CN113461995B - Preparation method of polylactic acid material with anti-adhesion sterilization function - Google Patents

Preparation method of polylactic acid material with anti-adhesion sterilization function Download PDF

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CN113461995B
CN113461995B CN202110830495.0A CN202110830495A CN113461995B CN 113461995 B CN113461995 B CN 113461995B CN 202110830495 A CN202110830495 A CN 202110830495A CN 113461995 B CN113461995 B CN 113461995B
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polylactic acid
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adhesion
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CN113461995A (en
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王向红
王格格
陈金周
刘旭影
杨会歌
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Zhengzhou University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

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Abstract

The invention discloses a polylactic acid material with anti-adhesion and sterilization functions, which comprises the following steps: 1) stirring and dissolving biodegradable material polylactic acid in a good solvent, adding a poor solvent to realize phase separation, and fully stirring to obtain a coating solution; 2) uniformly coating the solution obtained in step 1 on a polylactic acid sheet, and drying; 3) stripping the top layer polylactic acid by using an adhesive tape to obtain a super-hydrophobic surface; 4) dispersing chlorophyll in anhydrous ethanol, coating onto the superhydrophobic surface of polylactic acid, and drying. The surface of the material has the super-hydrophobic property of resisting the initial adhesion of bacteria and can kill the adhered bacteria through photodynamic. The super-hydrophobic and photodynamic synergistic antibacterial mode has the advantages of less bactericide consumption, high sterilization efficiency, good antibacterial long-acting property and strong controllability, and can not induce bacteria to generate drug resistance. The polylactic acid material with the anti-adhesion and sterilization functions prepared by the method is non-toxic and harmless, has good biological and environmental compatibility, and can be used for resisting bacterial infection in medical or packaging materials.

Description

Preparation method of polylactic acid material with anti-adhesion and sterilization functions
Technical Field
The invention relates to the field of antibacterial infection, in particular to a preparation method of a polylactic acid material with an anti-adhesion sterilization function.
Background
The life health concerns the livelihood of the people and the harmony of the society, and the health needs of the people are rapidly increased in the global environment of the new crown epidemic situation. It is counted that nosocomial infections have become the sixth largest "killer". Medically related infections or nosocomial infections occur after a medical facility receives treatment, resulting in infections secondary to the original condition of the patient treated by the medical facility. Approximately 7% of patients in developed countries suffer nosocomial infections, with an infection rate in intensive care units of over 50% today. According to the centers for disease prevention and control, the average cost of treating nosocomial infections has exceeded $ 200, greatly increasing the cost of medical care. The problem of iatrogenic infection caused by pathogenic bacteria adhered to the surface of medical instruments or implants is endless in use, and the problem of iatrogenic infection caused by pathogenic bacteria adhered to the surface of medical instruments or implants becomes one of the biggest hidden dangers to the health of patients in the global scope, and seriously threatens the public health safety of society. Therefore, it is necessary to develop a biomedical material with high-efficiency anti-adhesion antibacterial property and sterilization property. In recent years, photodynamic antibacterial therapy has unique advantages in that it has high bactericidal activity and does not produce bacterial resistance. Photodynamic antibacterial therapy utilizes light to activate photosensitizers, which produce singlet oxygen to cause bacterial damage and even death. Singlet oxygen reacts with the bacterial cell wall phospholipid membranes, polypeptides and nucleic acids, resulting in bacterial inactivation. The singlet oxygen has strong oxidability, multi-site inactivation and no specific target, and does not generate bacterial drug resistance.
Antimicrobial strategies can be divided into both passive anti-bacterial adhesion and active sterilization. Passive anti-adhesion type surfaces are primarily intended to reduce or inhibit the chance of bacterial infection through strategies such as weakening the interaction between bacteria and the surface or interfering with biofilm formation, such as constructing superhydrophobic coatings that resist initial adhesion of bacteria, are more biocompatible, but once individual bacteria adhere to the surface, the anti-adhesion functional polymer does not prevent bacterial proliferation and infection development. The active sterilization type surface usually utilizes a physical or chemical method to fix an antibacterial agent, such as quaternary ammonium salt, antibiotics, chitosan, silver ions and the like, on the surface of a substrate material, and performs a sterilization function through an action mode of release or contact and the like; the antibacterial agent has high sterilization efficiency, but quaternary ammonium salt, antibacterial peptide, metal ions and the like have certain cytotoxicity, and can gradually cover sterilization groups along with accumulation of dead bacteria, so that the sterilization efficiency is influenced, and most of the antibacterial agents can cause environmental pollution and generate serious antibiotic resistance and high cytotoxicity. In recent years, an antibacterial adhesion-sterilization synergistic function surface construction strategy is continuously developed, and by combining two methods of stain resistance and sterilization, the bacterial adhesion quantity can be reduced, bacteria can be effectively killed, the infection risk can be greatly reduced, and the biocompatibility is better.
Polylactic acid (PLA) is considered to be one of the most promising materials for solving environmental and energy problems at present due to its excellent biocompatibility and biodegradability, and has a good application prospect in food packaging and biomedicine. However, PLA has no bactericidal properties by itself and cannot meet its needs in food packaging and biomedical applications. Therefore, there is a need to develop an environmentally friendly PLA material having significant antibacterial properties and no drug resistance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of a polylactic acid material with an anti-adhesion sterilization function.
Based on the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polylactic acid material with an anti-adhesion sterilization function, comprising the following steps:
(1) dissolving polylactic acid into a good solvent to obtain a polylactic acid solution, and then adding a poor solvent into the polylactic acid solution to be uniformly mixed to obtain a coating solution;
(2) coating the coating solution obtained in the step (1) on a polylactic acid substrate, drying and stripping to obtain a super-hydrophobic surface;
(3) and (3) dissolving chlorophyll in ethanol to obtain a chlorophyll solution, coating the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
According to the preparation method, preferably, the concentration of the chlorophyll solution in the step (3) is 1-5 [ mu ] mol/L; more preferably, the concentration of the chlorophyll solution is 1. mu. mol/L.
According to the above preparation method, preferably, the chlorophyll is chlorophyll a.
According to the preparation method, preferably, the concentration of the polylactic acid solution in the step (1) is 1-5 wt%; more preferably, the polylactic acid solution has a concentration of 5 wt%.
According to the above production method, preferably, the volume ratio of the good solvent to the poor solvent of the coating solution in the step (1) is 1: (0.3-0.9).
According to the above preparation method, preferably, the good solvent in step (1) is dichloromethane or trichloromethane; the poor solvent is a mixed solution of any three of n-butanol, absolute ethyl alcohol, isopropanol, n-propanol, butyl acetate and ethyl acetate.
According to the preparation method, the poor solvent is preferably a mixed solution of absolute ethyl alcohol, n-butyl alcohol and butyl acetate, wherein the volume usage ratio of the absolute ethyl alcohol, the n-butyl alcohol and the butyl acetate is (1-1.5): 1-1.5); more preferably, the volume ratio of the absolute ethyl alcohol to the n-butyl alcohol to the butyl acetate is 1:1: 1.
According to the above preparation method, preferably, in the step (2), the drying specifically comprises the following steps: drying for 6-18 h at room temperature, and then drying for 40-60 h at the temperature of 30-60 ℃; more preferably, the drying is carried out first at room temperature for 12h and then at a temperature of 40 ℃ for 48 h.
According to the above preparation method, preferably, in the step (2), the coating is any one of dripping coating, dipping, spraying and spin coating; more preferably, the coating is performed by dropping.
According to the preparation method, preferably, the stripping in the step (2) adopts an adhesive tape sticking and pressing stripping process, the pressure is 3-20N, and the adhesive tape is a plastic-based adhesive tape; more preferably, the pressure is 10N and the tape is a biaxially oriented polypropylene-based or polyvinyl chloride tape.
According to the preparation method, preferably, in the step (2), the polylactic acid substrate is a polylactic acid sheet or plate with the thickness of 1-6 mm, and the polylactic acid sheet or plate is formed by injection molding, hot press molding or calendaring.
In a second aspect, the invention provides a polylactic acid material with an anti-adhesion sterilization function, which is prepared by the preparation method of the first aspect.
According to the polylactic acid material with the anti-adhesion sterilization function, preferably, the polylactic acid material is sterilized by using photodynamic light, the wavelength of the light is 600-700 nm, and the power is 8-12 w; more preferably, the light has a wavelength of 650nm and a power of 10 w.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention utilizes a poor solvent assisted phase separation method to prepare a polylactic acid super-hydrophobic surface, then fixes chlorophyll on the super-hydrophobic surface, and makes the chlorophyll generate active oxygen through illumination to destroy the phospholipid layer of cells, thereby achieving the purposes of killing bacteria adhered on the surface of the material and achieving the efficient synergistic antibacterial effect of super-hydrophobicity and photodynamic.
(2) The anti-adhesion efficiency of the prepared polylactic acid material with the anti-adhesion and sterilization functions on escherichia coli and staphylococcus aureus is more than 50%, the sterilization efficiency can reach more than 60%, the synergistic antibacterial effect of the super-hydrophobic anti-bacterial adhesion and the photodynamic sterilization is as high as 100%, the polylactic acid material has good antibacterial durability, and the broad-spectrum and long-acting multiple antifouling and antibacterial functions can be realized.
(3) The invention uses the non-toxic and harmless chlorophyll from biological extraction as a photosensitizer, adopts a photodynamic sterilization mode for sterilization, is a clean and renewable energy source, can realize fixed-point sterilization after being started, can control the generation amount of active oxygen through illumination, and has no residue when being used compared with the traditional antibacterial agents such as quaternary ammonium salt, silver ions, antibiotics and the like, so that the environment pollution can not be caused, and the bacterial drug resistance can not be generated.
(4) The invention adopts biodegradable polylactic acid as a substrate and raw materials, does not need to introduce low surface energy materials such as organic silicon, organic fluoride or fluorosilane which are difficult to be biologically degraded for modification, does not need to add micro/nano inorganic particles, and has good biocompatibility and environmental friendliness.
(5) The good solvent and the poor solvent used in the invention are easy to volatilize, the organic solvent is easy to be recycled and reused in the process of implementing the process, and the clean production of zero emission is easy to realize.
(6) The preparation method has the advantages of simple preparation process, time saving, high efficiency, low cost and easy realization of large-scale or industrial production.
Drawings
FIG. 1 is an antibacterial experiment chart of a sample prepared in example 1 and comparative examples 1 to 3 of the present invention against Staphylococcus aureus; wherein a is the sample prepared in comparative example 1, b is the sample prepared in comparative example 2, c is the sample prepared in comparative example 3, and d is the sample prepared in example 1;
FIG. 2 is an experimental chart of the antibacterial effect of the samples prepared in example 1 and comparative examples 1 to 3 of the present invention on Escherichia coli; wherein a is the sample prepared in comparative example 1, b is the sample prepared in comparative example 2, c is the sample prepared in comparative example 3, and d is the sample prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
Example 1:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butanol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in an oven at 40 ℃ for 48h, and peeling off the polylactic acid pattern surface by using a biaxially oriented polypropylene-based adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 1 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a forced air drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Example 2:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butyl alcohol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in a 40 ℃ oven for 48h, and peeling off the surface of the polylactic acid pattern by using a biaxially oriented polypropylene adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 0.5 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a blast drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Example 3:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butanol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in a 40 ℃ oven for 48h, and peeling off the surface of the polylactic acid pattern by using a biaxially oriented polypropylene adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 2 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a forced air drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Example 4:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butyl alcohol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in a 40 ℃ oven for 48h, and peeling off the surface of the polylactic acid pattern by using a biaxially oriented polypropylene adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 3 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a forced air drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Example 5:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butanol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in an oven at 40 ℃ for 48h, and peeling off the polylactic acid pattern surface by using a biaxially oriented polypropylene-based adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 4 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a blast drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Example 6:
a preparation method of a polylactic acid material with an anti-adhesion sterilization function comprises the following steps:
(1) dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butanol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution;
(2) dripping the coating solution obtained in the step (1) on a hot-press formed polylactic acid sheet substrate with the thickness of 2mm, wherein the coating solution per unit area is 0.3mL/cm2Drying in a 40 ℃ oven for 48h, and peeling off the surface of the polylactic acid pattern by using a biaxially oriented polypropylene adhesive tape to obtain a super-hydrophobic surface;
(3) and (3) dissolving the chlorophyll A in ethanol, performing ultrasonic treatment for 3min to prepare a chlorophyll solution with the concentration of 5 mu mol/L, dripping the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying in a forced air drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
Comparative example 1:
a hot press-molded polylactic acid sheet having a thickness of 2mm was selected as comparative example 1.
Comparative example 2:
dissolving chlorophyll A in ethanol, performing ultrasonic treatment for 3min to obtain a chlorophyll solution with a concentration of 1 mu mol/L, dripping the chlorophyll solution on the surface of a polylactic acid sheet which is formed by hot pressing and has a thickness of 2mm, and drying in a forced air drying oven at 40 ℃ for 12h to obtain the polylactic acid material with the surface containing chlorophyll.
Comparative example 3:
dissolving 1.2g of polylactic acid into 24mL of dichloromethane to obtain a polylactic acid solution, and then adding 30mL of a poor solvent (a mixed solution of absolute ethyl alcohol, n-butanol and butyl acetate in a volume ratio of 1:1: 1) into the polylactic acid solution to uniformly mix to obtain a coating solution; then, the coating solution was applied dropwise onto a hot-press-molded polylactic acid sheet substrate having a thickness of 2mm, the coating solution per unit area being 0.3mL/cm2After drying in an oven at 40 ℃ for 48h, the biaxially oriented polypropylene-based tape was usedStripping off the surface of the polylactic acid pattern to obtain the polylactic acid material with the super-hydrophobic surface.
The products prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to static water contact angle test and adhesion resistance and sterilization efficiency test of escherichia coli and staphylococcus aureus, and the results are shown in table 1, and the specific test methods are as follows:
contact angle test: 5 mu L of ultrapure water is dripped on the surface of the sample, and the static water contact angle data of the sample is measured by a contact angle tester (JC200A, Shanghai) and the average value is calculated.
Anti-adhesion test: immersing the surface of the sample into 1mL of solution of escherichia coli/staphylococcus aureus for 2.5h, taking out the sample, slightly cleaning the sample, desorbing bacteria attached to the surface in an ultrasonic mode, diluting the desorbed bacteria liquid, and then performing plate laying counting to obtain the total bacterial adhesion A; the anti-adhesion efficiency was calculated by the formula of R ═ B-a)/B × 100% from the total bacterial adhesion number B obtained by the same treatment of the original base material, i.e., the sample obtained in comparative example 1.
And (3) sterilization experiment: immersing the sample into 1mL of solution of escherichia coli or staphylococcus aureus for 2.5h, taking out, slightly cleaning, irradiating for 30min under visible light with the power of 10W and the wavelength of 650nm, diluting the bacteria liquid after ultrasonic desorption, and paving and counting to obtain the total number of bacteria C; the total bacterial adhesion B obtained by the same treatment of the original substrate material, i.e., the sample obtained in comparative example 1, was calculated by the formula R ═ B-C)/B × 100% to obtain the bactericidal efficiency.
TABLE 1 static Water contact Angle, anti-adhesion Rate of Escherichia coli to Staphylococcus aureus, and Sterilization efficiency data for samples prepared in examples 1 to 6 and comparative examples 1 to 3
Figure BDA0003175356540000071
As can be seen from table 1, the water contact angles of the samples prepared in examples 1 and 3 to 6 of the present invention are all above 150 °, the anti-adhesion efficiencies to escherichia coli and staphylococcus aureus are all above 50%, the sterilization efficiencies to escherichia coli and staphylococcus aureus are all above 97%, and when the chlorophyll concentration is 1 μmol/L, the sterilization effect of the prepared material is the best, and the sterilization effect can reach 100%.
The antibacterial effect of the samples prepared in the example 1 and the comparative examples 1 to 3 on staphylococcus aureus and escherichia coli is researched by adopting a coating plate method, and the results are shown in fig. 1 and fig. 2.
As can be seen from fig. 1, the number of staphylococcus aureus colonies of the sample prepared in comparative example 2 is reduced compared to the sample prepared in comparative example 1, and the result shows that chlorophyll has a certain bactericidal effect under light and a photodynamic bactericidal effect; the colony number of the sample prepared in the comparative example 3 is reduced from that of the sample prepared in the comparative example 1, which shows that the polylactic acid super-hydrophobic surface has a certain anti-bacterial adhesion effect, while the colony number of the sample prepared in the invention example 1 is almost 0, the surface polylactic acid super-hydrophobic surface and the photodynamic synergistic effect have a remarkable anti-staphylococcus aureus effect, and the anti-adhesion and sterilization synergistic effect can reach 100% of sterility.
As can be seen from fig. 2, the number of escherichia coli colonies of the sample prepared in comparative example 2 was reduced compared to the sample prepared in comparative example 1, and the results showed that chlorophyll had a certain bactericidal effect under light irradiation and had photodynamic bactericidal action; the colony number of the sample prepared in the comparative example 3 is reduced from that of the sample prepared in the comparative example 1, which shows that the polylactic acid super-hydrophobic surface has a certain antibacterial adhesion effect, while the colony number of the sample prepared in the embodiment 1 is almost 0, the synergistic effect of the surface polylactic acid super-hydrophobic surface and the photodynamic has a remarkable escherichia coli resistant effect, and the anti-adhesion and sterilization synergistic effect can reach 100% of sterility.
The foregoing description of the embodiments is provided to enable one of ordinary skill in the art to make and use the invention and is provided for enabling those skilled in the art to make and use the invention with various modifications as are suited to the particular use contemplated and the general principles defined herein are fully contemplated as having benefit of the present teachings. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a polylactic acid material with an anti-adhesion sterilization function is characterized by comprising the following steps:
(1) dissolving polylactic acid into a good solvent to obtain a polylactic acid solution, and then adding a poor solvent into the polylactic acid solution to be uniformly mixed to obtain a coating solution;
(2) coating the coating solution obtained in the step (1) on a polylactic acid substrate, drying and stripping to obtain a super-hydrophobic surface;
(3) and (3) dissolving chlorophyll in ethanol to obtain a chlorophyll solution, coating the chlorophyll solution on the super-hydrophobic surface obtained in the step (2), and drying to obtain the polylactic acid material with the anti-adhesion and sterilization functions.
2. The method according to claim 1, wherein the concentration of the chlorophyll solution in the step (3) is 1 to 5. mu. mol/L.
3. The method according to claim 2, wherein the concentration of the polylactic acid solution in the step (1) is 1 to 5 wt%.
4. The method according to claim 3, wherein the volume ratio of the good solvent to the poor solvent in the coating solution in the step (1) is 1 (0.3-0.9).
5. The method according to claim 4, wherein the good solvent in step (1) is dichloromethane or chloroform; the poor solvent is a mixed solution of any three of n-butyl alcohol, absolute ethyl alcohol, isopropanol, n-propanol, butyl acetate and ethyl acetate.
6. The method according to claim 5, wherein the poor solvent is a mixture of absolute ethyl alcohol, n-butyl alcohol and butyl acetate, and the volume ratio of absolute ethyl alcohol to n-butyl alcohol to butyl acetate is (1-1.5): 1-1.5.
7. The preparation method according to claim 1, wherein in the step (2), the drying comprises the following specific steps: drying for 6-18 h at room temperature, and then drying for 40-60 h at the temperature of 30-60 ℃.
8. The method according to claim 1, wherein in the step (2), the coating is any one of dropping coating, dipping, spraying and spin coating.
9. The preparation method according to claim 1, wherein the peeling in the step (2) adopts a tape sticking pressure peeling process, the pressure is 3-20N, and the tape is a plastic-based tape.
10. The polylactic acid material with the anti-adhesion and sterilization functions, which is prepared by the preparation method of any one of claims 1 to 9.
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