CN114344571B - Antibacterial material and preparation method and application thereof - Google Patents
Antibacterial material and preparation method and application thereof Download PDFInfo
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- CN114344571B CN114344571B CN202111523081.XA CN202111523081A CN114344571B CN 114344571 B CN114344571 B CN 114344571B CN 202111523081 A CN202111523081 A CN 202111523081A CN 114344571 B CN114344571 B CN 114344571B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 76
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 25
- 239000000783 alginic acid Substances 0.000 claims abstract description 23
- 229920000615 alginic acid Polymers 0.000 claims abstract description 23
- 229960001126 alginic acid Drugs 0.000 claims abstract description 23
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 20
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 18
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 18
- 229960003237 betaine Drugs 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 208000019206 urinary tract infection Diseases 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 229920002379 silicone rubber Polymers 0.000 description 13
- 241000588770 Proteus mirabilis Species 0.000 description 9
- 241000191963 Staphylococcus epidermidis Species 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000004945 silicone rubber Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000001635 urinary tract Anatomy 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Materials For Medical Uses (AREA)
Abstract
The application discloses an antibacterial material which is formed by the complex crosslinking of alginic acid and zwitter-ion copolymer and copper ions. The zwitterionic polymer end can prevent bacteria from adhering due to good hydrophilicity, so that an anti-adhesion effect is achieved, and an anti-adhesion layer is formed; meanwhile, copper ions can be intelligently released according to environmental changes, so that the aim of sterilization is fulfilled, and the method is particularly suitable for clinical urinary tract infection.
Description
Technical Field
The application relates to an antibacterial material, and belongs to the field of biomedical high polymer materials.
Background
Infection with implantable medical devices is a serious problem facing current clinical practice. The antibacterial coating is constructed on the surface of the device to inhibit the adhesion, growth and reproduction of bacteria, is an effective means for resisting infection, and is one of the research hotspots in the field of biomedical materials at present.
The conventional antibacterial coating is roughly classified into an anti-adhesion type and a sterilization type, and the antibacterial effect is achieved by inhibiting adhesion of bacteria or killing bacteria. Clinical application finds that a coating which exerts an antibacterial/bactericidal function by means of a single mechanism has certain limitations, and particularly has a poor long-term antibacterial effect. For example, anti-adhesion coatings can inhibit, but not completely prevent, the deposition of bacteria on a surface, and small amounts of bacteria that reach the surface can still multiply and grow to form a biofilm; the bactericidal groups contacting the bactericidal coating are generally positively charged and tend to adsorb bacterial residues, covering the bactericidal active and causing failure; the release of the biocide is effected after the surface of the release biocidal coating is covered by the deposition of other substances. The coatings have single antibacterial mechanism and poor long-term antibacterial effect, and cannot fundamentally solve the problem of coating failure caused by the propagation of bacteria on the surface or the covering of residues on the surface.
The multi-mechanism coating with anti-adhesion and bactericide release functions is constructed, and the antibacterial capability of the surface of the material can be effectively improved. However, the surface-loaded bactericide has the problems of easy consumption, biological toxicity of high-concentration bactericide and the like. How to design a response mechanism, the coating can selectively regulate and control the release of the bactericide according to environmental changes, and the antibacterial capability of the coating is intelligently regulated, so that the probability of infection and complication is reduced, the coating is a very interesting problem in the field of antibacterial materials, and has an important clinical application prospect.
Disclosure of Invention
In view of the deficiencies of the prior art, according to one aspect of the present application, an antimicrobial material is provided.
An antibacterial material, which is characterized by comprising a substrate, alginic acid and a complex compound of a zwitterionic copolymer and copper ions.
The antibacterial material is formed by the copolymer of alginic acid and zwitterion and copper ion through complex crosslinking. The zwitterionic polymer end can prevent bacteria from adhering due to good hydrophilicity, so that an anti-adhesion effect is achieved, and an anti-adhesion layer is formed; meanwhile, copper ions can be intelligently released according to environmental changes, the aim of sterilization is achieved, and a sterilization layer is formed. The antibacterial performance of the surface of the implantation instrument is improved through the dual mechanism synergistic effect of the anti-adhesion layer and the sterilization layer.
Optionally, the copper ion-alginic acid-zwitterionic copolymer has a copper ion content of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 μ g/cm 2 Or a value in a range between any two values.
Optionally, the alginic acid-zwitterionic copolymer has a zwitterion selected from at least one of a carboxylate betaine zwitterion, a sulfonate betaine zwitterion, and a phosphate betaine zwitterion.
Optionally, the substrate is selected from at least one of a metal substrate and a polymer material substrate.
In a second aspect of the present invention, there is provided a method for preparing the above antibacterial material.
A method for preparing an antibacterial material comprises the following steps:
(1) obtaining an aqueous solution containing alginic acid-zwitterionic copolymer;
(2) obtaining an aqueous solution containing copper ions;
(3) immersing the substrate in an aqueous solution containing copper ions to obtain a substrate with the surface coated by the aqueous solution containing copper ions;
(4) and soaking the substrate with the surface coated by the aqueous solution of copper ions in the aqueous solution of alginic acid-zwitter ion copolymer for reaction to obtain the antibacterial material.
The preparation method of the copolymer of alginic acid and zwitterion comprises the following steps:
dissolving alginic acid in 1-5% (v/v) in water, heating the solution to 60 ℃ and maintaining the temperature during the reaction, then adding the initiator ammonium persulfate or potassium persulfate, previously keeping the reaction system in an oxygen-free environment by argon or nitrogen degassing, bubbling argon or nitrogen again into the mixture for 30min, and then gradually adding the zwitterionic monomer aqueous solution to the mixture by using a syringe within 30min, wherein the molar ratio of the zwitterionic monomer to the alginic acid units is 1: 1, the reaction time is 6 h. After the reaction, dialysis was performed for three days using a cellulose membrane (molecular weight cut-off of 12,000), and the product was collected after lyophilization.
Alternatively, in step (1), the mass concentration of the solution of the copolymer of alginic acid and zwitterion is any value or a range of any two values determined among 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%.
Alternatively, the copper ion concentration of the aqueous solution in the step (2) is any value or any two values in a determined range of 1mmol/L, 1.5mmol/L, 2mmol/L, 2.5mmol/L, 3mmol/L, 3.5mmol/L, 4mmol/L, 4.5mmol/L, 5mmol/L, 5.5mmol/L, 6mmol/L, 6.5mmol/L and 7 mmol/L.
The copper ions are at least one of copper chloride solution, copper sulfate solution, copper nitrate solution and copper acetate solution.
Optionally, the immersion time in step (3) is any value or values in any two value determination ranges of 3min, 6min, 9min, 12min, 15min, 18min, 21min, 24min, 27min, 30min, 33min, 36min, 39min, 42min, and 45min, and the immersion time in step (4) is any value or values in any two value determination ranges of 5min, 10min, 15min, 20min, 25min, 30min, 35min, and 40 min.
In a third aspect of the invention, there is provided an anti-infective use of the above-described antimicrobial material as an implantable medical device.
The antibacterial material and the antibacterial material prepared by the preparation method are applied to infection resistance of implantable medical devices.
Preferably, the implantable medical device comprises a urinary tract implantable medical device.
The beneficial effect that this application can produce includes:
(1) the antibacterial material prepared by the application has a dual-mechanism synergistic antibacterial effect, firstly, the zwitterionic polymer end can prevent bacteria from being adhered to form an anti-adhesion layer, and meanwhile, the copper ions can be released to further kill the bacteria to form a dual-antibacterial effect.
(2) The antibacterial material provided by the application is formed by crosslinking based on the complexation between copper ions and alginic acid-zwitter-ion copolymer, an initiator, a crosslinking agent and a catalyst are not required to be additionally added, the operation is simple and easy, the residue problem is avoided, and the industrial application is facilitated; meanwhile, the complexing crosslinking network structure endows the antibacterial material with good self-repairing performance.
(3) The copper ions in the antibacterial material provided by the application can be free NH in the surrounding environment 3 Is released "intelligently" as free NH in solution 3 When the concentration of (2) is increased, the release of copper ions is accelerated, and the preparation is particularly suitable for clinical urinary tract infection.
Drawings
FIG. 1: the antibacterial material structure of the embodiment and the antibacterial action schematic diagram of the antibacterial material structure under different pH conditions are adopted in the application.
FIG. 2: example 1 used in this application at different pH (with different NH concentrations) 3 ) Response behavior under conditions.
FIG. 3: blank substrate (silicone rubber), comparative example 1 and the silicone rubber of the application example 1, and count result graphs after 4 hours of bacterial adsorption of alginate-copper ion and alginic acid and zwitter ion and copper ion complex modified surfaces respectively.
FIG. 4: scanning electron microscope photographs of blank substrates (silicon rubber), comparative example 1 and the silicon rubber of the application example 1 and the complex modified surfaces of alginic acid-copper ions and alginic acid and zwitterions and copper ions after bacteria adsorption for 4 hours are respectively carried out.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Example 1
(1) Preparing to obtain alginic acid-zwitter ion copolymer;
alginic acid was dissolved in water at 3% (v/v), the solution was heated to 60 ℃ and maintained at this temperature during the reaction, then the initiator ammonium persulfate was added, the reaction system was previously kept in an oxygen-free environment by argon degassing, argon was bubbled through the mixture for a further 30min, followed by gradual addition of the aqueous solution of the carboxylate betaine zwitterionic monomer to the mixture within 30min using a syringe, wherein the molar ratio of the carboxylate betaine zwitterionic monomer to the alginic acid was 1: 1, the reaction time is 6 h. After the reaction, dialysis was performed for three days using a cellulose membrane (molecular weight cut-off of 12,000), and the product was collected after lyophilization.
(2) Copper sulfate is adopted to prepare a copper ion solution, the solvent is water, and the concentration of copper ions is 7 mmol/L;
(3) preparing copolymer solution of alginic acid-carboxylate betaine type zwitter ions, wherein the solvent is water, and the mass concentration of the water is 8%;
(4) soaking the high molecular base material silicon rubber in the copper ion solution for 45 min;
(5) soaking the high molecular base material silicone rubber in alginic acid and carboxylate betaine type amphoteric ion copolymer solution for 40 min; thus obtaining the silicone rubber coated with the coating.
The coating materials were placed in 25mL 10mM ammonia in water at 37 deg.C and 250rpm with stirring10min, the research finds that the coating material in the ammonia water solution with low concentration has no obvious change, but in the ammonia water solution with high concentration, the gel structure is partially destroyed and is distributed in the whole centrifuge tube, which is caused by the copper ions and free NH in the coating material 3 Resulting in the formation of copper ammonia complex and the release of copper ions from the coating material, see fig. 2. It was demonstrated that the copper ions in the coating could be based on free NH in the surrounding environment 3 Is "intelligently" released. The release diagram is shown in fig. 1.
The coating material was placed in 25mL of 100mM ammonia in water due to the copper ions and free NH in the coating material 3 Copper ammonia complex is generated, copper ions are quickly released from the hydrogel, and the gel structure is disintegrated. The gel structure was stable in low concentration ammonia solution (10 mM).
Selecting gram-negative bacteria proteus mirabilis and gram-positive bacteria staphylococcus epidermidis as test strains, carrying out an antibacterial experiment and counting, and simultaneously carrying out antibacterial performance characterization by adopting a scanning electron microscope.
The results of Proteus mirabilis show that the counting results of the bacteria on the surfaces modified by silicon rubber, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 4.5 multiplied by 10 7 2.3 x 10 7 Sum of 0.18X 10 7 And (4) respectively. The situation of bacteria adsorption for 4 hours is shown in a scanning electron micrograph of figure 4, so that the bacteria adsorbed by alginic acid-zwitterion-copper ions are the least, and the coating is proved to have a good antibacterial effect on proteus mirabilis.
The result of staphylococcus epidermidis shows that the counting results of the bacteria on the surfaces modified by silicon rubber, alginic acid-copper ions and alginic acid-zwitterion-copper ions after being adsorbed for 4 hours are respectively 2.2 multiplied by 10 7 0.8 x 10 7 Sum of 0.4X 10 6 And (4) respectively. The situation of bacteria adsorption for 4 hours is shown in a scanning electron microscope picture of figure 4, so that the bacteria adsorbed by alginic acid-zwitterion-copper ions are the least, and the coating is proved to have a good antibacterial effect, so that the coating has a good antibacterial effect on staphylococcus epidermidis.
Example 2
The experimental procedure is the same as in example 1, except that
The volume concentration of alginic acid in the step (1) is 5% (v/v), and the zwitterionic monomer is a sulfonate betaine type zwitterionic monomer;
copper nitrate is adopted in the step (2), and the concentration of copper ions is 1 mmol/L;
in the step (3), the mass concentration of the copolymer of alginic acid and the sulfonate betaine type zwitterion is 1%;
in the step (4), the substrate material is a titanium sheet, and the titanium sheet is soaked in the copper ion solution for 3 min;
the soaking time in the step (5) is 5 min.
The results of Proteus mirabilis show that the counting results of bacteria on the surfaces of titanium sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 6.3 multiplied by 10 7 4.5 x 10 7 Sum of 1.4X 10 7 And (4) respectively.
The result of staphylococcus epidermidis shows that the counting results of bacteria on the surfaces of titanium sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 4.3 multiplied by 10 7 2.2 x 10 7 Sum of 3.6X 10 6 And (4) respectively.
Example 3
The procedure is as in example 1 except that
The volume concentration of alginic acid in the step (1) is 1% (v/v), and the zwitterionic monomer is phosphate betaine type zwitterionic monomer;
copper chloride is adopted in the step (2), and the concentration of copper ions is 3 mmol/L;
in the step (3), the mass concentration of the copolymer of alginic acid and the sulfonate betaine type zwitterion is 2%;
in the step (4), the substrate material is a stainless steel sheet, and the stainless steel sheet is soaked in the copper ion solution for 5 min;
the soaking time in the step (5) is 10 min.
The results of Proteus mirabilis show that the counting results of the bacteria on the surfaces of the stainless steel sheet, the alginic acid-copper ion and the alginic acid-zwitterion-copper ion after being adsorbed for 4 hours are respectively 8.5 multiplied by 10 7 5.2X 10 pieces of 7 2.1 × 10 7 And (4) respectively.
The results of staphylococcus epidermidis show that the counting results of bacteria on the surfaces of the stainless steel sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 5.1 multiplied by 10 7 1.9 x 10 7 Sum of 1.6X 10 6 And (4) respectively.
Example 4
The procedure is as in example 1 except that
Copper acetate is adopted in the step (2), and the concentration of copper ions is 4 mmol/L;
in the step (3), the mass concentration of the copolymer of alginic acid and carboxylate betaine type zwitterion is 3%;
soaking the silicon rubber in the copper ion solution for 10min in the step (4);
the soaking time in the step (5) is 15 min.
The results of Proteus mirabilis show that the counting results of the bacteria on the surfaces modified by silicon rubber, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 4.5 multiplied by 10 7 3.2 x 10 7 Sum of 0.83X 10 7 And (4) respectively.
The results of staphylococcus epidermidis show that the counting results of the bacteria on the surfaces modified by silicon rubber, alginic acid-copper ions and alginic acid-zwitterion-copper ions after being adsorbed for 4 hours are respectively 2.2 multiplied by 10 7 1.3 x 10 7 Sum of 1.6X 10 6 And (4) respectively.
Example 5
The experimental procedure is the same as in example 2, except that
The concentration of copper ions in the step (2) is 5 mmol/L;
in the step (3), the mass concentration of the copolymer of alginic acid and the sulfonate betaine type zwitterion is 5%;
in the step (4), the substrate material is a titanium sheet, and the titanium sheet is soaked in the copper ion solution for 20 min;
the soaking time in the step (5) is 25 min.
The results of Proteus mirabilis show that the counting results of bacteria on the surfaces of titanium sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 6.3 multiplied by 10 7 2.5 x 10 7 0.6 sum10 7 And (4) respectively.
The result of staphylococcus epidermidis shows that the counting results of bacteria on the surfaces of titanium sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 4.3 multiplied by 10 7 1.6X 10 7 Sum of 1.3X 10 6 And (4) respectively.
Example 6
The experimental procedure is as in example 3, except that
The concentration of copper ions in the step (2) is 2 mmol/L;
in the step (3), the mass concentration of the copolymer of alginic acid and the sulfonate betaine type zwitterion is 6%;
in the step (4), the substrate material is a stainless steel sheet, and the stainless steel sheet is soaked in the copper ion solution for 25 min;
the soaking time in the step (5) is 30 min.
The results of Proteus mirabilis show that the counting results of the bacteria on the surfaces of the stainless steel sheet, the alginic acid-copper ion and the alginic acid-zwitterion-copper ion after being adsorbed for 4 hours are respectively 8.5 multiplied by 10 7 4.8 x 10 7 Sum of 1.8X 10 7 And (4) respectively.
The results of staphylococcus epidermidis show that the counting results of bacteria on the surfaces of the stainless steel sheets, alginic acid-copper ions and alginic acid-zwitterions-copper ions after being adsorbed for 4 hours are respectively 5.1 multiplied by 10 7 2.3 x 10 7 Sum of 1.6X 10 6 And (4) respectively.
Comparative example 1
Experimental procedure copper example 1, with the exception that
In the step (1), no carboxylate betaine type zwitterionic monomer is added.
The alginic acid-copper ions finally obtained are subjected to the absorption experiments of the proteus mirabilis and the staphylococcus epidermidis, and the counting results after 4 hours of absorption are respectively 2.3 multiplied by 10 7 Sum of 0.8X 10 7 The technical results obtained for example 1, comparative example 1, blank sample (silicone rubber) are shown in fig. 3.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (7)
1. An antibacterial material, which is characterized by comprising a substrate, alginic acid and a complex compound of a zwitterionic copolymer and copper ions;
the preparation method of the antibacterial material comprises the following steps:
(1) alginic acid was dissolved in 1-5% v/v in water, the solution was heated to 60 ℃ and maintained at this temperature during the reaction, then the initiator ammonium persulfate or potassium persulfate was added, the reaction system was previously kept in an oxygen-free environment by argon or nitrogen degassing, argon or nitrogen was bubbled into the mixture for a further 30min, then an aqueous zwitterionic monomer solution was gradually added to the mixture over a period of 30min using a syringe, wherein the molar ratio of zwitterionic monomer to alginic acid units was 1: 1, reacting for 6 hours, dialyzing for three days by using a cellulose membrane after reaction, and collecting a product after freeze-drying;
(2) obtaining an aqueous solution containing copper ions;
(3) immersing the substrate in an aqueous solution containing copper ions to obtain a substrate with the surface coated by the aqueous solution containing copper ions;
(4) and soaking the substrate with the surface coated by the aqueous solution of copper ions in the aqueous solution of alginic acid-zwitter ion copolymer for reaction to obtain the antibacterial material.
2. The antimicrobial material of claim 1, wherein the complex of alginic acid and the zwitterionic copolymer with copper ions has a copper ion content of 1-20 μ g/cm 2 。
3. The antibacterial material according to claim 1, wherein in the complex of alginic acid and the zwitterionic copolymer with copper ions, the zwitterion thereof is at least one selected from the group consisting of carboxylate betaine zwitterion, sulfonate betaine zwitterion and phosphate betaine zwitterion.
4. The antimicrobial material of claim 1, wherein the substrate is selected from at least one of a metal substrate and a polymeric substrate.
5. The antibacterial material according to claim 1, wherein in the step (1), the mass concentration of the solution of alginic acid and the zwitterionic copolymer is 1-8%.
6. The antibacterial material according to claim 1, wherein in the aqueous solution of copper ions in the step (2), the molar concentration of the copper ions is 1 to 7 mmol/L;
the copper ions are at least one of copper chloride solution, copper sulfate solution, copper nitrate solution and copper acetate solution.
7. The antibacterial material according to claim 1, wherein the immersion time in step (3) is 3 to 45min, and the immersion time in step (4) is 5 to 40 min.
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