CN112293416B - Environment-friendly non-release CS-b-PEG (polyethylene glycol) antibacterial micelle and preparation method thereof - Google Patents
Environment-friendly non-release CS-b-PEG (polyethylene glycol) antibacterial micelle and preparation method thereof Download PDFInfo
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- CN112293416B CN112293416B CN202010619165.2A CN202010619165A CN112293416B CN 112293416 B CN112293416 B CN 112293416B CN 202010619165 A CN202010619165 A CN 202010619165A CN 112293416 B CN112293416 B CN 112293416B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- 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
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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
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
Abstract
The invention discloses an environment-friendly non-release antifouling preparation CS-b-PEG (polyethylene glycol) antibacterial micelle and a preparation method thereof. First under an inert atmosphereWilliamsonIntroducing allyl into the tail end of polyethylene glycol to prepare allyl-polyethylene glycol (allyl-PEG); then synthesizing copolymer chitosan-one by a free radical polymerization method, wherein the initiator is potassium persulfate (KPS)bPolyethylene glycol (CS-b‑PEG），CS‑bThe PEG copolymer can be self-assembled into the nano micelle after being directly dissolved in an aqueous medium. CS-bPEG micelles can be triggered directly by the attached bacteria, reversing the charge and exposing CS to kill the bacteria. Compared with an alkaline environment, the prepared antibacterial micelle has more excellent antibacterial performance in an acidic solution. The material disclosed by the invention is environment-friendly, has acid-base cycle stability and an excellent antibacterial effect, and provides a thought for exploring the research of non-release antifouling agents in the marine field.
Description
Technical Field
The invention relates to an environment-friendly non-release antifouling antibacterial micelle and a preparation method thereof, belonging to the technical field of marine antibacterial and nano composite materials.
Background
Biofouling is an undesirable process in the marine environment that can endanger ships and marine facilities, including accelerating metal corrosion, affecting the normal use of marine facilities, and affecting the production and quality of aquaculture. The biofilm produced by the bacteria can provide sufficient conditions for other organisms of the colony to inhibit bacterial growth as a key issue. Therefore, the antibacterial agent can effectively prevent the antifouling process. Up to now, heavy metal ions (e.g. Ag)+，Cu+And Cu2+) And its composite materials are the most commonly used antibacterial agents in our lives. However, the biotoxicity of these ions presents a significant hazard to the marine environment. Moreover, due to the uncontrolled nature of these antimicrobial agents, the useful life may be limited by the rapid release rate. Therefore, it is necessary to develop an antibacterial agent having controlled-release characteristics. Enzyme-responsive, pH-responsive and temperature-responsive materials are currently the main strategies for achieving release control properties. Notably, secretion produced by bacterial metabolism may reduce the minicircleThe pH of the environment. Therefore, compared with other initiation methods (such as enzyme reaction), the pH response antibacterial agent has broad-spectrum sterilization property and has wider application prospect.
Synthetic polymer systems can thus be applied in a wide range of fields by selecting and matching different properties, the polymers can meet the requirements of different application scenarios, such as controlled drug delivery and release systems; a coating capable of interacting with and reacting to the environment; performance was analyzed by detecting very small concentrations. Among these, segmented copolymers, especially amphiphilic block copolymers, have become an area of increasing interest to researchers. As a precursor of the nano micelle, a polymer with antibacterial performance and response capability to the environment is selected to synthesize the amphiphilic block copolymer, so that the fields of drug delivery and release and the design concept of the antibacterial field can be widened, and even the application in the field of marine antifouling can be explored.
At present, pH response materials such as nano-micelle and nano-capsule are widely applied in the fields of drug release, antibiosis and antifouling. The magnolol-loaded pH-sensitive polymer doxorubicin conjugate nano-micelle is developed by poplar and the like, and has a synergistically enhanced anti-transfer effect. Huo et al discovered that the addition of a pH responsive capsaicin @ chitosan nanocapsule to a coating effectively reduced the release of capsaicin and extended its useful life in a marine environment. Although polymers with "reservoir" functionality can control the effective release of the agent at a particular pH. In this condition, the reduced amount of agent limits the antimicrobial properties and shortens the useful life of the material. In most cases, the charge of the polymer will change at different pH values, which results in a change in the structure of the shell, thereby achieving the agent or drug release behavior. Inspired by this phenomenon and the adaptability of amphiphilic block copolymers, we propose a nanomicelle having a structurally variable property under different pH conditions by the charge change of a functional polymer, which process does not result in the release of an antibacterial agent.
Disclosure of Invention
Aiming at the problem that the service life of a coating is still limited after the antifouling agent is intelligently controlled and released at present, the invention aims to provide a method for preparing the antifouling coatingProvides an environment-friendly non-release antifouling agent CS-bThe PEG antibacterial micelle and the preparation method of the material are provided to realize the application in the field of marine antifouling bacteriostasis.
The nano micelle has better antibacterial performance than pure CS due to the increased dispersibility after PEG is introduced. Meanwhile, PEG can coat CS cores in alkaline environments, but CS is exposed to the environment after the solution becomes acidic due to bacterial proliferation. In this process, the size of the nanomicelles increases sharply, which is caused by protonation of the amino group on CS. The size of the nanomicelle is sharply increased, which is caused by protonation of the amino group on CS. The cycling stability results indicate that reversible changes in the expansion and contraction of the nanomicelles are achieved during alternating pH (pH 8.5 and pH 5) for 3 cycles due to the continuous protonation and deprotonation of the network nanomicelles. The reversible structure nano micelle not only protects the effective part, but also prolongs the CS-b-antibacterial properties of PEG nanomicelles. By the synergistic effect between the antibacterial ability in CS and the antibacterial effect in PEG, excellent antibacterial performance is achieved.
The purpose of the invention is realized by the following technical scheme:
(1) by passingWilliamsonIntroducing allyl into the tail end of polyethylene glycol to prepare allyl-polyethylene glycol (allyl-PEG);
(2) synthesis of block copolymer chitosan-one by radical polymerizationbPolyethylene glycol (CS-b-PEG）；
（3）CS-bThe PEG copolymer can be self-assembled into micelle after being directly dissolved in an aqueous medium, the nano micelle is stirred for a period of time, and the pH is adjusted by adding NaOH aqueous solution. Filtering the micelle solution by a filter membrane to remove large aggregates, and freeze-drying and storing;
the step (1) mentioned aboveWilliamsonThe method comprises the following steps: the solvent is anhydrous Tetrahydrofuran (THF), sodium hydride (NaH) and allyl bromide (allyl-Br) under the nitrogen atmosphere.
The free radical polymerization method in the step (2) is that CS is dispersed in acetic acid aqueous solution (0.1 vt percent) and an initiator is potassium persulfate (KPS).
The stirring time in the step (3) is 3 days, and the diameter of the filter membrane is 0.45 mu m.
The CS-b-PEG nano micelle prepared by the method is approximately spherical and has the particle size of about 30 nm. The prepared micelle has no release behavior of any bactericide, and the zeta potential of the micelle is changed from +15.87 +/-0.64 mV to-1.96 +/-1.09 mV under the state that the micelle is changed from acid to alkali, and meanwhile, the particle size of the micelle is increased from 30 nm to 51 nm, which takes about 90 minutes, so the micelle has excellent antibacterial performance in an acid solution compared with an alkaline environment.
The invention is provided withWilliamson'sSynthesis method and radical polymerization method for preparing block copolymer CS-bPEG, self-assembly in water into CS-b-PEG nanomicelles. Due to the difference in solubility, PEG coats the CS surface in an alkaline environment and protects the CS. Due to the protonation and deprotonation process of the amino groups in CS, CS-b-PEG micelles can be directly triggered by bacteria, reversing the charge and exposing CS to contact killing of the bacteria. CS-bPEG micelle has excellent bacteriostatic performance against staphylococcus aureus and pseudomonas aeruginosa, and the micelle shows that the micelle has circulation stability and still maintains good bacteriostatic action. Thanks to the action of the non-releasing bactericide, the bacteria-triggered micelle can prolong the service life of the antifouling agent in marine applications.
Drawings
FIG. 1 is CS-bSchematic synthesis of PEG block copolymers.
Wherein, the first step is to introduce allyl at the end of polyethylene glycol. The second step is the preparation of CS-b-a PEG block copolymer.
FIG. 2 is CS-b-a projection electron microscopy image (a) and a dynamic light scattering image (b) of PEG nanomicelles (pH 5).
FIG. 3 shows the reaction of the reaction solution of pH 5 (a)2) And pH 8.5 (a)3) CS-bScanning electron microscope image of morphology of PEG-nanomicelle-treated Staphylococcus aureus, control group (a)1) (ii) a Respectively at pH 5 (b)2) And pH 8.5 (b)3) Lower use of CS-b-PEG nano-micelle treated Pseudomonas aeruginosa morphology scanning electron microscope image, control group (b)1). The scale bar is 2 μm.
FIG. 4 shows CS-bZeta potential (a) value of PEG nanomicelles and micelle size variation (b).
FIG. 5 is a graph of 6 CS-bThe number (a) and the bacteriostatic rate (b) of staphylococcus aureus and pseudomonas aeruginosa of PEG nanomicelles.
Where the initial representation is the preparation of nanomicelles suspended in a pH 8.5 solution. 1. 2, 3, 4, 5 represent alternating treatments at different times of pH 5 according to the pH 8.5 solution, respectively. All tests were repeated at least 3 times.
Detailed Description
The technical solution of the present invention is further explained by the specific embodiments with reference to the drawings.
The following examples are merely illustrative and are only for explaining and illustrating the technical solution of the present invention, and are not to be construed as limiting the technical solution of the present invention.
Example 1:
(1) the whole process was carried out under a nitrogen atmosphere by first completely dissolving 20 g of polyethylene glycol in 100 mL of tetrahydrofuran, and slowly adding sodium hydride (0.28 g) to the above ice-water bath solution with stirring, and then dropping dried tetrahydrofuran (50 mL) and allyl bromide (1.48 g) into the reaction mixture. The mixture was further stirred at room temperature for 48 hours. After the reaction, the mixture was centrifuged to remove the solution, and the residue was dissolved with chloroform. Centrifugation was again performed, and the solvent was evaporated by vacuum-rotary evaporator to obtain allyl-PEG as a white powder.
(2) Under a nitrogen atmosphere, chitosan (2 g) was completely dispersed in an aqueous acetic acid solution (10 mL, 0.1 vt%). Then, 0.05 g of the initiator potassium persulfate was dissolved in the solution and slowly stirred at room temperature for 30 minutes. allyl-PEG was slowly poured into the above solution and reacted at 50 ℃ for 4 hours. After the reaction, an appropriate amount of acetone was added to wash the solution. The precipitate was obtained by centrifugation once and washed with acetone and deionized water 1: 1 washing the precipitate with the mixed solution and washing 3 times to removeUnreacted homopolymer. Finally, the obtained product CS-bThe PEG copolymer was freeze dried and stored in a vacuum apparatus.
（3）CS-bThe PEG copolymer can be self-assembled into the micelle after being directly dissolved in an aqueous medium. The nanomicelle was stirred for three days with gentle stirring. The micellar solution was filtered through a 0.45 μm filter to remove large aggregates and then freeze-dried. The product was obtained as a white powder and stored under vacuum.
Example 2 (effect example):
CS-b-synthesis and performance testing of PEG nanomicelles:
(1) synthesis scheme of nanomicelle:
as can be seen from FIG. 1, CS-bThe preparation of the PEG block copolymer is carried out in two stages, the first stage being carried out byWilliamsonThe synthesis method of (3) introduces allyl group at the end of polyethylene glycol to prepare allyl-polyethylene glycol (allyl-PEG). The second step is to synthesize the block copolymer chitosan-one by adding initiator potassium persulfate (KPS) to carry out free radical polymerizationbPolyethylene glycol (CS-b-PEG). As can be seen from FIG. 2, CS-bThe PEG nanomicelles are approximately spherical and the micelle size is about 30 nm at pH 5.
(2) And (3) testing the sterilizing effect:
respectively dispersing the staphylococcus aureus and pseudomonas aeruginosa bacterial suspensions treated by normal saline (control group) into a liquid culture medium and putting the two bacterial suspensions treated by nano-micelle with pH 5 and pH 8.5 into a shaking incubator and culturing for 20 hours, then dehydrating by using ethanol, and observing the state of live/dead bacteria by using a scanning microscope to determine CS-bThe antibacterial mechanism of PEG nanomicelles.
FIG. 3 shows the reaction of the reaction solution of pH 5 (a)2) And pH 8.5 (a)3) CS-b-scanning electron microscopy image of morphology of staphylococcus aureus treated with PEG nanomicelle, a1Is a control group; respectively at pH 5 (b)2) And pH 8.5 (b)3) Lower use of CS-b-PEG Nanopamicelle treated Pseudomonas aeruginosa topography scanningElectron microscope image b1Is a control group. As can be seen in the figure, both Staphylococcus aureus and Pseudomonas aeruginosa showed a smooth and healthy appearance after treatment with pH 8.5 nanomicelle, as well as normal bacteria (see FIG. 3 a)1And b1). This indicates that the nanomicelle at pH 8.5 has very weak or no bactericidal properties. When using CS-bThe PEG nanomicelles treated staphylococcus aureus and pseudomonas aeruginosa, the bacterial membranes roughened, wrinkled and perforated, indicating that they were completely irreversibly destroyed. This indicates CS-bThe PEG nano-micelle has high antibacterial efficiency at pH 5, and the antibacterial performance of the nano-micelle is similar to that of pure chitosan. This means that in alkaline solutions, the polyethylene glycol is located outside the nanomicelle, while the chitosan is protected in the core. Since chitosan cannot contact with bacteria, the cell membrane remains normal after nanomicelle treatment in alkaline solution. When the pH value of the environment is reduced, the size of the nano-micelle is increased continuously, and the chitosan is exposed in the solution, thereby causing CS-bThe antibacterial performance of the-PEG nano-micelle is shown.
(3) Test of cycle performance and cycle bacteriostatic performance
Adding CS-bPEG nanomicelles were immersed in PBS solution at pH 8.5 and stirred for 90 minutes. The zeta potential and DLS curves of the micelles were evaluated. Then CS-bThe PEG micelle suspension was left to stand in PBS solution at pH 5 for another 120 minutes, and then the zeta potential and DLS data were measured again. This process was repeated 3 times. Each set of micelles was taken to evaluate antibacterial performance.
mu.L of the bacterial suspension was placed in sterile PBS solution containing LB (volume ratio 1: 1), respectively. After mixing in PBS solutions of different pH, 1 mL of CS-bPEG micelle suspension (1 mg/mL) was treated and incubated at 37 ℃ for 4 hours in a shaking incubator, then diluted with sterile physiological saline, and finally 20. mu.L of the mixture was spread on the surface of the solid medium. Spread evenly with a triangular spatula until the surface is dry and free of scratches, and then the petri dish is placed in a constant temperature and humidity chamber for 20 hours and all tests are repeated at least three times. And (3) evaluating the circulating bacteriostatic performance of the bacteria by combining a colony counting method and a sterilization rate formula.
As the bacteria metabolize, the pH at the interface of the bacterial material may change from alkaline or neutral to acidic. After the bacteria are killed by the released biocide and removed from the surface of the structure, the pH of the environment gradually returns to neutral or alkaline. In order to maintain the antibacterial property of the nano-micelle, CS-bPEG nanomicelles must restore structure after the pH of the environment increases to alkaline. Therefore, the size and zeta potential of nanomicelles treated in alkaline and acidic environments were evaluated sequentially. The size of the nanomicelles after alternating pH (pH 8.5 and pH 5) was measured by DLS, and the results are shown in fig. 4 and 5. This indicates that the zeta potential alternates between positive and negative with alternating pH. Six changes in structure also occurred. It can be clearly seen that CS-bThe structural change of PEG nanomicelles is reversible. After 3 cycles, CS-bThese dimensions of PEG nanomicelles are about 63 nm at pH 5 and 40 nm at pH 8.5, respectively. After 3 cycles, the size of the nanomicelles increased by nearly 10 nm compared to the initial size of about 30 nm (pH 8.5). This may be due to natural expansion behaviour. At the same time, these zeta potential values are negative at pH 8.5 and positive at pH 5 after 3 cycles, which indicates that the pH response characteristic can be maintained at least 6 times and still remain relatively stable. Specifically, the initial zeta potential of the nanomicelle was-3.99. + -. 0.96 mV, and the curves for the other alkaline solutions were-2.38. + -. 0.82 mV, -1.16. + -. 0.97 and-0.98. + -. 1.10 mV, respectively. The data for the acid solutions were + 15.87. + -. 0.64mV, 23.37. + -. 2.97mV and 28.20. + -. 3.16mV, respectively. Thus, CS-bPEG nanomicelles can repeat pH response and at least 6 structural inversions at alternating pH values.
The results of the colony counting method in FIG. 5 show that the bacteriostatic effect of the sample is slightly decreased with the increase of the number of alternating pH values, which corresponds to FIG. 3. The bacteriostatic action on staphylococcus aureus and pseudomonas aeruginosa is still respectively 83.62% and 78.23% after 5 times of reversible structure (alternate pH). Showing excellent cycling stability of the nanomicelle. This indicates that CS-bThe PEG nano-micelle can keep larger bacteriostatic action in the environment.
The above are throughWilliamson'sA synthesis method and a free radical polymerization method,preparation of Block copolymer CS-bPEG, self-assembly in water into CS-bDetails of several of the PEG nanocolloids. It should be noted that the present invention is not limited to the above-described embodiments; for a person skilled in the art, modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (6)
1. A preparation method of an environment-friendly non-release antifouling CS-b-PEG antibacterial micelle is characterized by comprising the following steps:
(1) preparing allyl-polyethylene glycol (allyl-PEG) by introducing an allyl group to the end of polyethylene glycol by the Williamson method;
(2) synthesizing a segmented copolymer chitosan-b-polyethylene glycol (CS-b-PEG) at a certain temperature by a free radical polymerization method;
(3) the CS-b-PEG copolymer can be self-assembled into micelle after being directly dissolved in an aqueous medium, the nano micelle is stirred for a period of time, filtered by a filter membrane, and then freeze-dried for storage.
2. The method according to claim 1, wherein the Williamson method in step (1) comprises: and (3) under an inert gas atmosphere, wherein the solvent is anhydrous tetrahydrofuran, sodium hydride and allyl bromide.
3. The process according to claim 1, wherein the radical polymerization in step (2) is carried out by dispersing CS in an aqueous acetic acid solution, the initiator is potassium persulfate, and the reaction temperature in a water bath is 40 to 80 ℃.
4. The method according to claim 1, wherein the stirring in the step (3) is carried out for 3 days, the diameter of the filter is 0.45. mu.m, and the size of the micelle is 30 nm.
5. An environment-friendly non-release antifouling formulation CS-b-PEG antibacterial micelle, which is characterized in that: the antibacterial micelle is prepared by the method according to any one of claims 1 to 4.
6. The use of the antibacterial micelle of claim 5 in the field of marine bacteriostasis.
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