericidal properties. Fig. 9 is a graph showing the sterilization rates of the respective groups of samples, which correspond to the results of fig. 8, and examples 1, 2, and 3 exhibited good pH-responsive sterilization performance. The killing effect of each set of samples on s. As shown in FIG. 10, the bacteria on the surface of the comparative example were smooth and smooth, indicating that the survival state was good, whereas the bacteria on the surface of examples 1 to 3 all had intact morphology at pH7.4, and the bacteria on the surface of examples 1 to 3 were dented, collapsed and some of the bacterial contents leaked out at pH 5.5.
FIG. 11 is XPS Cu2p high resolution spectra from example 6, with Cu deposited alone 2+ The presence of Cu element was also detectable by/TA, demonstrating the success of the modification.
FIGS. 12 and 13 are the deposition of Fe alone 3+ [ theta ] or Cu 2+ The antibacterial effect of/TA or the alternate deposition of both was studied, and it can be seen from FIG. 12 that Fe is deposited alone 3+ [ theta ] or Cu 2+ The antibacterial effect of/TA, or both, alternately deposited (against S.sureus) is comparable, but as can be seen from FIG. 13, PP-Cu/TA (3) is more effective than PP-Fe/TA (3); the alternating of the two (PP-FCT (3)) had the strongest antimicrobial effect (against e. Coli) compared to the deposition alone, which further validated our previous hypothesis, namely Cu 2+ The antibacterial property of the/TA complex coating is TA and Cu 2+ The synergistic effect of (A) and (B).
The results prove that the coating has a good pH response type controlled-release sterilization effect.
To sum up, the embodiment provides a simple and efficient method for preparing the tannin/metal ion complex coating on the surface of the medical polypropylene hernia patch material (implant material), overcomes the defects that the original polypropylene hernia repair material has no obvious antibacterial performance and cannot effectively cope with iatrogenic infection, and the prepared coating has a good pH response type controlled-release sterilization effect, so that the polypropylene hernia patch modified material with the tannin/metal complex coating on the surface is obtained, and the polypropylene hernia patch is endowed with the pH response type controlled-release sterilization performance. Based on the good affinity of TA, the coating has good universality on a base material, and the base material is not limited to a polypropylene hernia patch material and can be applied to antibacterial modification of various implant materials, such as metal-based implant materials, ceramic implant materials and other polymer implant materials.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A pH response type controlled release bactericidal coating is characterized in that:
comprising N layers of Fe 3+ A tannin complex layer, wherein N is 1-6;
or, M layer of Cu 2+ A tannin complex layer, wherein M is 1-6;
or alternatively deposited S layers of Fe 3+ Tannin complex layer and S layer Cu 2+ A tannin complex layer, wherein S is 1 to 6.
2. The pH-responsive controlled-release bactericidal coating according to claim 1, characterized in that:
the S layers of Fe deposited alternately 3+ Tannin complex layer and S layer Cu 2+ The tannin complex layer is composed of Fe 3+ Tannin complex layer and Cu 2+ The tannin complex layers are alternately deposited from bottom to top.
3. The method for preparing the pH-responsive controlled-release bactericidal coating according to claim 1 or 2, characterized in that:
immersing the implant material subjected to surface activation treatment in Fe for N times 3+ In a tannin mixed solution;
or immersing the implant material subjected to surface activation treatment in Cu for M times 2+ In a tannin mixed solution;
or alternatively immersing the implant material subjected to the surface activation treatment in Fe for S times 3+ Tannin mixed solution and Cu 2+ In a tannin mixed solution;
finally, obtaining a pH response type controlled release bactericidal coating on the surface of the implant material;
wherein the time length of each immersion is 2-10 min, and after each immersion is finished and taken out, the immersion liquid is firstly placed into ultrapure water for rinsing, and then is dried at the temperature of 40-60 ℃ for next immersion.
4. The method for preparing the pH-responsive controlled-release bactericidal coating according to claim 3, wherein:
firstly, the implant material subjected to surface activation treatment is subjected to Fe 3+ Immersing in tannin mixed solution, oven drying, and adding Cu 2+ Immersing in the tannin mixed solution, and repeating for S times.
5. The method for preparing the pH-responsive controlled-release bactericidal coating according to claim 4, wherein:
each time in Fe 3+ Immersing in the tannic acid mixed solution for 2min;
each time in Cu 2+ Immersing the tannin mixed solution for 5min;
the drying temperature is 60 ℃ each time.
6. The method for preparing the pH-responsive controlled-release bactericidal coating according to claim 5, wherein:
Fe 3+ the preparation process of the tannin mixed solution is as follows:
taking equal volume of tannic acid solution and equal volume of FeCl 3 Mixing the solution uniformly, wherein the tannic acid and FeCl 3 The molar ratio of (A) to (B) is 1: 1-3;
tannic acid solution and FeCl 3 The solution is prepared from ultrapure water as solvent, and tanninThe molar concentration of the acid solution is 10mM, and the pH value is 7.4-7.8;
Cu 2+ the preparation process of the tannin mixed solution is as follows:
taking equal volume of tannic acid solution and equal volume of CuCl 2 Mixing the solution with tannic acid and CuCl 2 The molar ratio of (A) to (B) is 1: 1-3;
tannic acid solution and CuCl 2 The solutions all used ultrapure water as a solvent, the molarity of the tannic acid solution was 10mM, and the pH was 7.4-7.8.
7. The method for preparing the pH-responsive controlled-release bactericidal coating according to any one of claims 3 to 6, wherein:
the implant material is a metal-based implant material, a ceramic implant material or a polymer implant material.
8. Use of a pH-responsive controlled-release bactericidal coating according to claim 1 or 2 for the antimicrobial modification of an implant material.
9. An implant material, comprising: on which a pH-responsive controlled release bactericidal coating as claimed in claim 1 or 2 is deposited.
10. A method for the antimicrobial modification of an implanted material, comprising: after the implant material has been cut to the desired size, it is modified by the method according to any of claims 3 to 7.
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