CN114016002A - Antibacterial composite coating with self-regeneration function and preparation method thereof - Google Patents
Antibacterial composite coating with self-regeneration function and preparation method thereof Download PDFInfo
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- CN114016002A CN114016002A CN202011636308.7A CN202011636308A CN114016002A CN 114016002 A CN114016002 A CN 114016002A CN 202011636308 A CN202011636308 A CN 202011636308A CN 114016002 A CN114016002 A CN 114016002A
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
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Abstract
The invention relates to the technical field of antibiosis, in particular to an antibacterial composite coating with a self-regeneration function and a preparation method thereof. The antibacterial composite coating is attached to the base material and is formed by alternately compounding a plurality of antibacterial layers and a plurality of degradable layers; wherein the thickness of the antibacterial layer is 0.2-2 mu m, and the thickness of the degradable layer is 0.1-1 mu m. The antibacterial composite coating has a good antibacterial effect, and the antibacterial layer on the surface layer loses antibacterial capability by adopting the degradable layers and the antibacterial layers which are alternately compounded, and then the antibacterial layer is degraded and falls off, so that the exposed new antibacterial layer continues the antibacterial capability.
Description
Technical Field
The invention relates to the technical field of antibiosis, in particular to an antibacterial composite coating with a self-regeneration function and a preparation method thereof.
Background
In the field of medical devices, the requirements for antimicrobial properties are high, such as indwelling catheters, whose antimicrobial properties are directly linked to the treatment and recovery of the patient. Indwelling catheters are one of the most common medical devices in clinical medicine, and have a primary function of passive urination of patients. Urination by using an indwelling catheter is an effective urination means for critically ill patients and patients suffering from urinary incontinence. Since the insertion of a catheter is an invasive procedure in the human body, once the indwelling catheter becomes contaminated with bacteria, it is very likely to cause urinary tract infection and related complications in the human body. If the catheter is frequently replaced, great extra pain is brought to the patient, and the medical cost and the economic pressure of the patient are increased
It was found by analysis that a single bacterium on a catheter could form a biofilm within 24 hours, which was difficult to eradicate with antibiotics because the bacteria inside the biofilm were protected by the extracellular matrix. Therefore, only the ability to inhibit the formation of bacterial biofilms is fundamental to the problem of eradicating bacteria. The key to inhibiting biofilm formation is the ability to kill bacteria that initially colonize the surface of the material, thereby preventing the spread, proliferation and transfer of bacteria.
One prevents the formation of biofilms by preparing surfaces with bactericidal functions. Such an antibacterial surface having only a bactericidal function has a good bactericidal effect in a short time, but the bactericidal function of the material surface is gradually lost with the adhesion of bacterial debris and bacterial secretions, and biofilm formation still occurs. In order to improve the function of the antibacterial coating, some surfaces are prepared which can switch the sterilization and repulsion functions under the stimulation of external light, temperature, humidity, etc. These surfaces are effective in killing bacteria in contact and subsequently releasing contaminants under external stimuli, but these external stimuli are difficult to use inside the human body, so the antimicrobial problem of the surfaces of the indwelling device remains unsolved.
Indwelling medical device the ideal antimicrobial surface of an indwelling medical device is required to be able to both kill bacteria in contact and to completely detach all cellular debris from the surface under physiological conditions without external stimuli. The difficulty in achieving this is that most antimicrobial surfaces with contact sterilization rely on electrostatic attraction between the positive charge on the surface and the negative charge on the bacterial membrane, but this is also the reason for bacterial cells and debris being adsorbed. This increases the difficulty of implementing the solution.
In summary, bacteria adhering to the surface of medical equipment including indwelling catheters cannot be eradicated, and this causes problems of increased medical difficulty and increased medical cost. There is a need for a new solution to this problem.
Although the prior art proposes to increase the antibacterial property by discarding the surface layer and the attached substance and regenerating a new antibacterial surface, the related preparation method has complicated steps and higher requirements on conditions.
Disclosure of Invention
The invention aims to solve the antibacterial problem and provides an antibacterial composite coating with a self-regeneration function.
Meanwhile, the invention also provides a specific preparation method for the antibacterial composite coating.
Specifically, the invention provides an antibacterial composite coating with a reproducible function constructed on the surface of a base material by an initiated chemical vapor deposition method and a corresponding preparation method. The antibacterial composite coating prepared by the preparation method can achieve a good sterilization effect. The scheme of the invention is that the degradation characteristic of the degradable layer in the composite coating on the substrate is utilized, and the antibacterial layer falls off along with the degradable layer after the degradable layer is degraded, so that a new antibacterial layer is completely exposed, and the new antibacterial layer has a brand new antibacterial effect; thereby leading the material to recover good sterilization and antibiosis capability again.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an antibacterial composite coating with self-regeneration function is attached to a base material and is formed by alternately compounding a plurality of antibacterial layers and a plurality of degradable layers; wherein the thickness of the antibacterial layer is 0.2-2 mu m, and the thickness of the degradable layer is 0.1-1 mu m.
In order to solve the problem that the existing material can not achieve long-term antibiosis, a composite polymer antibacterial coating structure is prepared by an initiation type chemical vapor deposition method, and a degradable layer and an antibacterial layer are alternately arranged on the antibacterial coating; and when the antibacterial layer on the upper layer loses the antibacterial effect, the degradable layer falls off to expose a new antibacterial layer, so that the antibacterial effect is continued. In the prepared composite coating, the antibacterial layer has a good sterilization effect in an initial sterilization test, and after the degradable layer falls off, a new antibacterial layer is completely exposed and can recover the good sterilization capability again.
Preferably, the antibacterial layer is a positively charged polymer, and the degradable layer is a polymer capable of undergoing a hydrolysis reaction in a physiological environment. The antibacterial property of the positively charged polymer is utilized for antibiosis, and the degradable layer is required to be hydrolyzed, so that the degradable layer can fall off after hydrolysis.
Preferably, the antibacterial composite coating is prepared by an initiation type chemical vapor deposition method.
Preferably, the antibacterial layer is a polymer with quaternary ammonium salt cationic group monomer, or
Copolymer of monomer with quaternary ammonium salt cationic group and olefin monomer with two or more than two ethylene double bonds.
Preferably, the degradable layer is: a polymer containing an ethylenic double bond and an acid anhydride group monomer,
A copolymer of a monomer having an ethylenic double bond and an acid anhydride group and an olefin monomer having two or more ethylenic double bonds,
One or more of copolymers of monomers containing vinyl double bonds and acid anhydride groups and olefin water-soluble monomers with vinyl double bonds.
For example, the antibacterial layer is poly (dimethylaminostyrene-ethylene glycol diacrylate) and the degradable layer is polymethacrylic anhydride.
In addition, the preparation method of the antibacterial composite coating specifically comprises the following steps:
step 1: placing a base material to be loaded with the antibacterial composite coating in a vacuum reaction chamber with an alloy heating wire, and keeping the temperature of the base material at 30-50 ℃;
step 2: alternately preparing the antibacterial composite coating of the antibacterial layer and the degradable layer on the base material by adopting an initiation type chemical vapor deposition method; wherein:
the preparation process of the antibacterial layer comprises the following specific steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, vaporizing the monomer A, the monomer B and the initiator respectively, and then introducing the monomer A, the monomer B and the initiator into the reaction cavity, wherein the flow of the monomer A and the monomer B is 0.1-10 sccm, and the flow of the initiator is 0.5-10 sccm; reacting for 10-60 min to make the thickness of the antibacterial layer be 0.1-1 μm;
the preparation of the degradable layer is carried out in one of the following ways:
the first method is as follows: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer C and the initiator, and then mixing and introducing the monomer C and the initiator into the reaction cavity, wherein the flow rates of the monomer C and the initiator are 0.1-10 sccm and 0.5-10 sccm respectively; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
the second method comprises the following steps: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer B, the monomer C and the initiator, mixing, and introducing into the reaction cavity, controlling the flow of the monomer B and the monomer C at 0.1-10 sccm, controlling the flow of the initiator at 0.5-10 sccm, and reacting for 5-60 min to enable the thickness of the degradable layer to be 0.2-2 mu m;
the third method comprises the following steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, then respectively heating and vaporizing the monomer C, the monomer D and the initiator, mixing and introducing the monomer C, the monomer D and the initiator into the vacuum reaction cavity, wherein the flow ranges of the monomer C and the monomer D are 0.1-10 sccm, and the flow range of the initiator is 0.5-10 sccm; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
in the above, the monomer A is a monomer containing quaternary ammonium salt cations;
the monomer B is an olefin monomer containing two or more ethylenic double bonds;
the monomer C is a monomer containing ethylenic double bonds and anhydride groups;
the monomer D is an olefin water-soluble monomer with an ethylenic double bond.
The method adopts an initiation type chemical vapor deposition method, and can adjust the components and the thickness of the degradable layer in real time by utilizing the advantages of vapor deposition to obtain the degradable layers with different degradation times, thereby preparing the renewable antibacterial composite coating with different regeneration times.
Preferably, the monomer A is one or more of dimethylaminomethylstyrene, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
The invention prepares the renewable antibacterial coating by initiating chemical vapor deposition. The composite coating is prepared by replacing the introduced monomer, so that the regeneration of the antibacterial coating is realized.
Preferably, the monomer B is one or more of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2, 4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane and divinylbenzene.
Preferably, the monomer C is one or more of acrylic anhydride, methacrylic anhydride and maleic anhydride.
Preferably, the initiator is one or more of di-tert-butyl hydroperoxide, di-tert-amyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile and perfluorobutanesulfonyl fluoride.
Further, the saturated vapor pressure of the monomer A is 0.01 mmHg to 4 mmHg, the saturated vapor pressure of the monomer B is 0.01 mmHg to 4 mmHg, the saturated vapor pressure of the monomer C is 0.01 mmHg to 4 mmHg, and the saturated vapor pressure of the monomer D is 0.01 mmHg to 4 mmHg.
Through long-term research, the inventor of the present application adopts an initiation type chemical vapor deposition method, and uses a monomer containing a quaternary ammonium salt cationic group and a monomer containing a crosslinking ethylene double bond to deposit a layer of antibacterial layer on the surface of a catheter, then uses anhydride polymers with different degradation kinetics as an intermediate degradable layer, and finally continuously prepares the antibacterial layer containing the monomer containing the quaternary ammonium salt cationic group and the monomer containing the crosslinking ethylene double bond on the surface of the material. The composite material has a good sterilization function in a bacterial solution, can release pollutants on the surface layer in the degradation process, and can recover the sterilization capability again.
The invention has the beneficial effects that: the antibacterial composite coating has a good antibacterial effect, and the antibacterial layer on the surface layer loses antibacterial capability by adopting the degradable layers and the antibacterial layers which are alternately compounded, and then the antibacterial layer is degraded and falls off, so that the exposed new antibacterial layer continues the antibacterial capability. This results in the surface of the material carrying the antimicrobial composite coating being able to have antimicrobial capabilities for a long period of time. The preparation method provided by the invention has simple process, does not need any solvent in the preparation process, can form the antibacterial composite coating on the surface of the medical base material such as a catheter and the like, and ensures the formation and continuous maintenance of the sterile environment on the surface of the medical base material.
Drawings
FIG. 1 is a schematic structural diagram of a self-regenerating antibacterial coating obtained by the present invention.
FIG. 2 shows the infrared and contact angle data before and after degradation for the sample of example 1.
Figure 3 shows XPS data before and after degradation of the sample in example 1.
FIG. 4 shows an SEM image of the sample of example 3 during the antibacterial test.
Figure 5 shows an SEM image of the single layer coating of comparative example 1.
Fig. 6 shows SEM images during the antibacterial test of comparative example 1.
In fig. 1: 1 antibacterial layer, 2 degradable layer and 3 base material.
Detailed Description
The representative embodiments based on the figures will now be further refined. The following description is not intended to limit the embodiments to one preferred embodiment, but to cover alternatives, modifications, and equivalents, which may be included within the spirit and scope of the described embodiments as defined by the appended claims.
The invention provides an antibacterial coating with a self-regeneration function, as shown in figure 1, the antibacterial composite coating is attached to a base material and is formed by alternately compounding a plurality of antibacterial layers and a plurality of degradable layers; wherein the thickness of the antibacterial layer is 0.2-2 mu m, and the thickness of the degradable layer is 1-1 mu m.
The antibacterial layer is a polymer with positive electricity, and the degradable layer is a polymer capable of undergoing a hydrolysis reaction in a physiological environment. The antibacterial layer and the degradable layer are alternately prepared into the antibacterial composite coating by adopting an initiation type chemical vapor deposition method.
Specifically, the antibacterial layer is a polymer with a quaternary ammonium salt cationic group monomer, or a copolymer of the quaternary ammonium salt cationic group monomer and an olefin monomer with two or more than two ethylenic double bonds.
The degradable layer is: a polymer containing an ethylenic double bond and an acid anhydride group monomer,
A copolymer of a monomer having an ethylenic double bond and an acid anhydride group and an olefin monomer having two or more ethylenic double bonds,
One or more of copolymers of monomers containing vinyl double bonds and acid anhydride groups and olefin water-soluble monomers with vinyl double bonds.
A preparation method of an antibacterial composite coating with a self-regeneration function specifically comprises the following steps:
the method specifically comprises the following steps:
step 1: placing a base material to be loaded with the antibacterial composite coating in a vacuum reaction chamber with an alloy heating wire, and keeping the temperature of the base material at 30-50 ℃;
step 2: alternately preparing the antibacterial composite coating of the antibacterial layer and the degradable layer on the base material by adopting an initiation type chemical vapor deposition method; wherein:
the preparation process of the antibacterial layer comprises the following specific steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, vaporizing the monomer A, the monomer B and the initiator respectively, and then introducing the monomer A, the monomer B and the initiator into the reaction cavity, wherein the flow of the monomer A and the monomer B is 0.1-10 sccm, and the flow of the initiator is 0.5-10 sccm; reacting for 10-60 min to make the thickness of the antibacterial layer be 0.1-1 μm;
the preparation of the degradable layer is carried out in one of the following ways:
the first method is as follows: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer C and the initiator, and then mixing and introducing the monomer C and the initiator into the reaction cavity, wherein the flow rates of the monomer C and the initiator are 0.1-10 sccm and 0.5-10 sccm respectively; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
the second method comprises the following steps: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer B, the monomer C and the initiator, mixing, and introducing into the reaction cavity, controlling the flow of the monomer B and the monomer C at 0.1-10 sccm, controlling the flow of the initiator at 0.5-10 sccm, and reacting for 5-60 min to enable the thickness of the degradable layer to be 0.2-2 mu m;
the third method comprises the following steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, then respectively heating and vaporizing the monomer C, the monomer D and the initiator, mixing and introducing the monomer C, the monomer D and the initiator into the vacuum reaction cavity, wherein the flow ranges of the monomer C and the monomer D are 0.1-10 sccm, and the flow range of the initiator is 0.5-10 sccm; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
in the above, the monomer A is a monomer containing quaternary ammonium salt cations;
the monomer B is an olefin monomer containing two or more ethylenic double bonds;
the monomer C is a monomer containing ethylenic double bonds and anhydride groups;
the monomer D is an olefin water-soluble monomer with an ethylenic double bond.
In the above, the monomer A is a monomer containing quaternary ammonium salt cations; specifically, the monomer A is one or more of dimethylaminomethylstyrene, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. The saturated vapor pressure of the monomer A is 0.01 mmHg to 4 mmHg, and the saturated vapor pressure of the monomer B is 0.01 mmHg to 4 mmHg.
The monomer B is an olefin monomer containing an ethylenic double bond; more specifically, the monomer B is one or more of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2, 4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane and divinylbenzene.
The monomer C is a degradable monomer containing anhydride; specifically, the monomer C is a monomer containing an ethylenic double bond and an acid anhydride group. The saturated vapor pressure of the monomer C is 0.01 mmHg to 4 mmHg.
The monomer D is an olefin water-soluble monomer with an ethylenic double bond. The saturated vapor pressure of the monomer D is 0.01 mmHg to 4 mmHg.
The initiator is one or more of di-tert-butyl hydroperoxide, di-tert-amyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile and perfluorobutanesulfonyl fluoride.
Example 1:
the monomer A is dimethyl amino methyl styrene, the monomer B is ethylene glycol acrylate, the monomer C is methacrylic anhydride, an initiation formula chemical vapor deposition method is adopted to prepare the antibacterial coating, and di-tert-butyl peroxide is used as an initiator.
Starting coating, placing the medical catheter on a sample table of a reaction cavity, wherein the temperature of the sample table is 37 ℃, starting a mechanical pump, vacuumizing the reaction cavity until the vacuum degree is 400 mtorr, and keeping the vacuum degree; heating a hot wire of the reaction cavity to 220 ℃; heating the monomer A and the monomer B to gasify the monomers, and controlling the flow rates of the monomers to be 0.7 sccm and 0.08 sccm respectively; the temperature of the initiator di-tert-butyl hydroperoxide is controlled at 25 ℃, and the flow rate is controlled at 0.5 sccm; the deposition time is 45 min, the thickness of the coating is about 800 nm, and the coating is an antibacterial layer.
And then closing valves of pipelines in which the monomer A and the monomer B are positioned, independently introducing the monomer C and the di-tert-butyl hydroperoxide, controlling the flow rates of the monomer C and the di-tert-butyl hydroperoxide to be 0.8 sccm and 0.45 sccm respectively, depositing for 18 min, and obtaining a degradable layer with the thickness of about 600 nm.
And then closing a valve of a pipeline in which the monomer C is positioned, and repeatedly introducing the monomer A and the monomer B for flow control to prepare the antibacterial layer with the thickness of 800 nm.
As shown in figure 1, the surface antibacterial coating of the medical catheter obtained in example 1 is 2.2 μm.
The concentration is selected to be 106Escherichia coli and Staphylococcus aureus (CFU/mL) the samples obtained in example 1 were subjected to antibacterial tests.
The primary antibacterial data show that the surface of the sample has excellent bactericidal effect on escherichia coli and staphylococcus aureus, and the bactericidal rate is as high as more than 95%.
And after the primary sterilization test is finished, continuing performing the sterilization test on the sample, and finding that the sterilization rate is gradually reduced.
The sample is soaked in PBS buffer with pH =7.4, and the intermediate degradable layer is gradually degraded, and the specific degradation process is shown in table 3.
And subsequently, infrared and contact angle tests are carried out on the surface of the degraded sample, and the peak position of the special functional group of the degraded sample is not obviously changed compared with the antibacterial layer on the surface layer, and the contact angle is not obviously different as shown in figure 2. The removal of the degradation layer is thorough, and the new antibacterial layer can be fully exposed.
The XPS test also further demonstrated that the degradable layer was completely degraded, leaving the surface of the material together with the surface antimicrobial layer as shown in fig. 3. The new antibacterial layer is completely exposed, the sterilization function is recovered again, and the sterilization rate of the antibacterial layer on escherichia coli and staphylococcus aureus reaches over 90 percent, which is shown in tables 1 and 2.
Example 2:
the monomer A, the monomer B, the monomer C and the initiator in the monomer A and the initiator in the example 1 are unchanged, and the flow rates of the monomer A, the monomer B and the initiator used for deposition are respectively 0.7 sccm, 0.08 sccm and 0.6 sccm; the hot wire of the reaction cavity is heated to 220 ℃, the vacuum degree of the cavity is 200 mtorr, the vacuum degree is kept, the temperature of the sample stage is 37 ℃, the deposition time is 45 min, the thickness of the coating is about 800 nm, and the coating is an antibacterial layer.
And then closing a valve of a pipeline in which the monomer A is positioned, introducing the monomer B, the monomer C and an initiator di-tert-butyl hydroperoxide, controlling the flow rates of the monomer B, the monomer C and the initiator di-tert-butyl hydroperoxide to be 0.07 sccm, 0.8 sccm and 0.45 sccm respectively, depositing for 8 min, and obtaining a degradable layer with the plating thickness of about 600 nm.
Then the valve of the pipeline where the monomer C is positioned is closed, the flow control of the monomer A and the monomer B is repeatedly led in, the thickness of the antibacterial layer is consistent with 800 nm, and the antibacterial layer is formed.
The concentration is selected to be 106(CFU/mL) of E.coli and S.aureus vs. example 2The resulting samples were tested for antimicrobial activity.
The primary antibacterial data show that the surface of the sample has excellent bactericidal effect on escherichia coli and staphylococcus aureus, and the bactericidal rate is as high as more than 95%. After the primary sterilization test is finished, the sterilization test is continued on the sample, and the sterilization rate is gradually reduced, which is specifically shown in tables 1 and 2.
The sample was soaked in PBS buffer with pH =7.4 and the degradable layer was gradually degraded, the degradation process is shown in table 3.
After the degradable layer is sufficiently degraded, the degradable layer and the surface antibacterial layer are separated from the surface of the material. At this time, the new antibacterial layer is completely exposed, the sterilization function is recovered again, and the sterilization rate of the antibacterial layer to escherichia coli and staphylococcus aureus reaches more than 90 percent as shown in table 1.
Example 3:
the monomer D was replaced by the monomer B in example 2. Other preparation conditions were the same as in example 2.
Starting coating, placing the medical catheter on a sample table of a reaction cavity, wherein the temperature of the sample table is 37 ℃, starting a mechanical pump, vacuumizing the reaction cavity until the vacuum degree is 400 mtorr, and keeping the vacuum degree; heating a hot wire of the reaction cavity to 220 ℃; heating the monomer A and the monomer B to gasify the monomers, and controlling the flow rates of the monomers to be 0.7 sccm and 0.08 sccm respectively; the temperature of the initiator di-tert-butyl hydroperoxide is controlled at 25 ℃, and the flow rate is controlled at 0.45 sccm; the deposition time is 18 min, and the thickness of the coating is about 800 nm.
Then closing a valve of a pipeline in which the monomer A is positioned, introducing the monomer C, the monomer D and an initiator, controlling the flow rates of the monomer C and the initiator to be 0.8 sccm and 0.2 sccm respectively, depositing for 18 min, and obtaining a degradable layer with the thickness of about 600 nm;
the same method is adopted to prepare the antibacterial layer with the thickness of 600 nm on the degradable layer.
The concentration is selected to be 106Escherichia coli and Staphylococcus aureus (CFU/mL) the samples obtained in example 3 were subjected to antibacterial tests.
The primary antibacterial data show that the surface of the sample has excellent bactericidal effect on escherichia coli and staphylococcus aureus, and the bactericidal rate is as high as more than 95%, specifically shown in tables 1 and 2. And after the primary sterilization test is finished, continuing performing the sterilization test on the sample, and finding that the sterilization rate is gradually reduced.
The sample was soaked in PBS buffer with pH =7.4, and the intermediate degradable layer was gradually degraded, and the degradation process of the degradable layer is shown in table 3.
SEM observation of the surface of the sample during degradation as shown in FIG. 4 shows that the bacteria on the surface of the initial material are rarely analyzed because the surface of the material has good bactericidal effect. A large amount of bacteria are gradually accumulated on the surface of the material along with the prolonging of time, which indicates that the material no longer has good sterilization function. After the material is soaked in the PBS buffer solution for 24 hours, a small amount of bacteria are observed to be distributed on the surface of the material, which indicates that the bacteria adhered to the surface of the material are separated from the surface of the material along with the degradation of the degradable layer. The sterilization rate of the antibacterial agent on escherichia coli and staphylococcus aureus reaches over 90 percent, and concretely, the antibacterial agent is shown in tables 1 and 2, and the fact that the new antibacterial layer is completely exposed is proved, and the sterilization function is recovered again.
Comparative example 1:
comparative example 1 only one antibiotic layer was prepared.
The method comprises the following specific steps: starting coating, placing the medical catheter on a sample table of a reaction cavity, wherein the temperature of the sample table is 37 ℃, starting a mechanical pump, vacuumizing the reaction cavity until the vacuum degree is 400 mtorr, and keeping the vacuum degree; heating a hot wire in the reaction cavity to 220 ℃; heating the monomer A and the monomer B to gasify the monomers, and controlling the flow rates of the monomers to be 0.7 sccm and 0.08 sccm respectively; the temperature of the initiator di-tert-butyl hydroperoxide is controlled at 25 ℃, and the flow rate is controlled at 0.45 sccm; the deposition time is 45 min, and the thickness of the coating is about 800 nm.
The single-function antibacterial coating is obtained in the comparative example 1 in the figure 5. The concentration is selected to be 106(CFU/mL) of Escherichia coli and Staphylococcus aureus were subjected to the antibacterial test on the sample obtained in comparative example 1.
The primary antibacterial data show that the surface of the sample has excellent bactericidal effect on escherichia coli and staphylococcus aureus, and the bactericidal rate is as high as more than 95%. And after the primary sterilization test is finished, continuing performing the sterilization test on the sample, and finding that the sterilization rate is gradually reduced. The appearance of the sample for the antibacterial test is observed as shown in figure 6.
The surface is adhered with a large amount of dead bacteria, bacterial secretion and the like, so that the sterilization function is gradually lost, and the sterilization function cannot be recovered, which indicates that the material is not suitable for long-term sterilization.
Table 1: the antibacterial effect of the products on escherichia coli is shown.
| Sterilizing rate (%) | First sterilization | Second sterilization | The PBS is soaked to expose a new antibacterial layer |
| Comparative example 1 | 98.7 | 21.3 | |
| Example 1 | 98.5 | 23.5 | 94.3 |
| Example 2 | 96.8 | 20.1 | 95.6 |
| Example 3 | 98.5 | 19.7 | 95.6 |
Table 2: the antibacterial effect of the products on staphylococcus aureus is shown.
| Sterilizing rate (%) | First sterilization | Second sterilization | The PBS is soaked to expose a new antibacterial layer |
| Comparative example 1 | 99.2 | 17.5 | |
| Example 1 | 99.3 | 21.6 | 95.0 |
| Example 2 | 98.9 | 17.5 | 97.2 |
| Example 3 | 97.1 | 22.0 | 96.4 |
Table 3: data table of degradation rates of degradable layers in composite coatings prepared in examples 1, 2, and 3 at different degradation times (soaking times).
| Rate of degradation | 30 min | 1 h | 3 h | 12 h | 24 h |
| Example 1/PMAH | 20% | 50% | 100% | / | / |
| Example 2/P (MAH-co-MAA） | 100% | / | / | / | / |
| Example 3/P (MAH-co-EGDA） | 10% | 25% | 40% | 70% | 100% |
To sum up, adopt the technical scheme of this application to prepare antibiotic composite coating, this kind of antibiotic composite coating can utilize the degradation characteristics of degradable layer, after the antibiotic layer on top layer loses antibacterial property, degrade the degradable layer to get rid of the antibiotic layer that has lost antibacterial property that will load on it, expose new antibiotic layer, thereby make the substrate (catheter) that has this kind of antibiotic composite coating resume antibiotic effect again, finally reached long-term antibiotic effect.
For purposes of explanation, specific nomenclature is used in the above description to provide a thorough understanding of the described embodiments. It will be apparent to those skilled in the art that certain modifications, combinations, and variations can be made in light of the above teachings.
Claims (10)
1. An antibiotic composite coating with self-regeneration function, which is attached to a substrate, is characterized in that: the antibacterial composite coating is formed by alternately compounding a plurality of antibacterial layers and a plurality of degradable layers; wherein the thickness of the antibacterial layer is 0.2-2 mu m, and the thickness of the degradable layer is 0.1-1 mu m.
2. The antibacterial composite coating with self-regeneration function according to claim 1, wherein: the antibacterial layer is a polymer with positive electricity, and the degradable layer is a polymer capable of undergoing a hydrolysis reaction in a physiological environment.
3. The antibacterial composite coating with self-regeneration function according to claim 1, wherein: the antibacterial composite coating is prepared by adopting an initiation type chemical vapor deposition method.
4. The antibacterial composite coating with self-regeneration function according to claim 1, wherein: the antibacterial layer is a polymer with quaternary ammonium salt cationic group monomer, or
Copolymer of monomer with quaternary ammonium salt cationic group and olefin monomer with two or more than two ethylene double bonds.
5. The antibacterial composite coating with self-regeneration function according to claim 1, wherein: the degradable layer is: a polymer containing an ethylenic double bond and an acid anhydride group monomer,
A copolymer of a monomer having an ethylenic double bond and an acid anhydride group and an olefin monomer having two or more ethylenic double bonds,
One or more of copolymers of monomers containing vinyl double bonds and acid anhydride groups and olefin water-soluble monomers with vinyl double bonds.
6. A method for preparing an antibacterial composite coating with self-regeneration function according to any one of the preceding claims, which is characterized in that: the method specifically comprises the following steps:
step 1: placing a base material to be loaded with the antibacterial composite coating in a vacuum reaction chamber with an alloy heating wire, and keeping the temperature of the base material at 30-50 ℃;
step 2: alternately preparing the antibacterial composite coating of the antibacterial layer and the degradable layer on the base material by adopting an initiation type chemical vapor deposition method; wherein:
the preparation process of the antibacterial layer comprises the following specific steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, vaporizing the monomer A, the monomer B and the initiator respectively, and then introducing the monomer A, the monomer B and the initiator into the reaction cavity, wherein the flow of the monomer A and the monomer B is 0.1-10 sccm, and the flow of the initiator is 0.5-10 sccm; reacting for 10-60 min to make the thickness of the antibacterial layer be 0.1-1 μm;
the preparation of the degradable layer is carried out in one of the following ways:
the first method is as follows: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer C and the initiator, and then mixing and introducing the monomer C and the initiator into the reaction cavity, wherein the flow rates of the monomer C and the initiator are 0.1-10 sccm and 0.5-10 sccm respectively; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
the second method comprises the following steps: keeping the vacuum degree of the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, respectively heating and vaporizing the monomer B, the monomer C and the initiator, mixing, and introducing into the reaction cavity, controlling the flow of the monomer B and the monomer C at 0.1-10 sccm, controlling the flow of the initiator at 0.5-10 sccm, and reacting for 5-60 min to enable the thickness of the degradable layer to be 0.2-2 mu m;
the third method comprises the following steps: keeping the vacuum degree in the reaction cavity at 100-1000 mTorr and the temperature at 180-300 ℃, then respectively heating and vaporizing the monomer C, the monomer D and the initiator, mixing and introducing the monomer C, the monomer D and the initiator into the vacuum reaction cavity, wherein the flow ranges of the monomer C and the monomer D are 0.1-10 sccm, and the flow range of the initiator is 0.5-10 sccm; reacting for 5-60 min to make the thickness of the degradable layer be 0.2-2 μm;
in the above, the following steps:
the monomer A is a monomer containing quaternary ammonium salt cations;
the monomer B is an olefin monomer containing two or more ethylenic double bonds;
the monomer C is a monomer containing ethylenic double bonds and anhydride groups;
the monomer D is an olefin water-soluble monomer with an ethylenic double bond.
7. The method of claim 6, wherein: the monomer A is one or more of dimethyl amino methyl styrene, dimethyl amino ethyl methacrylate and diethylamino ethyl methacrylate.
8. The method of claim 6, wherein: the monomer B is one or more of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2, 4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane and divinylbenzene.
9. The method of claim 6, wherein: the monomer C is one or more of acrylic anhydride, methacrylic anhydride and maleic anhydride.
10. The method of claim 6, wherein: the initiator is one or more of di-tert-butyl hydroperoxide, di-tert-amyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile and perfluorobutanesulfonyl fluoride.
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| CUICUI SU 等: ""Solvent-Free Fabrication of Self-Regenerating Antibacterial Surfaces Resisting Biofilm Formation"", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 13, pages 10553 - 10563 * |
| FRANZISKA DORNER 等: ""Toward Self-Regenerating Antimicrobial Polymer Surfaces"", 《ACS MACRO LETTERS》, vol. 4, pages 1337 - 1340, XP055681010, DOI: 10.1021/acsmacrolett.5b00686 * |
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| Publication number | Publication date |
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| CN114016002B (en) | 2024-06-14 |
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