CN107602901B - Biological-resistant coating material for catalyzing bacterial cracking by high-density grafted acid groups, and preparation method and application thereof - Google Patents
Biological-resistant coating material for catalyzing bacterial cracking by high-density grafted acid groups, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anti-biofilm material for catalyzing bacterial lysis by high-density grafting acid groups, and a preparation method and application thereof. Activating the material by using plasma to enable the material to generate surface free radicals; and then exposing the material to air to generate an active oxygen reaction center, adding the material into an excessive unsaturated monomer containing acid groups to start surface polymerization reaction, and after the reaction is finished, cleaning and drying to obtain the anti-biofilm material with the surface grafted with high-density acid groups to catalyze the bacterial cracking. The surface of the material is grafted with high-density acid groups to generate a super-hydrophilic surface which can catalyze bacteria to crack so as to express the function of antibiosis, particularly the function of anti-biofilm. The material of the invention has wider application because no antibacterial agent with high biological toxicity, environment-friendliness, such as quaternary ammonium salt, metal ion and the like is used. Because antibiotic embedding is avoided, the risks of drug resistance, superbacteria generation and outbreak and runaway of epidemic diseases are reduced.
Description
Technical Field
The invention belongs to the field of super-hydrophilic, antibacterial and anticorrosive materials, and particularly relates to a novel antibacterial, anticorrosive and anti-biofilm technology without antibacterial agents and metal ions, in particular to an anti-biofilm material for high-density grafting acid group catalytic bacterial cracking, and a preparation method and application thereof.
Background
Human survival and health continue to be threatened by various bacterial viruses. A large number of microorganisms exist in the human living environment, and from the aspects of fiber clothing, household appliances, sanitary ceramic products, plastic films, steel products for construction, coating, disinfection treatment of drinking water and the like, which are commonly used daily, the microorganisms can rapidly propagate under proper temperature and nutrients, so that the phenomena of deterioration, putrefaction, mildew, wound suppuration infection and the like of substances are caused, and the health of human beings is seriously threatened.
In recent years, people are more aware of the long-term struggle with bacterial microorganisms due to the events such as escherichia coli epidemic situation and the like, and people in daily life are increasingly unable to leave antibacterial technology, so that antibacterial materials become one of the hotspots for the research and development of new materials at present. The antibacterial material is a novel functional material with sterilization and bacteriostasis performance, the core component of the antibacterial material is an antibacterial agent, and a small amount of the antibacterial agent is added into a common material to prepare the antibacterial material. At present, there are 3 main types of antibacterial materials, which are natural antibacterial materials, organic antibacterial materials and inorganic antibacterial materials. The research on natural antibacterial materials and organic antibacterial materials is early, the natural antibacterial materials and the organic antibacterial materials are various, and the application is limited due to the defects of toxicity, long-acting property, non-high temperature resistance and the like. Inorganic antibacterial materials are a class of antibacterial materials developed in recent 20 years, and mainly include a semiconductor photocatalytic type, a metal ion metal oxide type and the like. The antibacterial material has the advantages of good chemical stability, good thermal stability, no toxicity, broad spectrum and the like, and has great advantages in the application of products such as plastics, fibers, coatings, ceramics and the like. Among inorganic antibacterial materials, inorganic antibacterial agents whose antibacterial active ingredients are metals are the most widely studied antibacterial agents at present, and among them, silver-based inorganic antibacterial materials which have strong bactericidal activity and are nontoxic are more studied. The earliest organic antibacterial agents were antibiotics, small molecule quaternary ammonium salts and quaternary phosphonium salts. In recent years, studies have focused on the introduction of heteroatoms such as oxygen and sulfur into the hydrophobic chain and unsaturated alkyl groups into the quaternary nitrogen to contribute to the improvement of antibacterial activity. These derivatives have strong basicity and are capable of attracting negatively charged bacteria to bind their free activity and cause "contact death". In addition, under the force of an electric field, negative charges on cell walls and cell membranes are deformed due to uneven distribution, which causes physical rupture, and substances such as water and proteins in cells overflow, causing a phenomenon of "bacterial solution" to die. However, the organic antibacterial agent has poor temperature resistance, dissolution and precipitation phenomena, and short service life. In order to improve the performance of organic antibacterial agents and reduce the irritation and toxicity of the organic antibacterial agents to the environment and human beings, the antibacterial agents with slow release, long acting, high efficiency and low toxicity are developed, and the polymer antibacterial agents are prepared by polymerizing the monomer compounds of the antibacterial agents or fixing the molecules of the antibacterial agents on a high-molecular carrier. The polymer antibacterial agent is favored due to its advantages of low toxicity, stability, antibacterial durability, easy modification and the like. And the modification and modification of the polymer can flexibly introduce inorganic and organic antibacterial groups to synthesize various antibacterial agents with different requirements, so as to prepare the high-molecular organic antibacterial material with high performance and high selectivity. The polymer quaternary ammonium salt is put into practical use in many production and living fields.
The main problems of the existing antibacterial materials are that the components of the organic antibacterial agent are all cationic groups, and the biological toxicity is high. The metal ions are toxic and can cause environmental pollution. The existing cation and metal ion method is not suitable for being widely applied for a long time and is not suitable for medical use. In the medical field, surface embedding of antibiotics is used in a variety of implantable devices. Widespread and long-term use can exacerbate drug resistance, leading to superbacteria, outbreaks, and loss of control.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a novel antibacterial and antiseptic technology without using antibacterial agent and metal ions in order to solve the problems of high biotoxicity, environment unfriendliness and drug resistance of antibiotics of organic quaternary ammonium salts and metal ions, in particular to an anti-biofilm material with a surface grafted with high-density acid groups for catalyzing bacterial lysis, and a preparation method and application thereof.
The invention firstly discloses a preparation method of an anti-biofilm material for high-density grafting acid group catalytic bacteria cracking, which comprises the following steps:
1) cleaning the surface of the material to remove particles and pollution on the surface of the material; such as the removal of particles and various possible organic and inorganic contaminations from the surface of the material by ultrasound assistance. Depending on the material, water, acid, alkali, organic solvent, etc. may be used.
2) Activating the material by using plasma to generate surface free radicals;
3) after the material is activated by plasma, the material is exposed to the air to generate active oxygen reaction centers,
4) adding the material into excessive unsaturated monomer containing acid group to start surface polymerization reaction, the polymerization reaction is carried out under the condition of no oxygen, the temperature is maintained at 25-95 ℃, the reaction time is 1-16 hours,
5) after the reaction is finished, cleaning the material to remove the monomer and a small amount of free polymer, and drying; to obtain the anti-biofilm material with the surface grafted with high-density acid groups for catalyzing the bacterial lysis.
Although various gases including oxygen and nitrogen are available, inert gases such as helium and argon are less harmful to the surface of the material, and helium or argon is preferably used as the gas for plasma activation.
The time of exposing the step 3) to the air is less than 30 min.
Many unsaturated acids may be used as the polymerization monomer in the step 4), and the unsaturated monomer containing an acid group according to the present invention may be one or more of acrylic acid, methacrylic acid, sorbic acid, cinnamic acid, vinylsulfonic acid, and propenylboronic acid.
In the polymerization reaction process of the step 4), the mass percentage concentration of the monomers is controlled to be more than 5%.
The material of the step 1) is a high molecular material or a metal material or various chemically inert composite materials.
The invention also discloses an anti-biofilm material with the surface grafted with high-density acid groups for catalyzing bacterial lysis, which is prepared by the method.
The surface carboxyl density of the anti-biofilm material with the surface grafted high-density acid groups for catalyzing bacterial lysis is more than 90 micrograms/square centimeter.
The invention also discloses an application of the material as an antibacterial material, and a super phospholipid catalytic interface is generated by utilizing high-density acid groups (carboxyl, sulfonic acid and boric acid) grafted on the surface of the material to cause the cracking of a lipid membrane so as to kill bacteria. The bacterial lipid membrane is taken as a target spot, is also effective to gram-positive bacteria, gram-negative bacteria and drug-resistant bacteria, and belongs to a super antibacterial material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the material of the invention has wider application because no antibacterial agent with high biological toxicity, environment-friendliness, such as quaternary ammonium salt, metal ion and the like is used.
(2) The technique is particularly suited for medical applications, especially implantable medical materials. Because antibiotic embedding is avoided, the risks of drug resistance, superbacteria generation and outbreak and runaway of epidemic diseases are reduced.
(3) The material of the invention takes the bacterial lipid membrane as a target spot, is also effective on gram-positive bacteria, gram-negative bacteria and drug-resistant bacteria, and belongs to a super antibacterial material.
(4) This process can produce a superhydrophilic surface.
(5) The method is simple, low in cost and suitable for polymer, metal and various chemically inert composite materials.
Detailed Description
1. Antibacterial latex catheter
Step one, cleaning a medical latex catheter (with the length of 1-4 cm and the inner diameter of 1 mm) by using ethanol, and drying;
secondly, placing the latex conduit in a plasma generator, vacuumizing, introducing argon into a reaction bin (less than 400 millitorr and 2.4 cubic meters per hour), and starting plasma excitation (output power is 80 watts and 3 minutes);
thirdly, placing the latex conduit activated by the plasma in the air for oxidizing for 70 minutes to generate an active reaction center, then placing the latex conduit in a container which is subjected to deoxidation treatment and contains 40% of acrylic acid aqueous solution, and sealing;
step four, carrying out polymerization reaction under an oxygen-free condition, maintaining the temperature at 70 ℃, and reacting for 12 hours;
and step five, after the reaction is finished, washing the latex catheter in an ultrasonic water bath by using water, 30% sodium hydroxide, purified water and ethanol respectively to remove monomers and free polymer, and drying under the condition of ultraviolet sterilization to obtain the antibacterial latex catheter.
2. An antibacterial silicon wafer.
Step one, a silicon wafer (about 1x1 cm, 1 mm in thickness) is respectively washed by 98 percent sulfuric acid, 2.0M NaOH, purified water and ethanol and dried;
secondly, placing the silicon wafer in a plasma generator, vacuumizing (1000 millitorr), introducing nitrogen into a reaction bin (1.2 cubic meters per hour), and starting plasma excitation (with output power of 100 watts) for 10 minutes;
activating the silicon wafer by using plasma, placing the silicon wafer in the air for oxidizing for 120 minutes to generate an active reaction center, then placing the silicon wafer in a 10% sorbic acid aqueous solution container which is subjected to deoxidation treatment in advance, and sealing;
step four, carrying out polymerization reaction under an oxygen-free condition, maintaining the temperature at 90 ℃, and reacting for 6 hours;
and step five, after the reaction is finished, cleaning the silicon wafer in an ultrasonic water bath by using water, 30% sodium hydroxide, purified water and ethanol respectively to remove monomers and free polymer, and drying under the condition of ultraviolet sterilization to obtain the antibacterial silicon wafer.
3. An antibacterial polyethylene terephthalate (PET) film.
Step one, a PET film (1x1 cm, 0.2 mm thick) for food is cleaned by ethanol and dried;
secondly, placing the PET film in a plasma generator, vacuumizing, introducing argon into a reaction bin (less than 800 millitorr and 1.8 cubic meters per hour), and starting plasma excitation (output power is 80 watts and 5 minutes);
activating a PET film by using plasma, placing the PET film in air for oxidizing for 60 minutes to generate an active reaction center, then placing a latex conduit in a 45% acrylic acid-containing aqueous solution container which is subjected to deoxidation treatment in advance, and sealing;
step four, carrying out polymerization reaction under an oxygen-free condition, maintaining the temperature at 80 ℃, and reacting for 6 hours;
and step five, after the reaction is finished, washing the PET film in an ultrasonic water bath by using water, 30% sodium hydroxide, purified water and ethanol respectively to remove monomers and free polymer, and drying under the condition of ultraviolet sterilization to obtain the antibacterial PET film.
3. And (3) testing main performances:
3.1. surface carboxyl determination: the amount of grafted carboxyl groups on the sample surface was determined by colorimetric method of toluidine blue-O staining. First, a 0.5 mmol toluidine blue-O solution having a pH of 10 was prepared. The grafted material was placed in toluidine blue-O solution and left at 60 ℃ for 6 hours. The material was washed with deionized water and sodium hydroxide solution (pH 9) to remove any free dye attached to the surface. Toluidine blue-O complexed on the material by carboxyl groups was then dissolved by 33% acetic acid and the amount of toluidine blue-O was determined by the optical density at 630 nm. The ratio between dye and carboxylic acid groups was 1:1, so that the surface carboxylic acid content and density could be calculated.
In one specific embodiment of the invention, cinnamic acid is used as a monomer, and the material is a PET film for food. The same plasma conditions were used, but different concentrations of cinnamic acid monomer were applied to initiate PET surface modification. The high monomer concentration versus high density graft surface is shown in table 1.
TABLE 1 Effect of monomer concentration on the acid group density on PET surface
3.2. Surface hydrophilicity measurement: the hydrophilicity and hydrophobicity of the material surface were measured by a contact angle instrument. A micro syringe is used for injecting 1.0 mu L of pure water sample to the surfaces of the materials of the control group and the experimental group, and the water contact angle is measured through a camera of a contact angle instrument and built-in software. The corresponding raw material was used as control without modification. The results are shown in Table 2.
3.3. Human tissue cytotoxicity assay: a sample of the material (silica gel catheter: 1.0 cm length, 1 mm inner diameter; PET film: 1X1 cm, 0.2 mm thickness; silicon wafer: about 1X1 cm, 1 mm thickness) was placed in a 6-dimensional plate, inoculated with human cells, and incubated with a medium containing bovine serum at 37 ℃ and 5% CO2After washing with physiological saline, the viable cells on the surface of the material sample were stained with MTT, and the number of viable cells was determined by a standard curve. The corresponding raw material was used as control without modification. Cytotoxicity (%) ═ 100 × (number of living cells in control group-number of living cells in antibacterial sample group)/number of living cells in control group. The results are shown in Table 2.
Table 2: hydrophilic (hydrolytic feelers) of the surface of materials and toxic consequences for human cells
As can be seen from table 2, the material treated by the method of the invention showed very good hydrophilicity compared to the raw material; i.e. the material surface is grafted with high-density acid groups to generate a super-hydrophilic surface. However, these high-density acid-based grafted high-density surfaces exhibit very good biocompatibility. The modified material surface has no obvious cytotoxicity to cells derived from different human tissues.
3.4. Antibacterial and anti-biofilm activity assays: a sample of the material (silica gel catheter: 1.0 cm length, 1 mm inner diameter; PET film: 1X1 cm, 0.2 mm thickness; silicon wafer: about 1X1 cm, 1 mm thickness) was placed in a suspension of bacteria (2X 104cfu/ml, E.coli, Staphylococcus aureus, Staphylococcus epidermidis) growing in the middle log phase for 2 hours so that the bacterial cells attached to the surface of the material. Free bacteria were carefully removed by washing and a sample of the material was transferred to TSBG (trypticase Soy Broth + 0.2% glucose) broth and incubated overnight at 37 ℃. After washing to remove free bacteria, biofilm formed on the surface of the material samples was evaluated for antibacterial and anti-biofilm activity by conventional Live/Dead and MTT assays. There are three control groups: 1) raw materials; 2) the raw material is treated by plasma, but no high molecular graft is generated; 3) the raw material is grafted with high-density alcohol-based polymer (polyallyl alcohol) through plasma treatment. Antibacterial activity (live/dead assay) 100 × dead cells/(dead cells + live cells); anti-biofilm activity (MTT assay) was 100 × anti-bacterial sample group live cells/control group live cells.
Table 3: results of antibacterial and biofilm Rate test (%)
Note: the 3 control groups (raw material, raw material treated by plasma but not grafted by polymer, raw material treated by plasma and grafted by high-density alcohol-based polymer (polyallyl alcohol)) have no significant difference, and do not show antibacterial or anti-biofilm activity (the antibacterial rate is less than 10%).
3.5. Long-term biofilm activity assay: a silicone rubber catheter sample (2-4 cm length, 1 mm inner diameter) was connected into a semi-closed bacterial culture system. The system was first filled with a suspension of bacteria (2X 104cfu/ml, E.coli, Staphylococcus aureus, Staphylococcus epidermidis) growing in the medium log phase and incubated at 37 ℃ for 4 hours. The system was then continuously perfused with fresh TSBG medium (flow rate 0.12 ml/min) for continuous culture and biofilm formation was observed by microscopy. At specific time points (1, 3, 5, 7, 14, 21 days), the silicone rubber catheters were taken out from the system, and the bacterial envelopes formed on the inner walls of the silicone rubber catheters were quantitatively analyzed by the MTT method. There were two control groups: 1) raw materials; 2) the raw material was plasma treated but without high molecular grafting. Anti-biofilm activity (MTT assay) was 100 × anti-bacterial sample group live cells/control group live cells.
Table 4: long term antibacterial (Staphylococcus aureus) biofilm test results
As can be seen from the results in Table 4, the silica gel catheter which was not grafted with the appropriate surface acid group did not have any bioactivity, and bacteria adhered to the catheter surface and rapidly developed a biofilm after continuous culture, and completely blocked the entire catheter inner tube within 2-3 days. In contrast, the silica gel catheter in example 1 had no bacterial adhesion and biofilm formation even after 21 days of continuous culture under the same experimental conditions. Catheters derived from modification with acrylic alcohols of similar structure but without acid groups did not exhibit any anti-biofilm activity as the original silica gel catheters.
Claims (6)
1. A method for preparing a biofilm-resistant material for catalyzing bacterial lysis by high-density grafted acid groups, wherein the carboxyl density on the surface of the biofilm-resistant material is more than 90 micrograms per square centimeter, and the method is characterized by comprising the following steps:
1) cleaning the surface of the material to remove particles and pollution on the surface of the material;
2) activating the material by using plasma to generate surface free radicals;
3) after the material is activated by plasma, the material is exposed to the air to generate active oxygen reaction centers, and the time of exposure to the air is 60 minutes, 70 minutes or 120 minutes;
4) adding the material into excessive unsaturated monomer containing acid group to start surface polymerization reaction, controlling the mass percentage concentration of the monomer to be more than 5%, carrying out the polymerization reaction under the oxygen-free condition, maintaining the temperature at 25-95 ℃, and reacting for 1-16 hours;
5) after the reaction is finished, cleaning the material to remove the monomer and a small amount of free polymer, and drying; to obtain the anti-biofilm material with the surface grafted with high-density acid groups for catalyzing the bacterial lysis.
2. The method according to claim 1, wherein the gas used for plasma activation in step 2) is helium or argon.
3. The method according to claim 1, wherein the unsaturated monomer containing an acid group in the step 4) is one or more of acrylic acid, methacrylic acid, sorbic acid, cinnamic acid, vinylsulfonic acid, and propenylboronic acid.
4. The method according to claim 1, wherein the material of step 1) is a polymer material or a metal material.
5. A biofilm-resistant material prepared by the method of claim 1 wherein the high density grafted acid groups catalyze the lysis of bacteria.
6. Use of the material of claim 5 as an antimicrobial material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387379B1 (en) * | 1987-04-10 | 2002-05-14 | University Of Florida | Biofunctional surface modified ocular implants, surgical instruments, medical devices, prostheses, contact lenses and the like |
| CN104311866A (en) * | 2014-10-08 | 2015-01-28 | 中国人民解放军第三O九医院 | Surface-modified vulcanized silicone rubber material and preparation method thereof |
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| JPH01275639A (en) * | 1988-04-28 | 1989-11-06 | Agency Of Ind Science & Technol | Surface modification |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387379B1 (en) * | 1987-04-10 | 2002-05-14 | University Of Florida | Biofunctional surface modified ocular implants, surgical instruments, medical devices, prostheses, contact lenses and the like |
| CN104311866A (en) * | 2014-10-08 | 2015-01-28 | 中国人民解放军第三O九医院 | Surface-modified vulcanized silicone rubber material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "PET非织造布表面改性及抗菌性能研究";何艳丽;《PET非织造布表面改性及抗菌性能研究"，何艳丽，中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20100515(第5期);第B024-17页 * |
| "Surface Characterization and Antibacterial Activity of Chitosan-Grafted Poly(ethylene terephthalate) Prepared by Plasma Glow Discharge";MAN WOO HUH, et al.;《Journal of Applied Polymer Science》;20011231;第81卷;第2769-2778页 * |
| "聚合物薄膜等离子体接枝丙烯酸类单体的研究";施来顺，等;《山东工业大学学报》;20001031;第30卷(第5期);第411-418页 * |
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Effective date of registration: 20220126 Address after: 310000 room 607, building 6, No. 600, Baiyang street, Qiantang District, Hangzhou City, Zhejiang Province Patentee after: Hangzhou Zhongke physicochemical Biomedical Technology Co.,Ltd. Address before: 310018 No.600, 21st Street, Hangzhou Economic and Technological Development Zone, Zhejiang Province Patentee before: HANGZHOU Research Institute TECHNICAL INSTITUTE OF PHYSICS AND CHEMISTRY CAS |