CN117003935A - Polymer drug-loaded nanoparticle with high encapsulation efficiency and application thereof in paint and surface film material - Google Patents
Polymer drug-loaded nanoparticle with high encapsulation efficiency and application thereof in paint and surface film material Download PDFInfo
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- CN117003935A CN117003935A CN202310658424.6A CN202310658424A CN117003935A CN 117003935 A CN117003935 A CN 117003935A CN 202310658424 A CN202310658424 A CN 202310658424A CN 117003935 A CN117003935 A CN 117003935A
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- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
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- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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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Abstract
The invention discloses a polymer drug-loaded nanoparticle with high encapsulation efficiency and application thereof in paint and surface film materials. The polymer drug-loaded nano-particles are prepared by emulsion polymerization, and antibacterial drugs with different log P values are loaded. The preparation process is simple, the product has small particle size, large molecular weight, high uniformity and high medicine encapsulation efficiency, and the substitution of the reactive surfactant for the non-reactive surfactant is realized. The polymer drug-loaded nano-particles can be used for preparing a coating. The slow-release antibacterial surface film material can be further prepared by a crosslinking film forming method by using the coating, and has the advantages of good mechanical property, good chemical resistance and high safety. The invention can be widely applied to various environments and material surfaces, including but not limited to surface modification of instruments, building materials and the like in living environments, medical environments and the like, thereby achieving lasting antibacterial effect.
Description
Technical Field
The invention belongs to the field of antibacterial materials. In particular to a preparation method of polymer drug-loaded nano particles with high encapsulation efficiency and application of the polymer drug-loaded nano particles in coating and surface film materials.
Background
Microorganisms are one of the oldest species on earth, are spread over all biota, and are widely present in the human production and living environment. Most microorganisms are harmless to humans and can be used to make foods, chemicals, etc. However, some microorganisms such as escherichia coli, staphylococcus aureus, aspergillus niger and the like can rapidly reproduce under proper environmental conditions, so that substances become moldy, spoilage, wound ulcer infection and the like are caused, and the human health is adversely affected.
The traditional antibacterial method comprises ultraviolet antibacterial, alcohol disinfection, high-temperature sterilization and the like, but the above strategies have the problems of short antibacterial time, repeated and complicated operation, limited use environment, potential safety risk and the like. For example, manuela Lualdi et al (BMC Effect Dis.2021, 21, 594) designed a complex ultraviolet LED lamp incorporating different aluminum layers to supplement the current hospital's cleaning and disinfection of SARS-CoV-2 contaminated surfaces, while improving safety but at a higher cost and with antimicrobial hysteresis. The surface modification strategy fundamentally endows the material with antibacterial property, overcomes the defects of the former, and the high polymer forms a compact and flat coating on the surface. Esmeryan, K.D. (Mater. Des.2018,160, 395-404) has been inspired naturally to reduce microbial attachment by using superhydrophobic structures, but does not possess bactericidal or bacteriostatic activity and still has a risk of contamination in non-hydrophobic areas; luyun Cai et al (J agric. Food chem.2020,68, 7453-7466) loaded antibacterial peptides with Pickering emulsions, but with lower drug loading and encapsulation rates and poor emulsion stability.
Therefore, it is necessary to establish a safer, more stable, and more durable method for antimicrobial. The slow-release antibacterial surface film material is a novel antibacterial strategy, and a layer of slow-release antibacterial film can be formed on the surface of the material, so that the continuous inhibition of surface microorganisms is realized. Compared with the traditional antibacterial method, the slow-release antibacterial surface film material has various advantages, such as strong controllability, lasting antibacterial effect, difficult migration, safety and innocuity to human body, etc. In conclusion, a stable and easily-obtained slow-release drug-carrying system is adopted, so that the surface antibacterial capability of various instrument materials is improved, and the method has important practical significance.
Disclosure of Invention
The invention aims to provide polymer drug-loaded nano-particles with high encapsulation efficiency and a preparation method thereof. The method has the advantages of mild condition, low cost, simple operation and easy industrialized production.
Another object of the present invention is to provide a film forming method of the above polymer drug-loaded nanoparticle. The method comprises a preparation method of the coating and a preparation method of a surface film material based on the coating.
The invention also aims to provide the application of the polymer drug-loaded nano-particles in slow-release antibacterial surface film materials.
In one aspect, the invention provides a polymer drug-loaded nanoparticle with high encapsulation efficiency and a preparation method thereof. Which is prepared by emulsion polymerization, comprising the steps of:
adding part of emulsifier into water, sequentially adding monomer and antibacterial agent, and magnetically stirring at 600rpm for 3-12h to obtain stable monomer pre-emulsion A; preparing a part of initiator into a solution B with the mass concentration of 3% -5% by using deionized water; preparing solution C of sodium bicarbonate and partial emulsifier with deionized water; preparing a part of initiator into a solution D with the mass concentration of 2% -3% by using deionized water; preparing oxidant into solution E with mass concentration of 4% -6% by using deionized water; preparing a solution F with the mass concentration of 4% -6% by using deionized water as a reducing agent; the pH regulator is prepared into a solution G with the mass concentration of 50% by using deionized water.
Adding a solution C into a 1L jacketed glass reaction kettle provided with a condensing tube, a thermometer and a stirring paddle, after nitrogen replacement, raising the reaction temperature to 85 ℃, and starting stirring; taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; continuously stirring for 20-30min; then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion is obtained after passing through a 200-mesh filter screen.
Preferably, the monomer used in the preparation process of the polymer drug-loaded nanoparticle can be one or more of styrene, acrylic monomer and methacrylic monomer; more preferably, it may be one or more of styrene, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, beta-hydroxypropyl methacrylate available from Yu Annai g chemical company; most preferably, the monomer may be styrene, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate.
Preferably, the initiator used in the preparation process of the polymer drug-loaded nano-particles can be peroxide, persulfate or azo initiator; more preferably, it is benzoyl peroxide, di-t-butyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, or azobisisobutylamino hydrochloride available from Yu Annai g chemical company; most preferably, the initiator species is azobisisobutyronitrile or azobisisobutyronitrile hydrochloride.
Preferably, the polymerThe redox system used in the preparation process of the drug-loaded nano-particles can be tert-butyl hydroperoxide/sodium metabisulfite, tert-butyl hydroperoxide/FF 6M, benzoyl peroxide/N, N-dimethylaniline, benzoyl peroxide/FF 6M, ammonium persulfate/sodium bisulphite or hydrogen peroxide/FF 6M; more preferably, the redox system may be t-butyl hydroperoxide/FF 6M. FF6M was purchased from Germany Chemical Co. The remaining reagents were purchased from Yu Annai g chemical company.
Preferably, the surfactant used in the preparation of the polymer drug-loaded nanoparticle may be one or two of non-reactive surfactants such as sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, and sodium secondary alkyl sulfonate available from Yu Annai g chemical reagent company, and reactive surfactants such as Adeka readas SE-10N, adeka readas SR-10, adeka readas SR-1025, adeka readas-10, adeka speeder-20, adeka speeder-30, or Adeka speeder-70 available from Adeka corporation; more preferably, it may be one or both of sodium dodecyl benzene sulfonate, ADEKAREASOAP SR-10 or ADEKAREASOAPER-30.
Preferably, the pH regulator used in the preparation process of the polymer drug-loaded nano-particles can be sodium carbonate, sodium bicarbonate, ammonia water, dimethylethanolamine, N-methylethanolamine, butylethanolamine and the like purchased from Ann Ji-Kai chemical reagent company; more preferably, dimethylethanolamine is available.
Preferably, the antibacterial drug loaded by the polymer drug-loaded nano-particles is an organic matter with the antibacterial effect and the log P range is 0.5-6, and the organic matter does not react with an initiator; more preferably, the organic matter with antibacterial effect with log P ranging from 1 to 3 is not reacted with the initiator; most preferably, n-butyl-1, 2-benzisothiazolin-3-one (CAS 4299-07-4), iodopropynyl butylcarbamate (CAS 55406-53-6), 2-phenoxyethanol (CAS 122-99-6) or ethylparaben (CAS 120-47-8) and does not react with the initiator. The above reagents were purchased from Yu Annai g chemical company.
Preferably, the ratio of the monomer addition amount to the water addition amount (W/W) used in the polymer nanoparticle preparation process may be 1:0.5 to 1:2, for example, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, etc., more preferably, the ratio of the monomer addition amount to the water addition amount is 1:1.1 to 1:1.2. Wherein the weight (W) is calculated in grams (g).
Preferably, the ratio (W/W) of the initiator addition to the monomer addition used in the preparation of the polymer drug-loaded nanoparticle may be 1% -10%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; more preferably, the ratio of the initiator addition amount to the monomer addition amount is 3% to 5%. Wherein the weight (W) is calculated in grams (g).
Preferably, the ratio (W/W) of the redox system addition to the monomer addition used in the preparation of the polymeric drug-loaded nanoparticle is 0.05% to 0.5%, for example 0.05%, 0.06%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%; more preferably, the ratio of the redox system addition amount to the monomer addition amount is 0.2%. Wherein the weight (W) is calculated in grams (g).
Preferably, the ratio (W/W) of the antimicrobial drug addition to the monomer addition used in the preparation of the polymer drug-loaded nanoparticle is 0.5% -10%, for example 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; more preferably, the ratio of the amount of the antibacterial agent to the amount of the monomer added is 1%. Wherein the weight (W) is calculated in grams (g).
Preferably, the reaction temperature used in the preparation process of the polymer drug-loaded nanoparticle can be: the first section is 80-90 ℃, the middle section is 60-70 ℃, the last section is 35-45 ℃, such as 80-65-40 ℃, 80-60-45 ℃, 85-65-45 ℃, 85-70-40 ℃, 85-70-45 ℃, 90-60-45 ℃, or 90-65-45 ℃, etc.; more preferably, the reaction temperature may be: the first section is 85 ℃, the middle section is 65 ℃, and the last section is 40 ℃.
Preferably, the ratio (W/W) of the amount of pH adjuster added to the amount of monomer added used in the preparation of the polymer drug-loaded nanoparticle may be 0.05% -2%, for example 0.05%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.5% or 2%; more preferably, the ratio of the addition amount of the pH adjustor to the addition amount of the monomer is 0.4%.0.8%. Wherein the weight (W) is calculated in grams (g).
Preferably, the stirring mode can be mechanical stirring, and the rotating speed is 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 900rpm, 1000rpm, 1250rpm, 1500rpm; more preferably, the stirring speed is 1000rpm.
Preferably, the antibacterial agent is added in the pre-emulsion or blended in the shell pre-emulsion by a core-shell polymerization mode; more preferably, the addition mode is blending addition in the shell pre-emulsion through a core-shell polymerization mode.
Preferably, the weight average molecular weight of the polymer drug-loaded nano-particles is 20000-40000, and the average particle diameter is 100-200nm.
In another aspect, the present invention provides a method of preparing a coating based on the polymer drug-loaded nanoparticle described above. Comprises the following steps of;
weighing the polymer nano particle water dispersion, placing the polymer nano particle water dispersion into a flask, adding deionized water with the mass ratio of 1:1 for diluting and dispersing, then adding additives such as 5% of cross-linking agent, 1.5% of film forming additive, 0.3% of wetting and leveling agent, 0.03% of defoaming agent and the like, stirring for 10min by using a magnetic stirrer at 800rpm, and fully dispersing various additives, wherein the adding ratio of the additive mass to the mass of the polymer nano particle water dispersion after water dilution is the ratio of the additive mass to the mass of the polymer nano particle water dispersion after water dilution.
Preferably, the crosslinking agent may be aqualin 268, aqualin 269, aqualin 270, aqualin 278 or aqualin 280, etc. available from the company of vantagon chemistry; more preferably, aqualin 268.
Preferably, the film forming aid may be ethylene glycol, propylene glycol, hexylene glycol, dipropylene glycol n-butyl ether, dipropylene glycol monomethyl ether, polyethylene glycol (molecular weight 200), ethylene glycol butyl ether acetate, or hexanediol diacetate, or the like; more preferably, dipropylene glycol monomethyl ether may be used.
Preferably, the wetting and leveling agent may be one or two of BYK-151, BYK-153, BYK-301, BYK-333, BYK-346, BYK-348 or BYK-361N, etc. available from Pick corporation; more preferably, one or both of BYK-333 or BYK-346 are possible.
Preferably, the defoamer may be Tego pre 5840, tego pre 5885, tego Airex 902W, surfynolAD01, surfynol MD20, surfynol 465, or the like, available from win-creation specialty chemicals (Shanghai) limited; more preferably, tegoAirex 902W.
In a third aspect, the present invention provides a surface film forming method based on the above coating. The coating is formed into a film on the surface of a substrate by a crosslinking film forming mode, and the method comprises the following steps:
1.00g of coating is weighed and dropped on the surface of a substrate, then a wet film coater is utilized to horizontally scrape a film on the surface of the substrate, and the surface film material is obtained after the water is volatilized and the rest is carried out.
Preferably, the substrate may be nylon cloth, glass plate, engineering plastic alloy plate (abs+pc), thermoplastic polyester Plate (PET), carbon fiber plate, or the like. The substrate includes, but is not limited to, the above substrate types.
In a fourth aspect, the present invention provides the use of a slow release antimicrobial surface film material as described above. The surface film material is prepared on the surfaces of various base materials through the simple, convenient, quick and reliable film forming process. The antibacterial effect of the material is evaluated by performing an antifungal and antibacterial test on the slow-release antibacterial surface film material. Meanwhile, a slow release capability test is carried out by using a water dialysis method, and the slow release effect of the material is evaluated. In addition, the biosafety of the surface film material was further studied. Thereby realizing the safe and efficient slow-release antibacterial effect of the common apparatuses in contact with people in the environment.
Compared with the prior art, the invention has the following beneficial effects:
firstly, a synthetic method of polymer drug-loaded nano-particles loaded with antibacterial drugs with different log P values at high encapsulation efficiency is established for the first time, and the drug encapsulation efficiency can reach more than 90%. The reactive surfactant is adopted to completely replace the traditional free surfactant, so that the potential toxicity of the polymer nanoparticle system is reduced, and the stability and uniformity of the aqueous dispersion are improved. Secondly, the water dispersion film forming process of the polymer drug-loaded nano particles is firstly applied to the field of antibacterial surface film forming. Based on the method, a transparent surface film material with higher mechanical strength and better chemical resistance can be prepared. The residual quantity of isocyanate groups in the crosslinking film forming method is less than 1%, so that the potential toxicity of the material is further reduced. Thirdly, the surface modification of various base materials based on the slow-release antibacterial surface material is realized, and further the surface antibacterial is realized. The prepared surface film material has better slow-release antibacterial performance and better biological safety evaluation, and can realize long-acting broad-spectrum antibacterial on common bacteria and mould.
Drawings
FIG. 1 is a graph of the test results of the chemical resistance of a slow-release antibacterial surface film material prepared based on polymer drug-loaded nanoparticles in the invention.
FIG. 2 is a graph of the detection result of the film forming process of the slow-release antibacterial surface film material prepared based on polymer drug-loaded nano-particles in the invention.
FIG. 3 is a graph showing the molding effect of a slow-release antibacterial surface film material prepared based on polymer drug-loaded nanoparticles in the invention.
FIG. 4 is a graph of the extract test results of a slow-release antimicrobial surface film material prepared based on polymer drug-loaded nanoparticles in the present invention.
FIG. 5 is a graph of the test results of the antifungal performance of a slow-release antimicrobial surface film material prepared based on polymer drug-loaded nanoparticles in the present invention.
FIG. 6 is a graph of antibacterial performance test results of a slow-release antibacterial surface film material prepared based on polymer drug-loaded nanoparticles in the present invention.
FIG. 7 is a graph showing the results of a slow release performance test of a slow release antimicrobial surface film material prepared based on polymer drug-loaded nanoparticles in the present invention.
Detailed Description
The following description of several preferred embodiments of the invention is presented to further illustrate the advantages of the invention, but is intended to be illustrative of the invention and not limiting in its scope.
Example 1: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.89g of sodium dodecyl benzene sulfonate and 2.50g of ADEKAREASOAP SR-10 into 55.50g of deionized water, sequentially adding 0.94g of styrene, 22.00g of methyl methacrylate, 79.60g of butyl methacrylate and 10.20g of hydroxyethyl methacrylate, and adding 1.04g of n-butyl-1, 2-benzisothiazolin-3-one by blending with the hydroxyethyl methacrylate, and stirring at a high speed for 3-12h to prepare a stable monomer pre-emulsion A;
Solution B was prepared from 0.06g of initiator azobisisobutyronimidine hydrochloride with 5.00g deionized water;
solution C was prepared from 0.20g sodium bicarbonate and 1.33g sodium dodecyl benzene sulfonate with 60.00g deionized water;
solution D was prepared from 0.19g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 mm rotation speed 1000 rpm). Taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3.5min, adding the solution B, and continuously stirring for 20-30min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8.9, and the polymer drug-loaded nanoparticle aqueous dispersion A-1 is obtained after passing through a 200-mesh filter screen. And (3) carrying out freeze-drying treatment on the A-1 by using a vacuum freeze dryer to obtain freeze-dried particles A-1G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-1 are as follows:
the appearance is milky white and blue, the pH is 9.57, the yield is 87.67%, and the solid content is 44.67%;
particle size analysis was performed on A-1 using a nanoparticle size and zeta potential analyzer, with an average particle size of 139.60nm and a polydispersity index (PDI) of 0.023;
stability analysis was performed on A-1 using a stability analyzer with a stability index (TsI) of 1.45;
molecular weight analysis of A-1G by Gel Permeation Chromatography (GPC) showed that the number average molecular weight was 32107 and the weight average molecular weight was 34772;
and detecting the drug encapsulation efficiency of the A-1G by using a High Performance Liquid Chromatograph (HPLC), wherein the encapsulation efficiency is 85.89 +/-0.64%.
Example 2: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.89g of sodium dodecyl benzene sulfonate and 2.50g of ADEKAREASOAP SR-10 into 55.50g of deionized water, sequentially adding 0.94g of styrene, 22.00g of methyl methacrylate, 79.60g of butyl methacrylate and 10.20g of hydroxyethyl methacrylate, dispersing 1.04g of n-butyl-1, 2-benzisothiazolin-3-one into a 33% system after blending with the hydroxyethyl methacrylate, and stirring at a high speed for 3-12 hours to prepare a stable monomer pre-emulsion A, H;
Solution B was prepared from 0.10g of initiator azobisisobutyronimidine hydrochloride with 5.00g of deionized water;
solution C was prepared from 0.20g sodium bicarbonate and 1.33g sodium dodecyl benzene sulfonate with 60.00g deionized water;
solution D was prepared from 0.32g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 mm rotation speed 1000 rpm). Taking 7.5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, adding solution B, and continuously stirring for 20-30min. Then, simultaneously dropwise adding the monomer pre-emulsion A and the solution D, uniformly adding the residual monomer pre-emulsion A within 2 hours, and uniformly adding the pre-emulsion H within the residual 1 hour in time; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion A-2 is obtained after passing through a 200-mesh filter screen. And (3) carrying out freeze-drying treatment on the A-2 by using a vacuum freeze dryer to obtain freeze-dried particles A-2G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-2 are as follows:
the appearance is milky white and blue, the pH is 9.37, the yield is 90.67%, and the solid content is 41.05%;
particle size analysis of A-2 was performed using a nanoparticle size and zeta potential analyzer, with an average particle size of 150.14nm and a polydispersity index (PDI) of 0.060;
stability analysis was performed on a-2 using a stability analyzer with a stability index (TsI) of 1.10;
molecular weight analysis of A-2G by Gel Permeation Chromatography (GPC) showed a number average molecular weight of 32016 and a weight average molecular weight of 34423;
and detecting the drug encapsulation efficiency of the A-2G by using a High Performance Liquid Chromatograph (HPLC), wherein the encapsulation efficiency is 95.06+/-0.79%.
Example 3: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.50gADEKA REASOAP ER-30 and 1.50gADEKA REASOAP SR-10 into 55.50g deionized water, sequentially adding 0.94g styrene, 22.00g methyl methacrylate, 79.60g butyl methacrylate and 10.20g hydroxyethyl methacrylate, and dispersing 1.04g n-butyl-1, 2-benzisothiazolin-3-one in a 33% system into another bottle after blending with the hydroxyethyl methacrylate, and stirring at a high speed for 3.12h to obtain a stable monomer pre-emulsion A, H;
Solution B was prepared from 0.10g of initiator azobisisobutyronimidine hydrochloride with 5.00g of deionized water;
solution C was prepared from 0.20g sodium bicarbonate, 0.50g ADEKAREASOAP ER-30 and 1.00gADEKA REASOAP SR-10 with 60.00g deionized water;
solution D was prepared from 0.32g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 nm rotation speed 1000 rpm). Taking 7.5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, adding solution B, and continuously stirring for 20-30min. Then, simultaneously dropwise adding the monomer pre-emulsion A and the solution D, uniformly adding the residual monomer pre-emulsion A within 2 hours, and uniformly adding the pre-emulsion H within the residual 1 hour in time; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion A-3 is obtained after passing through a 200-mesh filter screen. And (3) carrying out freeze-drying treatment on the A-3 by using a vacuum freeze dryer to obtain freeze-dried particles A-3G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-3 are as follows:
the appearance is milky white and blue, the pH is 9.22, the yield is 93.55%, and the solid content is 43.56%;
particle size analysis was performed on A-3 using a nanoparticle size and zeta potential analyzer, with an average particle size of 171.72nm and a polydispersity index (PDI) of 0.023;
stability analysis was performed on A-3 using a stability analyzer with a stability index (TSI) of 0.56;
molecular weight analysis of A-3G by Gel Permeation Chromatography (GPC) showed a number average molecular weight of 35016 and a weight average molecular weight of 36727;
and detecting the medicine encapsulation efficiency of the A-3G by using a High Performance Liquid Chromatograph (HPLC), wherein the encapsulation efficiency is 90.81+/-1.33%.
Example 4: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.50gADEKA REASOAP ER-30 and 1.50gADEKA REASOAP SR-10 into 55.50g deionized water, sequentially adding 0.94g styrene, 22.00g methyl methacrylate, 79.60g butyl methacrylate and 10.20g hydroxyethyl methacrylate, dispersing 1.04g iodopropynyl butylcarbamate into a 33% system after blending with the hydroxyethyl methacrylate, and stirring at high speed for 3.12h to prepare a stable monomer pre-emulsion A, H;
Solution B was prepared from 0.10g of initiator azobisisobutyronimidine hydrochloride with 5.00g of deionized water;
solution C was prepared from 0.20g sodium bicarbonate, 0.50g ADEKAREASOAP ER-30 and 1.00gADEKA REASOAP SR-10 with 60.00g deionized water;
solution D was prepared from 0.32g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 mm rotation speed 1000 rpm). Taking 7.5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, adding solution B, and continuously stirring for 20-30min. Then, simultaneously dropwise adding the monomer pre-emulsion A and the solution D, uniformly adding the residual monomer pre-emulsion A within 2 hours, and uniformly adding the pre-emulsion H within the residual 1 hour in time; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion A-4 is obtained after passing through a 200-mesh filter screen. And (3) carrying out freeze-drying treatment on the A-4 by using a vacuum freeze dryer to obtain freeze-dried particles A-4G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-4 are as follows:
the appearance is milky white and blue, the pH is 9.53, the yield is 90.08%, and the solid content is 40.15%;
particle size analysis was performed on A-4 using a nanoparticle size and zeta potential analyzer, with an average particle size of 156.06nm and a Polydispersity (PDI) of 0.073;
stability analysis was performed on a-4 using a stability analyzer with a stability index (TsI) of 0.54;
a-4 was subjected to molecular weight analysis by Gel Permeation Chromatography (GPC) and had a number average molecular weight of 35329 and a weight average molecular weight of 37136.
Example 5: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.50gADEKA REASOAP ER-30 and 1.50gADEKA REASOAP SR-10 into 55.50g deionized water, sequentially adding 0.94g styrene, 22.00g methyl methacrylate, 79.60g butyl methacrylate and 10.20g hydroxyethyl methacrylate, dispersing 1.04g 2-phenoxyethanol into a 33% system after blending with the hydroxyethyl methacrylate, and stirring at a high speed for 3-12h to prepare a stable monomer pre-emulsion A, H;
solution B was prepared from 0.10g of initiator azobisisobutyronimidine hydrochloride with 5.00g of deionized water;
Solution C was prepared from 0.20g sodium bicarbonate, 0.50g ADEKAREASOAP ER-30 and 1.00gADEKA REASOAP SR-10 with 60.00g deionized water;
solution D was prepared from 0.32g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 mm rotation speed 1000 rpm). Taking 7.5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, adding solution B, and continuously stirring for 20-30min. Then, simultaneously dropwise adding the monomer pre-emulsion A and the solution D, uniformly adding the residual monomer pre-emulsion A within 2 hours, and uniformly adding the pre-emulsion H within the residual 1 hour in time; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion A-5 is obtained after passing through a 200-mesh filter screen. And (5) carrying out freeze-drying treatment on the A-5 by using a vacuum freeze dryer to obtain freeze-dried particles A-5G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-5 are as follows:
the appearance is milky white and blue, the pH is 9.36, the yield is 91.48%, and the solid content is 40.97%;
particle size analysis was performed on A-5 using a nanoparticle size and zeta potential analyzer, with an average particle size of 145.37nm and a polydispersity index (PDI) of 0.046;
stability analysis was performed on A-5 using a stability analyzer with a stability index (TSI) of 0.58;
molecular weight analysis was performed on A-5G by Gel Permeation Chromatography (GPC) to obtain a number average molecular weight of 35974 and a weight average molecular weight of 37077.
Example 6: preparation and characterization of polymer drug-loaded nanoparticle aqueous dispersion
Adding 0.50gADEKA REASOAP ER-30 and 1.50gADEKA REASOAP SR-10 into 55.50g deionized water, sequentially adding 0.94g styrene, 22.00g methyl methacrylate, 79.60g butyl methacrylate and 10.20g hydroxyethyl methacrylate, dispersing 1.04g ethylparaben after blending with the hydroxyethyl methacrylate in a 33% system, and stirring at high speed for 3-12h to prepare a stable monomer pre-emulsion A, H;
solution B was prepared from 0.10g of initiator azobisisobutyronimidine hydrochloride with 5.00g of deionized water;
Solution C was prepared from 0.20g sodium bicarbonate, 0.50g ADEKAREASOAP ER-30 and 1.00gADEKA REASOAP SR-10 with 60.00g deionized water;
solution D was prepared from 0.32g of initiator azobisisobutyronimidine hydrochloride with 12.00g of deionized water;
solution E was prepared from 0.14g of 70% aqueous t-butyl hydroperoxide with 2.00g of deionized water;
0.12g BRUGGOLITE FF6M was prepared as solution F with 2.00g deionized water;
1.00G of the pH regulator dimethylethanolamine was made up into solution G with 1.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, and after nitrogen substitution, the reaction temperature was raised to 85 ℃ and stirring was started (d=40 mm rotation speed 1000 rpm). Taking 7.5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, adding solution B, and continuously stirring for 20-30min. Then, simultaneously dropwise adding the monomer pre-emulsion A and the solution D, uniformly adding the residual monomer pre-emulsion A within 2 hours, and uniformly adding the pre-emulsion H within the residual 1 hour in time; solution D was added at constant rate over 3h 15 min. After the completion of the dropwise addition, the reaction temperature was lowered to 65℃and the solution E and the solution F were simultaneously added dropwise, and the dropwise addition was completed within 30 minutes. After the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion A-6 is obtained after passing through a 200-mesh filter screen. And (5) carrying out freeze-drying treatment on the A-6 by using a vacuum freeze dryer to obtain freeze-dried particles A-6G.
The basic properties of the obtained polymer drug-loaded nanoparticle aqueous dispersion A-6 are as follows:
the appearance is milky white and blue, the pH is 9.31, the yield is 92.70%, and the solid content is 42.46%;
the particle size analysis of A-6 is carried out by utilizing a nano-particle size and zeta potential analyzer, the average particle size is 140.80nm, and the polydispersity index (PDI) is 0.032;
stability analysis was performed on A-6 using a stability analyzer with a stability index (TsI) of 0.61;
molecular weight analysis was performed on A-6G using Gel Permeation Chromatography (GPC) with a number average molecular weight of 36632 and a weight average molecular weight of 37774.
Example 7: preparation of functional coating and surface film material and performance test thereof
10g of polymer nanoparticle aqueous dispersion A-3 is weighed and placed in a flask, 10g of deionized water with the mass ratio of 1:1 is added for dilution and dispersion, then 1g of cross-linking agent Aquolin 268, 0.3g of film forming additive dipropylene glycol monomethyl ether, 0.3g of wetting leveling agent BYK-333 and BYK346, 0.03g of defoaming agent Tego Airex 902W are added, stirring is carried out for 10min by using a magnetic stirrer at 800rpm, after full dispersion, 1g of polymer nanoparticle aqueous dispersion is weighed and dripped on the surface of a substrate, and then a wet film coater is used for horizontally scraping films on the surfaces of nylon cloth, a glass plate, an engineering plastic alloy plate (ABS+PC), a thermoplastic polyester Plate (PET) and a carbon fiber plate, and standing is carried out, and after water is volatilized, surface film materials B-1, B-2, B-3, B-4 and B-5 are obtained.
Hardness tests were carried out on B-1 to B-4 by using a pencil scratch method. The dried material plate is placed on a horizontal table top, and during experiments, the pencil is fixed inside the instrument, so that the pencil is pressed down on the surface of the material at an angle of 45 degrees. The instrument was pushed to make the pencil scratch the surface of the material, and the pencil was pushed forward at a speed of 1mm/s for 8mm, and after 30s, it was observed whether the surface of the material was scratched or damaged. If the defects of 3mm and above appear, the pencil hardness is reduced, and the experiment is continuously carried out by adopting the same method; if no defects occur, the experiment is continued with increasing pencil hardness until defects of less than 3mm occur. The hardness of a material is expressed as the strongest pencil hardness that does not cause scratches and damage of 3mm or more to the surface of the material.
TABLE 1 Pencil scratch hardness test results
After the material is molded, the hardness test is carried out by utilizing a pencil scratch method. Except nylon cloth base material, the surface of other base materials can be tested. Experimental results show that after the slow-release antibacterial surface film material is formed on the surfaces of glass, ABS+PC, PET, carbon fiber and other base materials, film structures with certain hardness can be formed, and the hardness grades are above HB. At the same time, a continuous film structure can be formed on the nylon cloth surface.
And (3) performing chemical resistance test on the B-1 to B-5. The method for detecting the chemical resistance is as follows:
water resistance: the test solution is distilled water, the middle part of each plate is taken in the test area, water absorbing paper is put on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process. The experimental time is 24 hours, and the observation is carried out after the experimental time is placed for 24 hours.
Alkali resistance: the test solution is 10% Na 2 CO 3 The solution, the middle part of each plate is taken in the test area, the water absorbing paper is put on the test area, and the test area is sealed by a glass cover, so that the filter paper is kept wet in the test process. The experimental time is 24 hours, and the observation is carried out after the experimental time is placed for 24 hours.
Alcohol resistance: the test solution is 50% (volume fraction) ethanol solution, the middle part of each plate is taken in the test area, water absorbing paper is placed on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process. The experimental time is 24 hours, and the observation is carried out after the experimental time is placed for 24 hours.
Acid resistance: the test solution is 10% acetic acid solution, the middle part of each plate is taken in the test area, water absorbing paper is placed on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process. The experimental time is 24 hours, and the observation is carried out after the experimental time is placed for 24 hours.
TABLE 2 evaluation of the resistance to chemical transformation
The resistance test results are shown in figure 1 and table 3 below, and from the resistance test results, the surface film material prepared by using the polymer drug-loaded nano particles has better water resistance, alcohol resistance, acid resistance and alkali resistance on the surfaces of various base materials.
TABLE 3 test results of chemical resistance bear
Example 8: film formation process monitoring of surface film materials
10g of polymer nanoparticle aqueous dispersion A-3 is weighed and placed in a flask, 10g of deionized water with the mass ratio of 1:1 is added for dispersion, then 1g of cross-linking agent Aquolin 268, 0.3g of film forming additive dipropylene glycol monomethyl ether, 0.3g of wetting leveling agent BYK-333 and BYK-346 and 0.03g of defoaming agent TegoAirex 902W are added, stirring is carried out for 10min by using a magnetic stirrer at 800rpm, after full dispersion, 1g of polymer nanoparticle aqueous dispersion is weighed and dropped on the surface of a substrate, and then a wet film coater is used for horizontally scraping a film on the surface of a glass plate, and after moisture volatilizes, the surface film material B-6 is obtained.
And (3) dripping the material precursor on the surface of a probe of an attenuated total reflection-Fourier infrared spectrometer for experiments. The infrared spectrogram is acquired at a rate of 10 min/time in the first 12h, and the rest infrared spectrogram is acquired at a rate of 1 h/time. Characteristic peaks (2275-2250 cm) -1 ，1400-1350cm -1 ) And (3) comparing and analyzing, and drawing a change curve of isocyanate groups in the film forming process, so as to explore the film forming effect of the crosslinked film-formed material. The results are shown in FIG. 2. The isocyanate groups are consumed continuously over three days. Within the initial 10 hours, the reaction is rapid, the residual isocyanate content is rapidly reduced to below 40%, and then the reaction speed is gradually slowed down. After 3 days, the reaction was substantially completed and the residual amount of isocyanate groups<1%. The above results demonstrate that the material reacts further after curing to form a more dense structure; the residual amount of isocyanate is small, the potential toxicity of the material is reduced, and the feasibility of material molding is proved.
Example 9: preparation and application of surface film material on surfaces of various base materials and biological safety evaluation thereof
10g of polymer nanoparticle aqueous dispersion A-3 is weighed and placed in a flask, 10g of deionized water with the mass ratio of 1:1 is added for dilution and dispersion, then 1g of cross-linking agent Aquolin 268, 0.3g of film forming additive dipropylene glycol monomethyl ether, 0.3g of wetting leveling agent BYK-333 and BYK346, 0.03g of defoaming agent TegoAirex 902W are added, stirring is carried out for 10min by using a magnetic stirrer at 800rpm, after full dispersion, 1g of polymer nanoparticle aqueous dispersion is weighed and dropped on the surface of a substrate, and then a wet film coater is used for horizontally scraping films on the surfaces of nylon cloth, a glass plate, an engineering plastic alloy plate (ABs +PC), a thermoplastic polyester Plate (PET) and a carbon fiber plate, and standing is carried out, and after water is volatilized, surface film materials B-7, B-8, B-9, B-10 and B-11 are obtained, as shown in figure 3.
The material can form transparent hard films on the surfaces of five base materials, and has certain application value on the surfaces of most environmental instruments and building materials through physical and chemical property tests.
And determining possible residual impurities in the slow-release antibacterial surface film material. Membrane material B-7 was immersed in a beaker containing 2000mL of deionized water using a dialysis bag at 25 c, and stirred at 500 rpm. The soak was removed on day 7. And (3) measuring residual substances in the dialysate by utilizing HPLC, respectively testing samples which are possibly residual by utilizing HPLC, comparing peak shapes with peak positions, and calculating the residual quantity, so as to preliminarily judge the biosafety of the slow-release antibacterial material. Chromatographic column: c (C) 18 MP (2), 4.6X105 mm,5 μm; mobile phase: acetonitrile-water (90:10, v/v) gradient to 50:50; detection wavelength: 240nm/224nm; flow rate: 0.8mL/min; column temperature: 35 ℃; sample injection amount: 20. Mu.L.
The biosafety measurement results are shown in fig. 4 and table 4 below:
table 4 leachable test results in materials
Residual rate of cross-linking agent blended in material precursor after three days of complete curing<1, at the same time, the addition amounts of the film forming aids are low, and excessive dissolution of the rest of the film forming aids is not found in the detection process. Residual monomers and reactive surfactants in the polymerization process of the polymer nanoparticles are dissolved out in a small amount after 7 days of soaking. 1cm 2 Leachable content of material in water<0.04% of the monomer material is in a low level. This example 9 further demonstrates that the residual levels of various monomers, reactive surfactants, etc. are low within the material. The material is preliminarily proved to have certain biological safety.
Example 10: preparation of surface film material on surfaces of various base materials and slow-release antibacterial performance test thereof
10g of polymer nanoparticle aqueous dispersion A-3 is weighed and placed in a flask, 10g of deionized water with the mass ratio of 1:1 is added for dilution and dispersion, then 1g of cross-linking agent Aquolin268, 0.3g of film forming additive dipropylene glycol monomethyl ether, 0.3g of wetting leveling agent BYK-333 and BYK346 and 0.03g of defoaming agent Tego Airex 902W are added, stirring is carried out for 10min by using a magnetic stirrer at 800rpm, after full dispersion, 1g of polymer nanoparticle aqueous dispersion is weighed and dripped on the surface of a substrate, and then a wet film coater is used for horizontally scraping films on the surfaces of nylon cloth, a glass plate, an engineering plastic alloy plate (ABS+PC), a thermoplastic polyester Plate (PET) and a carbon fiber plate, and standing is carried out, and after water is volatilized, surface film materials B-12, B-13, B-14, B-15 and B-16 are obtained.
(1) Test of mold resistance:
the antibacterial test is carried out according to the antibacterial and mildew-proof wooden decorative board (JC/T2039-2010) and the film mildew resistance measuring method (GB/T1741-2020).
(a) Mold resistance tests were performed on the surface film materials B-12, B-13, B-14, B-15, B-16 using Aspergillus brasiliensis (Aspergillus brasiliensis, ATCC 16404), aspergillus niger (Aspergillus niger, CMCC 98003), penicillium citrinum (Penicillium citrinum, ATCC 1109), penicillium funiculosum (Penicillium funiculosum, CGMCC 3.3875), mucor racemosus (GDMCC 3.87) as experimental species. Transferring the preserved strain into PDA slant culture medium, culturing at 28deg.C for 12 days, with obvious mold layer on the surface, generating a large amount of spores, and taking out.
(b) Adding a small amount of sterile water into the cultured slant culture medium, slightly scraping surface mould spores by using an inoculating needle, transferring the mould spores into a conical flask, and adding about 50mL of Tween 80 physiological saline solution with the mass fraction of 0.05%. To this flask, 10 to 15 glass beads having a diameter of 5mm were added, and the flask was gently shaken for 15 minutes. Then, the glass funnel is plugged by absorbent cotton, filtered, counted and observed under a microscope by a blood cell counting plate, and stored for later use.
(c) 15mL of nutrient salt agar medium was added to a sterile petri dish (diameter 90 mm) and left to solidify. The blank sample and the sample are respectively paved on a culture medium, then 1mL of spore suspension is inoculated into 15mL of nutrient salt agar culture medium, after the mixture is uniformly mixed, the mixture is poured on the surfaces of the sample and a substrate, and then the culture is carried out at the temperature of 28 ℃ and the relative humidity of 92% RH. Each sample was run in 3 replicates.
(d) A negative control sample was placed on a sterile filter paper and the procedure was as described above in step 4. After 7 days of incubation under the same conditions, there should be apparent bacterial growth on the filter paper, otherwise the test should be considered ineffective.
(e) After 28 days, the surface mold growth was observed and the experimental results were recorded.
The results of the antifungal test are shown in FIG. 5 and Table 5:
TABLE 5 evaluation of test results for mold resistance
The surface of the filter paper in the negative control group grows to different degrees, different dominant strains grow in the three flat plates respectively, the mould layer on the surface of the filter paper is generated in a large quantity, the area of the mould layer is more than 70% of the total surface area of the filter paper, and the serious growth level is achieved. The surfaces of five blank control surfaces such as nylon cloth, glass plates, engineering plastic alloy plates (ABS+PC), thermoplastic polyester Plates (PET) and carbon fiber plates all have certain mold growth, obvious colonies appear at the edges, the interiors and the like of the material, the area of the colonies is more than 10% of the surface area of the blank control material, and the mold growth condition is in the 2-level or 3-level. The area of the surface of the experimental group material above 90% has no mould growth, and only part of the edges of the material have mould colonies; meanwhile, the growth of the peripheral mould is also restrained to a certain extent, and the mould growth basically reaches the 0 grade or 1 grade. Experimental results show that the material prepared by the experiment has a good anti-mildew effect and has a good inhibition effect on common mildew in the environment. After the material is molded and placed for one month, the material still has excellent antibacterial capability, and the antibacterial surface material is preliminarily proved to have a certain slow-release antibacterial effect.
(2) Antibacterial performance test:
the microorganism species which can grow in the use environments of instruments, building materials and the like are more, so that the daily application environment can be better simulated by adopting a mixed bacteria culture mode. The mixed culture of the escherichia coli and the staphylococcus aureus can simulate the mixed infection of microorganisms in real life, and is helpful to understand the interaction of the escherichia coli and the staphylococcus aureus in the co-growth environment and the influence of the interaction on a host. The experiment refers to an experiment method for the antibacterial property of plastic and plastic surfaces (GB/T31402-2015). Antibacterial detection is carried out on the surface film materials B-12, B-13, B-14, B-15 and B-16 by adopting a mixed culture mode of the two materials.
(a) The bacteria were pre-cultured and tested for antimycotic properties using E.coli (Escherichia coli, ATCC 6538) and Staphylococcus aureus (Staphylococcus aureus, ATCC 9739) as test species. The deposited strain was transferred to a slant medium and cultured at 35℃for 24 hours.
(b) Samples were prepared, comprising 12 sheets of slow release antimicrobial surface film material and untreated material attached to different substrates.
(c) Preparing inoculating solution, transferring the pre-cultured bacteria into 1/500NB culture solution, and diluting to bacteria concentration of 2.5X10 5 CFU/mL-10×10 5 CFU/mL.
(d) Inoculating the sample, placing the sample in a sterile culture dish, dripping the inoculating liquid onto the surface of the sample, covering a film and lightly pressing to diffuse the bacterial liquid, and then culturing for 24 hours at 35 ℃ under the condition of 95% relative humidity. And then recovering bacteria, recovering strains of the inoculated sample which is not subjected to antibacterial treatment, and fully flushing the sample.
(e) The number of viable bacteria was measured, and viable bacteria on the sample were counted after culturing according to the program. The number of viable bacteria was measured by plate culture, and the recovered solution was subjected to 10-fold gradient dilution, placed in sterile dishes, and then cultured at 35℃for 48 hours.
(f) As a result of the statistics, colonies were counted between 30.300 colonies, the number of colonies on each dilution dish was counted and 2 valid numbers were retained, and the dilution factor was recorded. Calculating the number of living bacteria, and calculating the number of living bacteria according to a formula (1).
Wherein:
n-sample per em 2 Viable count of (2);
average viable count of C-two culture medium surfaces;
d-dilution factor;
V-SCDLP medium for elution operation, mL;
a-surface area of film covered on surface of material, mm 2 。
The geometric mean of the number of viable bacteria recovered per set of samples was calculated and 2 significant digits were taken, and viable bacteria were counted as < V (volume of SCDLP broth used for elution, mL) if none of the agar plates had colonies at a certain dilution. When the average was calculated, if there were no bacteria at each dilution, it was recorded as V. For example: v=10 mL, and the average bacterial count was calculated to be 10.
(g) Calculation of antibacterial properties: in the case where the test is considered to be effective, the antibacterial property value is calculated by the formula (2).
R＝(U t -U 0 )-(A-U 0 )＝U t -A formula (2)
Wherein:
r-antibacterial property value;
U 0 log mean value of the number of bacteria immediately after inoculation of the sample without antibacterial treatment, CFU/cm 2 ；
U t Log mean value of bacterial count 24h after inoculation of the samples without antibacterial treatment, CFU/cm 2 ；
A-logarithmic average of bacterial count 24h after inoculation of antibacterial treated samples, CFU/cm 2 。
The antibacterial properties were tested as follows:
FIG. 6 shows the results of plate count culture at a dilution factor of 1, where the golden yellow colonies were Staphylococcus aureus and the white colonies were Escherichia coli. Under the same gradient, the test group grows almost aseptically, while the blank control group has obvious growth of staphylococcus aureus and escherichia coli.
TABLE 6 antibacterial Property values
The antibacterial property value was calculated based on the actual number of viable bacteria, and the calculation results are shown in table 6. The larger the value of the antibacterial property value, the stronger the antibacterial property is proved. The slow-release antibacterial surface film material has excellent antibacterial effect after being coated on the surfaces of five substrates, and has good experimental parallelism. The surface material used for 1 month still has excellent antibacterial effect, and further proves that the surface material has good slow-release antibacterial capability.
(3) And (3) slow release performance test:
after the antibacterial surface material is coated on the surface of the instrument, if the antibacterial surface material is used for a long time, the antibacterial surface material needs to have a certain lasting effect, so that the test of the slow release effect of the antibacterial surface material is particularly important. The water is dense and inseparable in the use process of the device, and the surface of the device is frequently wiped by the water, so that the slow release capability of the material can be laterally proved by exploring the medicine diffusion effect of the material in the water. Surface film material B-13 was immersed in a beaker containing 2000mL of deionized water using a dialysis bag at room temperature (25 c) and stirred at 500 rpm. And taking out the soaking solution at 0.5h, 1h, 2h, 3h, 4h, 8h, 16h, 24h, 36h, 48h, 72h, 4 days, 5 days, 6 days and 7 days, and replacing the dialyzate regularly. And testing the drug concentration in the soaking solution by using High Performance Liquid Chromatography (HPLC), preparing a slow release effect curve, and exploring the slow release effect. The experiment was repeated three times and the measurement results averaged. And calculating the accumulated released medicine amount according to a formula. The calculation formula of the accumulated drug release amount is as follows:
wherein:
E r -a cumulative drug release;
V e -displacement volume of water, mL;
V 0 -releasing the total volume of medium, mL;
C i -the concentration of the release liquid at the i-th displacement sampling;
m drug -the total mass of drug carried by the nanoparticle;
n-number of water changes.
Drug retention was measured by 7 day water dialysis and the results are shown in fig. 7. The medicine is slowly released within 7 days, the release rate is faster in the initial stage, and the medicine retention rate is reduced to below 90% within 2 days; and then its release rate gradually decreased, and its drug retention rate was 74.68% after 7 days. Preliminary proves that the composition has a certain medicine slow release effect in the environment.
According to the embodiment, the surface film materials on various base materials are subjected to the characterization of antibacterial property and slow release property, so that the antibacterial drug coated by the material can be mostly reserved within 7 days, and meanwhile, the antibacterial drug has excellent antibacterial and mildew-proof capabilities after 30 days.
Claims (8)
1. A polymer drug-loaded nanoparticle characterized by:
taking water as a dispersion medium; styrene, methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate are used as reaction monomers; one or two of non-reactive surfactant and reactive surfactant are used as surfactant; azo compounds are used as an initiator, emulsion polymerization is adopted to prepare polymer drug-loaded nanoparticle aqueous dispersion, and drugs are loaded in the polymerization process.
2. The polymeric drug-loaded nanoparticle of claim 1, wherein:
the preparation method comprises the following raw materials in percentage by mass: 0.2% -0.8% of styrene, 7% -12% of methyl methacrylate, 30% -35% of butyl methacrylate, 2% -7% of hydroxyethyl methacrylate, 0.1% -0.6% of antibacterial drugs, 0.5% -1.2% of initiator, 2% -3% of surfactant, 0.2% -0.5% of sodium bicarbonate, 0.01% -0.03% of redox system, 0.01% -0.03% of pH regulator and 50% -60% of deionized water;
the initiator is azobisisobutyronitrile or azobisisobutyronitrile hydrochloride;
the adopted surfactant is sodium dodecyl benzene sulfonate which is a non-reactive surfactant, and one or two of ADEKA REASAP SR-10 and ADEKA REASAP ER-30 which are reactive surfactants;
the redox system adopted comprises an oxidant and a reducing agent, wherein the oxidant is tert-butyl hydroperoxide, and the reducing agent is BRUGGOLITE FF6M;
the adopted pH regulator is dimethylethanolamine;
preferably, the antibacterial drug loaded by the polymer drug-loaded nano-particles is an organic matter with an antibacterial effect, wherein the range of log P of the organic matter is 0.5-6; more preferably, it is an organic substance having an antibacterial effect with a log P ranging from 1 to 3; most preferably, it is n-butyl-1, 2-benzisothiazolin-3-one (CAS 4299-07-4), iodopropynyl butylcarbamate (CAS 55406-53-6), 2-phenoxyethanol (CAS 122-99-6) or ethylparaben (CAS 120-47-8).
3. A preparation method of polymer drug-loaded nano-particles is characterized in that:
preparing a solution: adding part of emulsifier into water, sequentially adding monomer and antibacterial agent, and magnetically stirring at 600rpm for 3-12h to obtain stable monomer pre-emulsion A; preparing a part of initiator into a solution B with the mass concentration of 3% -5% by using deionized water; preparing solution C of sodium bicarbonate and partial emulsifier with deionized water; preparing a part of initiator into a solution D with the mass concentration of 2% -3% by using deionized water; preparing oxidant into solution E with mass concentration of 4% -6% by using deionized water; preparing a solution F with the mass concentration of 4% -6% by using deionized water as a reducing agent; preparing a pH regulator into a solution G with the mass concentration of 50% by using deionized water;
the reaction process comprises the following steps: adding a solution C into a 1L jacketed glass reaction kettle provided with a condensing tube, a thermometer and a stirring paddle, after nitrogen replacement, raising the reaction temperature to 85 ℃, and starting stirring; taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; continuously stirring for 20-30min; then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant speed over 3h 15 min; after the dripping is finished, the reaction temperature is reduced to 65 ℃, and simultaneously, the solution E and the solution F are dripped, and the dripping is finished within 30min; after the dripping is finished, the reaction temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 10min, the pH value is 8-9, and the polymer drug-loaded nanoparticle aqueous dispersion is obtained after passing through a 200-mesh filter screen.
4. The coating prepared by using the polymer drug-loaded nanoparticle as a main raw material according to claim 1, wherein:
the main formula takes water as a dispersion medium; taking the polymer nano-particle water dispersion as a formula main body; (2, 4, 6-trioxytriazine-1, 3,5 (2H, 4H, 6H) -tri-group) tri (hexamethylene) isocyanate is used as a cross-linking agent; alcohol ether substances are used as film forming auxiliary agents, and wetting leveling agents and defoaming agents are added.
5. The coating of claim 4, wherein:
the preparation method comprises the following raw materials in percentage by mass: 50% of polymer nanoparticle aqueous dispersion, 5% of cross-linking agent, 1.5% of film forming auxiliary agent, 0.3% of wetting leveling agent, 0.3% of defoaming agent and 50% of deionized water;
the cross-linking agent used was aqualin 268;
the adopted film forming additive is dipropylene glycol monomethyl ether;
the adopted wetting leveling agent is one or two of BYK-333 or BYK-346;
the defoamer used was Tego Airex 902W.
6. The slow-release antibacterial surface film material prepared by the coating of claim 4, which is characterized in that:
the polymer nanoparticle aqueous dispersion was weighed into a flask and added in a mass ratio of 1:1, adding 5% of a cross-linking agent, 1.5% of a film forming auxiliary agent, 0.3% of a wetting leveling agent and 0.03% of a defoaming agent, stirring for 10min by using a magnetic stirrer at 800rpm, weighing 1g of the solution after full dispersion, dripping the solution on the surface of a substrate, horizontally scraping a film on the surface of the substrate by using a wet film coater, standing, and volatilizing water to obtain a surface film material; the addition ratio of each auxiliary agent is the ratio of the mass of the auxiliary agent to the mass of the polymer nano particle water dispersion after water dilution.
7. The slow release antimicrobial surface film material of claim 6, wherein:
suitable substrates include wood, metal, plastic, glass and carbon fiber; preferably, suitable substrates include nylon cloth, glass sheets, engineering plastic alloy sheets (abs+pc), thermoplastic polyester sheets (PET), and carbon fiber sheets.
8. The slow release antimicrobial surface film material of claim 6, wherein:
can be applied to the surfaces of instruments, appliances and building materials which are common in environments including but not limited to living environments, medical environments and the like.
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