CN116836605B - Antibacterial and antifouling self-healing material, coating and preparation method thereof - Google Patents
Antibacterial and antifouling self-healing material, coating and preparation method thereof Download PDFInfo
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- CN116836605B CN116836605B CN202311014432.3A CN202311014432A CN116836605B CN 116836605 B CN116836605 B CN 116836605B CN 202311014432 A CN202311014432 A CN 202311014432A CN 116836605 B CN116836605 B CN 116836605B
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- antibacterial
- triclosan
- methyl
- trimethylamine
- oxide
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 56
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- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 claims abstract description 87
- NLYDHBBTVWMLFD-UHFFFAOYSA-N 2,4-dichloro-1-(4-chloro-2-methoxyphenoxy)benzene Chemical group COC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl NLYDHBBTVWMLFD-UHFFFAOYSA-N 0.000 claims abstract description 29
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
An antibacterial and antifouling self-healing material, a coating and a preparation method thereof are provided, the material is prepared from triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidine-2-yl) urea) ethyl methacrylate through free radical polymerization, wherein the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16, and the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidine-2-yl) urea) ethyl methacrylate is 10-40% of the sum of the mass of the triclosan methyl acrylate and the trimethylamine N-oxide. According to the invention, the random polymer PTTU is obtained by free radical polymerization of TCSA, TMAO, UPyMA monomers according to a certain proportion, so that the interaction between PTTU and cell membranes is improved, and further the antibacterial and antifouling properties of the material are remarkably improved, meanwhile, UPyMA not only enhances the interface binding force with a substrate, but also greatly improves the self-healing capacity of the material in an oral environment, thereby achieving the purpose of long-acting antifouling and preventing related oral diseases caused by bacterial infection.
Description
Technical Field
The invention relates to the field of oral high polymer materials, in particular to an antibacterial and antifouling self-healing material, a coating manufactured based on the material and a preparation method of the material.
Background
The dental deformity is one of three oral diseases, which not only affects the facial beauty of patients, but also affects the oral health and functions. With the improvement of oral health consciousness of people, the improvement of facial morphology of the jaw bone of a patient by adjusting the position and the direction of teeth through orthodontic treatment means such as stainless steel, ceramics, invisible tooth sockets and the like becomes a choice. However, biofouling such as bacteria and food residues is easily accumulated on the surface of materials used in the conventional orthodontic treatment means, and if the biofouling cannot be removed in time, plaque stagnation points are generated, so that the composition and quantity of bacteria are rapidly increased and develop to form a biofilm, and bacterial infectious oral diseases such as dental caries are induced.
In order to inhibit the formation and development of biofilms, the prior art has mainly inhibited the adhesion and proliferation of bacteria on the surface of dental appliances by physically coating or chemically grafting antibacterial agents and hydrophilic materials such as PEG (polyethylene glycol), zwitterionic and the like on the surface of the appliance. However, PEG is susceptible to autoxidation to form aldehydes or ethers in the presence of oxygen and metals, thereby losing the anti-protein adhesion function; when the conventional zwitterions such as carboxylic acid betaine, sulfobetaine and phosphorylcholine are applied to physiological environments, as body fluid contains a large amount of salt ions and various biomolecules, the conventional zwitterions have a charge shielding effect on the zwitterions, so that the hydration capacity of the zwitter-ions is reduced, and the anti-fouling performance of the zwitter-ions is reduced. In addition, the antibacterial and antifouling material inevitably generates damage or defects in the use process so as to influence the functions of the material, and the exogenous self-repair has the defects of limited repair times, difficulty in realizing function recovery and the like, so that the conventional antibacterial and antifouling material has short service life and is difficult to play a long-acting antifouling role.
Disclosure of Invention
An object of the present invention is to provide an antibacterial and anti-fouling self-healing material PTTU, which is formed by polymerizing three monomers of triclosan methyl acrylate (TCSA), trimethylamine N-oxide (TMAO) and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate (UPyMA) according to a certain proportion by free radicals, wherein an amphiphilic structure is formed by hydrophobic benzene rings and hydrophilic zwitterionic groups in molecular chains, so that interaction with cell membranes is improved, and thus antibacterial and anti-fouling properties of the material are remarkably improved, and at the same time, UPyMA serving as a multiple hydrogen bond donor not only enhances interface binding force with a substrate, but also greatly improves self-healing capability of the material in an oral environment, achieves a long-acting anti-fouling purpose, and prevents oral diseases related to bacterial infection.
The invention aims at realizing the following technical scheme:
An antibacterial and antifouling self-healing material is prepared from triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate through free radical polymerization, wherein the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16, and the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10-40% of the sum of the mass of the triclosan methyl acrylate and the mass of the trimethylamine N-oxide.
In the technical scheme, the raw materials of the antibacterial antifouling self-healing material comprise three monomers: triclosan methyl acrylate (TCSA), trimethylamine N-oxide (TMAO) and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate (UPyMA).
In the technical scheme, TMAO is different from the traditional zwitterion, and has more excellent hydration performance and pollution resistance and lower immunogenicity than PEG because of the very close distance between positive and negative charges; meanwhile, the dipolar effect of TMAO molecules is smaller, methyl exists around N +, only part of O - is exposed in the solution, the group distance between O - and N + is short, N + and other ions such as Na + have strong repulsive interaction, and damage caused by ions in salt solution is resisted, so that the anti-fouling agent has excellent anti-fouling capability in physiological environment.
In the technical scheme, UPyMA has quadruple hydrogen bonds, and based on interaction of multiple hydrogen bonds and ionic bonds, the interface binding force of the material and the corrector substrate is enhanced, and the antifouling coating can be quickly repaired at the temperature and humidity of the oral cavity, so that the aim of long-acting antifouling is fulfilled.
In the technical scheme, three monomers are subjected to free radical reaction according to a certain proportion, so that the antibacterial antifouling self-healing material obtained by random copolymerization well combines the advantages of the three monomers.
Specifically, TMAO is a hydrophilic salt-tolerant zwitterionic that forms an amphiphilic polymer structure upon combination with the hydrophobic antimicrobial TSCA. The amphiphilic polymer structure has hydrophobic benzene ring and hydrophilic zwitterionic groups, so that the amphiphilic polymer structure can be beneficial to interaction with cell membranes of bacteria, and further the antifouling performance of the surface of the material is remarkably improved. Further, experiments show that as the mass ratio of TMAO to TSCA of the prepared antibacterial and antifouling self-healing material is increased, the surface water contact angle of the material is gradually reduced, the hydrophilicity is enhanced, so that bacteria are not easy to adhere to the surface by utilizing hydration, the antifouling performance is improved, and meanwhile, the Minimum Inhibitory Concentration (MIC) and the Minimum Bactericidal Concentration (MBC) of the material show a change trend of decreasing first and then increasing. Therefore, the surface water contact angle, the minimum antibacterial concentration and the minimum antibacterial concentration of the material are comprehensively considered, and in the technical scheme, the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16.
The amphiphilic polymer structure formed by TMAO and TSCA has limited self-healing capacity, and the addition of UPyMA does not influence the antibacterial and antifouling capacity of the amphiphilic polymer structure in the material, and the self-healing capacity of the material can be greatly improved by utilizing the characteristic of multiple hydrogen bonds, so that the material can realize long-acting antifouling and sterilization. The self-healing ability of the material is positively correlated to the UPyMA content within a certain range, but when the UPyMA content is too high, the large number of hydrogen bonds in the material will make it difficult to separate and purify the polymer. Therefore, in the technical scheme, the mass of UPyMA in the raw materials is 10-40% of the sum of the masses of TMAO and TSCA.
Further, the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 4-12. In the technical scheme, when the mass ratio of TMAO to TSCA is 4-12, the surface water contact angle of the material is 18.94-43.45 degrees, the MIC is kept at 31.25 mug/mL, and the MBC is 31.25-62.5 mug/mL, so that a better antibacterial and antifouling level is achieved. In a partially preferred embodiment, the material has a mass ratio of TMAO to TSCA of 8 to 12, and more preferably a mass ratio of 12, and the material has a surface water contact angle of 18.94 DEG, and a MIC of 31.25 μg/mL and a MBC of 62.5 μg/mL, as measured, to better balance the antimicrobial and anti-fouling capabilities.
Further, the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10 to 20 percent of the sum of the mass of the triclosan methyl acrylate and the mass of the trimethylamine N-oxide. In some embodiments, UPyMA is present in an amount of 10-15% of the sum of the masses of TMAO and TSCA, and more preferably UPyMA is present in an amount of 10% of the sum of the masses of TMAO and TSCA.
The invention also provides a preparation method for preparing any antibacterial antifouling self-healing material, and the preparation method has the advantages of easily available raw materials and mild reaction conditions, and is beneficial to expanding production.
The preparation method of the antibacterial antifouling self-healing material specifically comprises the following steps:
Carrying out free radical polymerization reaction on triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidine-2-yl) urea) ethyl methacrylate to obtain the antibacterial and antifouling self-healing material;
Wherein the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16, and the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10-40% of the sum of the mass of the triclosan methyl acrylate and the mass of the trimethylamine N-oxide.
In one or more embodiments, the reaction is terminated after a few hours of radical polymerization of the three monomers by adding para-hydroxyanisole (MEHQ).
Further, the preparation of the triclosan methyl acrylate comprises the following steps: and adding an acid binding agent after triclosan is dissolved, and then slowly adding acryloyl chloride at a low temperature for esterification reaction to obtain the triclosan methyl acrylate. In the technical scheme, in the synthesis step of TCSA, triclosan (TCS) is dissolved and then added with an acid binding agent such as triethylamine, and then slowly added with acryloyl chloride at a low temperature for reaction for a plurality of hours. In one or more embodiments, the reaction temperature at which the acryloyl chloride is added is from 0 to 50. After the reaction is completed at the temperature, the yellow viscous liquid obtained through rotary evaporation, extraction and drying is TCSA. The synthetic route of TCSA is:
Further, the preparation of the trimethylamine N-oxide comprises the following steps: and (3) after the diethylenetriamine pentaacetic acid and the ultrapure water are fully and uniformly mixed, adding hydrogen peroxide and introducing oxygen, and then adding dimethylaminopropyl acrylamide into a reaction system for oxidation reaction to obtain the trimethylamine N-oxide. In some examples, in the synthetic step of TMAO, after diethylenetriamine pentaacetic acid (DTPA) and ultrapure water are mixed, stirring is vigorously performed until white powder is completely dissolved, then hydrogen peroxide is heated and added, oxygen is introduced, then dimethylaminopropyl acrylamide solution is slowly added into a reaction system, after the reaction is finished, water phase is extracted and collected, and the solution is repeatedly dissolved by absolute methanol and distilled under reduced pressure to obtain an oily brown product TMAO. The synthetic route of TMAO is:
Further, the preparation of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate comprises the following steps: dissolving 2-amino-4-hydroxy-6-methyl pyrimidine, adding isocyanoethyl methacrylate, rapidly cooling and continuously stirring to obtain 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate.
In the technical scheme, isocyanoethyl methacrylate is added after 2-amino-4-hydroxy-6-methylpyrimidine is fully dissolved. In one or more embodiments, the isocyanatoethyl methacrylate is added followed by vigorous stirring for 30 seconds, after which the mixture is rapidly placed in a water bath at 0℃and cooled and stirred continuously to gradually precipitate a white solid in order to prevent self-polymerization of the monomers. Subsequently, the white solid was dried after repeated centrifugal washing with acetone to obtain UPyMA. UPyMA the synthetic route is:
Further, after methyl triclosan acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate are mixed, azobisisobutyronitrile and 1, 4-butanediol diacrylate are added to the reaction system. In the technical scheme, the azo diisobutyl cyanide (AIBN) is taken as an initiator, and the 1, 4-butanediol diacrylate (BDDA) is taken as a cross-linking agent and added into a reaction system, so that the free radical reaction is facilitated.
Further, the reaction temperature is 60-90 ℃. Preferably, the reaction temperature is 70 to 80 ℃.
The invention also provides an antibacterial and antifouling self-healing coating based on any one of the antibacterial and antifouling self-healing materials, and particularly the coating is prepared by dissolving a certain concentration of antibacterial and antifouling self-healing material PTTU and then spin-coating by a spin-coating instrument.
In one or more embodiments, the spin-on concentration of PTTU is 10mg/mL. In some embodiments, the spin coating speed is 3000r/min, and the antibacterial antifouling self-healing coating is obtained after drying.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. According to the invention, the random polymer PTTU is obtained by free radical polymerization of TCSA, TMAO, UPyMA monomers according to a certain proportion, so that the interaction between PTTU and cell membranes is improved, and further the antibacterial and antifouling properties of the material are remarkably improved, meanwhile, UPyMA not only enhances the interface binding force with a substrate, but also greatly improves the self-healing capacity of the material in an oral environment, thereby achieving the purpose of long-acting antifouling and preventing related oral diseases caused by bacterial infection;
2. The PTTU prepared by the method can form a stable coating on the surface of the dental material through simple spin coating, so that the surface of the dental material is effectively modified, the operation is simple and convenient, and the long-acting antibacterial and antifouling capabilities of the dental material are obviously improved;
3. According to the invention, three monomers are effectively combined, the hydrophilia of PTTU is improved by utilizing an amphiphilic structure, the anti-fouling performance is improved by utilizing hydration, lower MIC and MBC are obtained, meanwhile, the added UPyMA can not influence the antibacterial and anti-fouling capabilities of amphiphilic high molecular structures in the material, and the self-healing capability of the material can be greatly improved by utilizing the characteristics of multiple hydrogen bonds, so that the material can realize long-acting anti-fouling and sterilization;
4. the preparation method has the advantages of easily available raw materials and mild reaction conditions, and is beneficial to the amplified production of PTTU materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a block flow diagram of a method for preparing an antimicrobial and anti-fouling self-healing material in accordance with an embodiment of the present invention;
FIG. 2 shows nuclear magnetic resonance and infrared spectra (FIG. d) of TCSA (FIG. a), TAMO (FIG. b), UPyMA (FIG. c) prepared according to an embodiment of the present invention;
FIG. 3 shows nuclear magnetic resonance and infrared spectra of PTTU prepared in an embodiment of the present invention;
FIG. 4 shows a surface SEM and AFM of PTTU coatings in accordance with an embodiment of the present invention;
FIG. 5 illustrates the anti-fouling ability of PTTU coatings to various bacteria in an embodiment of the present invention;
FIG. 6 illustrates interfacial bonding force and self-healing capacity of PTTU coatings in an embodiment of the present invention;
Figure 7 shows in vitro cytotoxicity of various coatings on HOK cells in an embodiment of the invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
All the raw materials of the present invention are not particularly limited in their sources, and can be commercially available or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytical purity or purity requirements conventional in the oral polymer field.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The expression of the substituents is not particularly limited in the present invention, and all of them are well known to those skilled in the art, and those skilled in the art can correctly understand the meaning based on the general knowledge.
Preparation of TCSA
6Mmol (1.74 g) of TCS was dissolved in 15mL of anhydrous DCM, 18mmol of triethylamine as an acid-binding agent (2.5 mL) was added dropwise at 0deg.C and 18mmol (1.44 mL) of acryloyl chloride was reacted for 30min, and the reaction was detected by thin layer chromatography on a silica gel plate. After 6h at room temperature, the reaction was stopped, and the crude product was distilled off under reduced pressure, extracted with a large amount of DCM, and dried over anhydrous Na 2SO4. The yellow viscous liquid obtained after the re-decompression rotary evaporation is stored in a refrigerator at the temperature of minus 20 ℃ for standby.
The nuclear magnetic and infrared spectra of TCSA are shown in figure 2.
[ Example 2] preparation of TMAO
80Mg of diethylenetriamine pentaacetic acid (DTPA) and 30mL of ultra pure water were added to the round bottom flask and vigorously stirred for 2 hours until the white powder was completely dissolved. After heating the oil bath to 60 ℃, 3.4mLH 2O2 (30%) was added and oxygen was vented. Subsequently, dimethylaminopropyl acrylamide (14.4 g) was dissolved in 10mL of ultrapure water and slowly dropped into a round-bottomed flask through a constant pressure funnel, and reacted at 60℃for 6 hours. The reaction product was extracted several times with DCM and the aqueous phase was collected, finally repeated with a large amount of anhydrous methanol and rotary distilled under reduced pressure to give the oily tan product TMAO which was stored in a-20 ℃ refrigerator for further use.
The nuclear magnetic and infrared spectra of TMAO are shown in FIG. 2.
Preparation of UPyMA [ example 3 ]
32Mmol (4.0 g) of 2-amino-4-hydroxy-6-methylpyrimidine was dissolved in 50mL of anhydrous DMSO, heated in an oil bath at 170℃for 10min to dissolve the solid completely, and the oil bath was removed. 35.2mmol (1.1 eq,5.5 g) of isocyanatoethyl methacrylate (ICEMA) are added immediately and stirred vigorously for 30 seconds, after which the mixture is rapidly placed in a water bath at 0℃and cooled and stirred continuously, a white solid gradually precipitates. The white solid was repeatedly washed by centrifugation with acetone three times (8000 r/min), dried under vacuum at 40℃and ground with a mortar and stored in a-20℃refrigerator for use.
The nuclear magnetic and infrared spectra of UPyMA are shown in figure 2.
PTTU preparation
[ Example 4]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 5mmol, TCSA was 2.5mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-1.
PTTU-1, the mass ratio of TMAO to TCSA is 1:1.
[ Example 5]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 6mmol, TCSA was 1.5mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-2.
PTTU-2, the mass ratio of TMAO to TCSA is 2:1.
[ Example 6]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 6.67mmol, TCSA was 0.83mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-3.
PTTU-3, the mass ratio of TMAO to TCSA is 4:1.
[ Example 7]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.05mmol, TCSA was 0.45mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-4.
PTTU-4, the mass ratio of TMAO to TCSA is 8:1.
[ Example 8]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.2mmol, TCSA was 0.3mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-5.
PTTU-5, the mass ratio of TMAO to TCSA is 12:1.
The nuclear magnetic and infrared spectra of PTTU-5 are shown in FIG. 3, wherein PTT 12:1 is a polymer containing only TMAO and TCSA in a mass ratio of 12:1, and PTTU-10% is PTTU-5.
[ Example 9]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.27mmol, TCSA was 0.23mmol, and UPyMA was 10% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-6.
PTTU-6, TMAO and TCSA in a mass ratio of 16:1
[ Example 10]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.2mmol, TCSA was 0.3mmol, and UPyMA was 20% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-7.
PTTU-7, the mass ratio of TMAO to TCSA is 12:1.
[ Example 11]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.2mmol, TCSA was 0.3mmol, and UPyMA was 30% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-8.
PTTU-8, the mass ratio of TMAO to TCSA is 12:1.
[ Example 12]
TCSA, TMAO and UPyMA prepared in examples 1-3 were mixed and dissolved in DMSO, wherein TMAO was 7.2mmol, TCSA was 0.3mmol, and UPyMA was 40% of the sum of TMAO and TCSA. Adding AIBN and BDDA to perform free radical polymerization at 70 ℃ for 24 hours, adding 100mg of MEHQ to terminate the reaction, cooling to room temperature at normal temperature, precipitating in glacial diethyl ether, dissolving with chloroform, repeating the precipitation and dissolving for three times to remove unreacted UPyMA monomers, and finally dialyzing in ultrapure water for 3 days to obtain PTTU-9.
PTTU-9, the mass ratio of TMAO to TCSA is 12:1.
PTTU Performance test
Example 13 antibacterial Property test
Comparative examples PTMAO, PTCSA, and PTTU-1 to PTTU-6 were formulated into BHI (brain heart infusion medium) solutions containing 5% DMSO, wherein PTMAO was a homopolymer of TMAO and PTCSA was a homopolymer of TCSA, and further sequentially diluted with BHI medium to prepare 100. Mu. Monomer/polymer solutions at a concentration, followed by addition of 100. Mu.L of S.mutans suspension (10 6 CFU/mL) and incubation in anaerobic conditions at 37℃for 24h. Since the monomers and polymers were turbid and had a certain absorbance after mixing with BHI medium, 5% DMSO-BHI solution without bacteria was added as a control, and the sterilization rate (B%) was calculated according to the following formula, in order to calculate their antibacterial rate more precisely:
Wherein ODcontrol, ODtest, ODblank and ODdb are OD values of 24h of incubation under anaerobic conditions for bacterial group, experimental group, blank medium group, 5% dmso-BHI material group, respectively.
The results of the experiments are shown in Table 1,
TABLE 1
| Test sample | Surface water contact angle (°) | MIC(μg/mL) | MBC(μg/mL) |
| PTMAO | 11.2 | ＞500 | ＞500 |
| PTCSA | 96.17 | ＞500 | ＞500 |
| PTTU-1 | 71.51 | 62.5 | 62.5 |
| PTTU-2 | 56.73 | 31.25 | 31.25 |
| PTTU-3 | 43.45 | 31.25 | 31.25 |
| PTTU-4 | 31.82 | 31.25 | 31.25 |
| PTTU-5 | 18.94 | 31.25 | 62.5 |
| PTTU-6 | 12.21 | 62.5 | 62.5 |
As shown in Table 1, PTMAO contained positively charged quaternary ammonium ions, but the overall antibacterial effect was not apparent after interaction with oxyanions. The antibacterial effect of PTCSA obtained by free radical polymerization is also insignificant, probably because the hydrophobic effect of the whole PTCSA chain is too strong, the steric hindrance is too great and the interaction with bacteria is reduced. The PTTU-1 to PTTU-6 designed by the invention has an amphiphilic structure because the molecular chain of the amphiprotic ionic compound contains a hydrophobic benzene ring and a hydrophilic zwitterionic group, and the amphiphilic structure is favorable for the interaction with bacterial cell membranes, so that the antibacterial performance of the amphiphilic compound is remarkably improved. In addition, as PTMAO content increases, the antibacterial effect of PTTU is firstly enhanced and then weakened, the change trend is small, and after PTTU is prepared into a corresponding functional coating, the hydrophilicity of the functional coating increases along with PTMAO content.
[ Example 14 ] PTTU surface topography and roughness of the coating
PTTU-5 prepared in example 8 was dissolved in DMSO to prepare a 10mg/mL polymer solution, and a PTTU coating was prepared on Si sheets using a spin coater at 3000r/min at room temperature. The surface morphology and roughness were examined by field emission scanning electron microscopy and atomic force microscopy.
The experimental results are shown in fig. 4, and the surface of the coating is smooth and uniform after the coating is coated with PTTU coating, and the surface morphology and roughness of the substrate are not changed, so that the PTTU coating is beneficial to maintaining the surface properties of the substrate with special morphology.
Antimicrobial and antifouling Properties of the PTTU coating
To more intuitively show the anti-protein adhesion ability of the surface, 2mg/mL FITC-labeled BSA and LZ were incubated with two sets of Ti plates for 2h under the same conditions, and after gently washing 3 times with PBS, the protein adhesion amount of the surface was observed with CLSM.
Similarly, all Ti sheets were immersed in BHI medium containing S.mutans (10 6 CFU/mL) for 12h, the bacterial suspension was aspirated, washed 3 times with PBS, stained with LIVE/DEAD BacLight KIT REAGENT at room temperature in the absence of light for 15min, gently washed 3 times and then observed with a laser confocal microscope.
The experimental results are shown in fig. 5, and the PTTU-5 coating surface has less protein and bacteria adhesion than the blank Ti sheet due to the excellent anti-fouling properties of PTTU coating. Because of the difference in charged and molecular weight of BSA and LZ, more LZ adheres to the surface of the blank Ti sheet.
[ Example 16 ] PTTU interface binding force and self-healing Performance test
Interfacial adhesion performance of PTTU was evaluated according to ASTM D1002 test standard. Briefly, 10mg/mL PTTU-5 solution was formulated and then coated over a 2.5X2.5 cm area of the front end of a Ti sheet as shown in FIG. 6a, and another equally sized area of the front end of the Ti sheet was overlaid over PTTU-5 coated Ti sheet. And carrying out lap shear adhesion test on the cured plate on a universal tensile machine, wherein the stretching speed is 2mm/min. All lap shear adhesion tests were performed at room temperature and each sample was measured 3 times in duplicate to reduce experimental error. As shown in FIG. 6b, the interfacial bonding strength of the PTTU-5 polymer was improved by about three times with respect to the bonding force (36.77 KPa) of PTMAO to the Ti sheet, the shear stress 102.84KPa of the PTTU-5 polymer to the Ti sheet. This result demonstrates that PTTU-10% has good adhesion to titanium metal substrates.
To investigate the self-healing properties of PTTU polymer coatings in the oral environment, the surface crack healing was observed with an optical microscope by scoring the crack on the surface of PTTU-5 polymer coating with a knife, placing it in a 37 ℃ water bath environment immersed in simulated saliva containing alpha-amylase (300 μg/mL) and lysozyme (20 μg/mL), simulating the oral environment. Before and after self-healing, PTTU-5 coatings were immersed in FITC-BSA solution (1 mg/mL) for 30min and their surface anti-fouling ability was observed with a fluorescence microscope.
The experimental results are shown in fig. 6c, wherein the first three graphs are the initial, crack and healing graphs of the coating observed by an optical microscope, and the second three graphs are the initial, crack and healing graphs of the coating observed by a fluorescence microscope. It can be seen that the original coating has good protein adhesion resistance, and the cracks destroy the surface structure of the coating, increase the surface roughness, reduce the hydrophilicity, and adsorb a large amount of protein. Almost no attached protein was found on the repaired coating. The above results indicate that the anti-fouling properties of PTTU-5 coatings in the oral environment are restored.
Example 17 in vitro cytotoxicity test
This example tested the experimental method for in vitro cytotoxicity of blank Ti flakes, PTMAO, PTCSA, PTT 12:1 and PTTU-5 polymer coatings, as follows:
Cytotoxicity of the coating was measured using oral keratinocytes (HOK), 2×10 5 HOK cells were seeded in 48-well plates, and after incubation in a carbon dioxide incubator for 24 hours and co-incubation of sterilized dental plaque with cells was continued for 24 hours (fig. 7 a) and 72 hours (fig. 7 b), respectively, their OD values at 450nm were measured with a microplate reader and their Cell activities (Cell activities) were calculated as follows:
Wherein ODcontrol, ODtest, ODblank is the OD value of the control, experimental and blank medium, respectively. The results of the experiment are shown in FIG. 7, wherein PTTU-5 coatings exhibited similar cellular activity compared to the control group, with substantially no cytotoxicity.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. An antibacterial and antifouling self-healing material is characterized in that the antibacterial and antifouling self-healing material is prepared from triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate through free radical polymerization, wherein the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16, and the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10-40% of the sum of the mass of the triclosan methyl acrylate and the trimethylamine N-oxide;
Wherein, the structural formula of triclosan methyl acrylate is:
the trimethylamine N-oxide has the structural formula:
the structural formula of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is as follows:
2. The antibacterial and antifouling self-healing material according to claim 1, wherein the mass ratio of trimethylamine N-oxide to triclosan methyl acrylate is 4-12.
3. The antibacterial and antifouling self-healing material according to claim 1, wherein the mass of 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10 to 20% of the sum of the mass of triclosan methyl acrylate and trimethylamine N-oxide.
4. The method for preparing the antibacterial and antifouling self-healing material according to claim 1, comprising the following steps:
Carrying out free radical polymerization reaction on triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidine-2-yl) urea) ethyl methacrylate to obtain the antibacterial and antifouling self-healing material;
Wherein the mass ratio of the trimethylamine N-oxide to the triclosan methyl acrylate is 1-16, and the mass of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate is 10-40% of the sum of the mass of the triclosan methyl acrylate and the mass of the trimethylamine N-oxide;
Wherein, the preparation of the triclosan methyl acrylate comprises the following steps: dissolving triclosan, adding an acid binding agent, and slowly adding acrylic chloride at a low temperature to perform esterification reaction to obtain the triclosan methyl acrylate;
The preparation of the trimethylamine N-oxide comprises the following steps: after sufficiently and uniformly mixing diethylenetriamine pentaacetic acid and ultrapure water, adding hydrogen peroxide and introducing oxygen, and then adding dimethylaminopropyl acrylamide into a reaction system for oxidation reaction to obtain the trimethylamine N-oxide;
The preparation of the 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate comprises the following steps: dissolving 2-amino-4-hydroxy-6-methyl pyrimidine, adding isocyanoethyl methacrylate, rapidly cooling and continuously stirring to obtain 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate.
5. The method for preparing an antibacterial and antifouling self-healing material according to claim 4, wherein after mixing triclosan methyl acrylate, trimethylamine N-oxide and 2- (3- (6-methyl-4-oxo-1, 4-dihydropyrimidin-2-yl) urea) ethyl methacrylate, azodiisobutyronitrile and 1, 4-butanediol diacrylate are added into the reaction system to perform free radical reaction.
6. The method for producing an antibacterial and antifouling self-healing material according to claim 5, wherein the free radical reaction temperature is 60 to 90 ℃.
7. An antibacterial and antifouling self-healing coating, which is characterized by comprising the antibacterial and antifouling self-healing material according to any one of claims 1 to 3, wherein the antibacterial and antifouling self-healing material is obtained by spin coating and drying after being dissolved.
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| CN107519497A (en) * | 2016-06-21 | 2017-12-29 | 浙江大学 | Application of the polymer of the oxidation tertiary amine group containing N as medicine or carrier |
| CN110218519A (en) * | 2019-05-09 | 2019-09-10 | 华南理工大学 | A kind of static state anti-pollution self demixing organosilicon coating and the preparation method and application thereof |
| CN110964155A (en) * | 2019-12-19 | 2020-04-07 | 四川大学 | Zwitterionic hydrogel with high anti-fouling performance and preparation method and application thereof |
| CN113461855A (en) * | 2021-07-05 | 2021-10-01 | 四川大学 | PH-responsive anti-fouling modified material, modified invisible correcting material and preparation method |
| CN116333216A (en) * | 2023-03-07 | 2023-06-27 | 中南大学 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
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| CN107519497A (en) * | 2016-06-21 | 2017-12-29 | 浙江大学 | Application of the polymer of the oxidation tertiary amine group containing N as medicine or carrier |
| CN110218519A (en) * | 2019-05-09 | 2019-09-10 | 华南理工大学 | A kind of static state anti-pollution self demixing organosilicon coating and the preparation method and application thereof |
| CN110964155A (en) * | 2019-12-19 | 2020-04-07 | 四川大学 | Zwitterionic hydrogel with high anti-fouling performance and preparation method and application thereof |
| CN113461855A (en) * | 2021-07-05 | 2021-10-01 | 四川大学 | PH-responsive anti-fouling modified material, modified invisible correcting material and preparation method |
| CN116333216A (en) * | 2023-03-07 | 2023-06-27 | 中南大学 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
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