CN115216039A - Preparation method and application of degradable antibacterial film - Google Patents
Preparation method and application of degradable antibacterial film Download PDFInfo
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- CN115216039A CN115216039A CN202210994106.2A CN202210994106A CN115216039A CN 115216039 A CN115216039 A CN 115216039A CN 202210994106 A CN202210994106 A CN 202210994106A CN 115216039 A CN115216039 A CN 115216039A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001661 Chitosan Polymers 0.000 claims abstract description 71
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 71
- 108010010803 Gelatin Proteins 0.000 claims abstract description 68
- 239000008273 gelatin Substances 0.000 claims abstract description 68
- 229920000159 gelatin Polymers 0.000 claims abstract description 68
- 235000019322 gelatine Nutrition 0.000 claims abstract description 68
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 62
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 229940048102 triphosphoric acid Drugs 0.000 claims abstract description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000005022 packaging material Substances 0.000 claims abstract description 6
- 239000003814 drug Substances 0.000 claims abstract description 5
- 238000013268 sustained release Methods 0.000 claims abstract description 4
- 239000012730 sustained-release form Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 164
- 239000002245 particle Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 230000003385 bacteriostatic effect Effects 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 14
- 101710134784 Agnoprotein Proteins 0.000 claims description 10
- 239000001226 triphosphate Substances 0.000 claims description 10
- 235000011178 triphosphate Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000002522 swelling effect Effects 0.000 abstract description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000000338 in vitro Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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Abstract
The invention discloses a preparation method and application of a degradable antibacterial film, wherein a gelatin solution containing silver nanoparticles is prepared by an ultraviolet radiation reduction method, then an ion crosslinking method is adopted, a graphene oxide dispersion solution is added into a carboxymethyl chitosan solution, then triphosphoric acid is added to prepare a carboxymethyl chitosan graphene oxide composite solution, finally the gelatin solution containing silver nanoparticles is added into the carboxymethyl chitosan graphene oxide composite solution for full reaction, then a tetrafluoroethylene plate is coated, and a film material with good swelling property, thermal stability, biocompatibility, degradability and antibacterial property is obtained by drying and film forming, and the degradable antibacterial film material can be applied to the field of packaging materials or drug sustained-release materials.
Description
The technical field is as follows:
the invention relates to the technical field of functional materials, in particular to a preparation method and application of a degradable antibacterial film.
The background art comprises the following steps:
carboxymethyl chitosan (CMCS) is a novel amphoteric biopolymer, and is widely used in the fields of drug encapsulation, food, tissue engineering, cosmetics, oxidation resistance, and antibiosis, due to its characteristics of non-toxicity, antibiosis, easy film formation, biodegradability, and biocompatibility.
However, CMCS alone hardly meets the requirement of bacteriostatic activity. Therefore, mineral nanoparticles or metal oxides and metal nanoparticles are introduced to improve the bacteriostatic activity. In addition, silver and silver oxide also have unique physical and chemical properties, are potential materials and are often compounded with CMCS to improve the bacteriostatic activity.
At present, some researches report the synthesis of CMCS-Ag and CMCS-AgO-Ag antibacterial materials, and the synthesis is applied to the fields of sewage treatment, packaging materials, drug delivery systems and the like. The adopted methods comprise a microwave reduction method, a chemical reduction method and the like, the process is complex, and chemical substance pollution exists.
The invention content is as follows:
the invention aims to provide a preparation method and application of a degradable antibacterial film, wherein a gelatin solution containing silver nanoparticles is prepared by an ultraviolet radiation reduction method, then an ion crosslinking method is adopted, a graphene oxide dispersion solution is added into a carboxymethyl chitosan solution, triphosphoric acid is added to prepare a carboxymethyl chitosan graphene oxide composite solution, finally the gelatin solution containing silver nanoparticles is added into the carboxymethyl chitosan graphene oxide composite solution to be fully reacted, then the mixture is coated on a tetrafluoroethylene plate, and the film is dried to form a film, so that the film material with better swelling property, thermal stability, biocompatibility, degradability and antibacterial property is obtained, and the film material can be applied to the field of packaging materials or drug sustained-release materials.
The invention is realized by the following technical scheme:
a preparation method of a degradable bacteriostatic film comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring to completely dissolve the gelatin to obtain a gelatin solution;
2) AgNO is added 3 Dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and placing the solution into an ultraviolet irradiation instrument for ultraviolet reduction to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution;
4) Adding graphene oxide into deionized water, and performing ultrasonic treatment to obtain a dispersed graphene oxide solution;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 10-50:50-90:1;
6) Slowly adding the gelatin solution containing the nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, and stirring at 30-60 ℃ until the mixture is uniformly mixed to obtain a mixed solution; the volume ratio of the gelatin solution containing the nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is (1);
7) And (3) pouring the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at 30-50 ℃ to obtain the degradable antibacterial film.
Preferably, the reduction time of step 2) is 1 to 12 hours.
Preferably, the mass concentration of the gelatin solution is 0.5 to 5wt%, more preferably 0.5 to 3wt%; agNO 3 The mass of (b) is 0 mass of the gelatin.1-1%, more preferably 0.1-0.5%; the mass concentration of the carboxymethyl chitosan in the carboxymethyl chitosan solution is 0.5-5wt%, and more preferably 0.5-3wt%; the mass concentration of the graphene oxide in the graphene oxide solution is 0.5-3mg/mL, more preferably 0.5-1.5mg/mL, and most preferably 1mg/mL; the concentration of the triphosphate in the triphosphate solution is 0.5-3mg/mL, more preferably 0.5-1.5mg/mL, and most preferably 1mg/mL.
Preferably, the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphate solution is 50:50:1.
the invention also protects the application of the degradable antibacterial film obtained by the preparation method, and the degradable antibacterial film can be used as an antibacterial packaging material or a sustained-release drug-loading material and applied to the fields of food or medicine.
The invention has the following beneficial effects:
1) The method comprises the steps of adding a graphene oxide dispersion solution into a carboxymethyl chitosan solution according to a proportion by adopting an ion crosslinking method, uniformly mixing, and adding triphosphoric acid, wherein a 4,4' -dimethyltriphenylmethane-2, 2', 5' -tetraisocyanate crosslinking agent is not required, and the method is safe and pollution-free organic solvent.
2) The method adopted by the invention is green and simple, and the prepared degradable film material has better swelling property, thermal stability and antibacterial property, can be used as a packaging material or a slow-release carrier material, and has important significance.
Description of the drawings:
FIG. 1 is a transmission electron microscope picture and a particle size distribution diagram of the degradable bacteriostatic thin film AgO/Ag/CMCS-GO-1h obtained in example 1.
FIG. 2 is a transmission electron microscope picture and a particle size distribution diagram of the degradable bacteriostatic film AgO/Ag/CMCS-GO-6h obtained in example 2.
FIG. 3 is a transmission electron microscope picture and a particle size distribution diagram of the degradable bacteriostatic film AgO/Ag/CMCS-GO-12h obtained in example 3.
FIG. 4 is a transmission electron microscope picture and a particle size distribution diagram of the degradable bacteriostatic film AgO/Ag/CMCS-GO-24h obtained in example 4.
Fig. 5 is a graph of thermal stability of the degradable bacteriostatic film materials obtained in examples 1-4 and comparative example 1.
Fig. 6 is a swelling chart of the degradable bacteriostatic film materials obtained in examples 1-4.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: preparation method of degradable antibacterial film
The method comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring until the gelatin is completely dissolved to obtain a gelatin solution with the mass concentration of 0.5 wt%;
2) Mixing AgNO with gelatin 0.1 wt% 3 Preparing a solution, dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and putting the solution into an ultraviolet irradiation instrument for ultraviolet reduction for 1 hour to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution with the mass concentration of 0.5 wt%;
4) Adding graphene oxide into deionized water, and carrying out ultrasonic treatment for 30min to obtain a dispersed graphene oxide solution with the mass concentration of 0.5mg/mL;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 50:50:1;
6) Slowly adding a gelatin solution containing nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, stirring at 40 ℃ until the mixture is uniformly mixed to obtain a mixed solution, wherein the volume ratio of the gelatin solution containing nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is 1;
7) And (3) casting the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at 35 ℃ to obtain the degradable antibacterial film.
Comparative example 1:
reference example 1, except that no graphene oxide solution was added.
The method comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring until the gelatin is completely dissolved to obtain a gelatin solution with the mass concentration of 0.5 wt%;
2) Mixing AgNO with gelatin 0.1 wt% 3 Preparing a solution, dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and putting the solution into an ultraviolet irradiation instrument for ultraviolet reduction for 1 hour to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution with the mass concentration of 0.5 wt%;
4) Slowly adding the gelatin solution containing the nano-silver particles into the carboxymethyl chitosan solution, and stirring at 40 ℃ until the gelatin solution containing the nano-silver particles and the carboxymethyl chitosan solution are uniformly mixed to obtain a mixed solution, wherein the volume ratio of the gelatin solution containing the nano-silver particles to the carboxymethyl chitosan solution is 1;
5) And (3) casting the mixed solution obtained in the step 4) on a tetrafluoroethylene plate, and drying for 24 hours at 35 ℃ to obtain the degradable antibacterial film.
Example 2: preparation method of degradable antibacterial film
The method comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring until the gelatin is completely dissolved to obtain a gelatin solution with the mass concentration of 2 wt%;
2) AgNO with the mass of 0.2 percent of gelatin mass 3 Preparing a solution, dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and putting the solution into an ultraviolet irradiation instrument for ultraviolet reduction for 6 hours to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution with the mass concentration of 2 wt%;
4) Adding graphene oxide into deionized water, and carrying out ultrasonic treatment for 30min to obtain a dispersed graphene oxide solution with the mass concentration of 1mg/mL;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 50:50:1;
6) Slowly adding a gelatin solution containing nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, and stirring at 40 ℃ until the gelatin solution containing nano-silver particles and the carboxymethyl chitosan graphene oxide composite solution are uniformly mixed to obtain a mixed solution, wherein the volume ratio of the gelatin solution containing nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is 1;
7) And (3) casting the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at 35 ℃ to obtain the degradable antibacterial film.
Example 3: preparation method of degradable antibacterial film
The method comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring until the gelatin is completely dissolved to obtain a gelatin solution with the mass concentration of 2 wt%;
2) AgNO with the mass of 0.2 percent of gelatin mass 3 Preparing a solution, dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and putting the solution into an ultraviolet irradiation instrument for ultraviolet reduction for 12 hours to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution with the mass concentration of 2 wt%;
4) Adding graphene oxide into deionized water, and performing ultrasonic treatment for 30min to obtain a dispersed graphene oxide solution with the mass concentration of 1mg/mL;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 50:50:1;
6) Slowly adding a gelatin solution containing nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, stirring at 40 ℃ until the mixture is uniformly mixed to obtain a mixed solution, wherein the volume ratio of the gelatin solution containing nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is 1;
7) And (3) casting the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at 35 ℃ to obtain the degradable antibacterial film.
Example 4: preparation method of degradable antibacterial film
The method comprises the following steps:
1) Dissolving gelatin in deionized water, and stirring until the gelatin is completely dissolved to obtain a gelatin solution with the mass concentration of 5wt%;
2) AgNO with the mass of 1 percent of gelatin mass 3 Preparing a solution, dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and putting the solution into an ultraviolet irradiation instrument for ultraviolet reduction for 24 hours to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution with the mass concentration of 5wt%;
4) Adding graphene oxide into deionized water, and carrying out ultrasonic treatment for 30min to obtain a dispersed graphene oxide solution with the mass concentration of 1mg/mL;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 50:50:1;
6) Slowly adding a gelatin solution containing nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, stirring at 40 ℃ until the mixture is uniformly mixed to obtain a mixed solution, wherein the volume ratio of the gelatin solution containing nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is 1;
7) And (3) casting the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at 35 ℃ to obtain the degradable antibacterial film.
Example 5: performance testing
The following performance tests were performed on the degradable bacteriostatic film materials prepared in examples 1-4.
1. Transmission electron microscopy testing
And detecting the size and size distribution of the nano-silver particles in the degradable antibacterial film material through a transmission electron microscope. The test results are shown in FIGS. 1-4.
2. Thermal performance testing
Thermogravimetric analysis was used for testing. The thermal performance results of the degradable bacteriostatic film materials prepared in examples 1-4 and comparative example 1 are shown in fig. 5.
3. Swelling test
The hydrogel material was placed in a centrifuge tube, deionized water and a PBS solution with pH =7.4 were added, respectively, and immersed in a 37 ℃ shaking water bath for 24 hours. After 24 hours, the sample was removed and weighed after wiping the surface moisture with filter paper. The water absorption and swelling properties of the samples were calculated according to the formulas, and the results are shown in FIG. 6.
Swelling ratio = (W) t -W 0 )/W 0 ×100％
W t Weight of sample in t time, W 0 Initial weight of sample.
4. In vitro bacterial inhibition test
Adopting escherichia coli and staphylococcus aureus as simulated bacteria, respectively adding 0.1mL of escherichia coli and staphylococcus aureus suspension diluted to 107cfu/mL into a sterile agar culture medium, fully and uniformly mixing the escherichia coli and staphylococcus aureus suspension, flatly paving an antibacterial film wafer with the diameter of 10mm on the surface of the culture medium, detecting the antibacterial effect of the film, culturing for 24 hours at 37 ℃, and observing and recording the diameter of an antibacterial zone of the film. The results of the radius data of the zone of inhibition are shown in table 1.
TABLE 1
From the above results, it can be seen that:
the average particle size of the AgO/Ag/CMCS-GO-1h material obtained in example 1 is 9.43nm, and most of the average particle size is distributed in the range of 8-10nm. Has better thermal stability and swelling property. The diameter of the in vitro bacteriostatic ring is 4.1mm of escherichia coli and 4.5mm of staphylococcus aureus.
The average particle size of the AgO/Ag/CMCS-GO-6h material obtained in example 2 is 5.34nm, and most of the average particle size is distributed in the range of 4-6nm.
Has better thermal stability and swelling property. The diameter of the in vitro bacteriostatic ring is 5.3mm of escherichia coli and 5.5mm of staphylococcus aureus.
The AgO/Ag/CMCS-GO-12h material obtained in example 3 has a minimum average particle size of 4.72nm, and the majority is distributed in the range of 4-5nm. Has the best thermal stability and swelling property. The in vitro bacteriostatic activity is best, the diameter of the in vitro bacteriostatic ring is 5.8mm of escherichia coli, and the diameter of staphylococcus aureus is 6.3mm.
The average particle size of the AgO/Ag/CMCS-GO-12h material obtained in example 4 is 7.01nm, and most of the average particle size is distributed in the range of 4-6nm. Has the best thermal stability and swelling property. The diameter of the in vitro bacteriostatic ring is 5.6mm of escherichia coli and 5.8mm of staphylococcus aureus, the ultraviolet reduction time is long, so that Ag nano particles are agglomerated and are large, and the bacteriostatic activity of the material is reduced.
Comparing example 1 with comparative example 1, it can be seen that: the addition of graphene oxide increased the bacteriostatic activity but decreased the thermal stability, see table 1 and fig. 5.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The preparation method of the degradable bacteriostatic film is characterized by comprising the following steps of:
1) Dissolving gelatin in deionized water, and stirring to completely dissolve the gelatin to obtain a gelatin solution;
2) Mixing AgNO 3 Dropwise adding the solution into the gelatin solution, continuously stirring until the solution is uniformly mixed, and placing the solution into an ultraviolet irradiation instrument for ultraviolet reduction to obtain the gelatin solution containing nano silver particles;
3) Dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution;
4) Adding graphene oxide into deionized water, and performing ultrasonic treatment to obtain a dispersed graphene oxide solution;
5) Adding a triphosphoric acid solution into the carboxymethyl chitosan solution and the graphene oxide solution, and stirring to obtain a carboxymethyl chitosan graphene oxide composite solution; the volume ratio of the carboxymethyl chitosan solution to the graphene oxide solution to the triphosphoric acid solution is 10-50:50-90:1;
6) Slowly adding the gelatin solution containing the nano-silver particles into the carboxymethyl chitosan graphene oxide composite solution, and stirring at 30-60 ℃ until the mixture is uniformly mixed to obtain a mixed solution; the volume ratio of the gelatin solution containing the nano-silver particles to the carboxymethyl chitosan graphene oxide composite solution is (1);
7) And (3) pouring the mixed solution obtained in the step 6) on a tetrafluoroethylene plate, and drying for 24 hours at the temperature of 30-50 ℃ to obtain the degradable antibacterial film.
2. The method according to claim 1, wherein the reduction time in the step 2) is 1 to 12 hours.
3. The process according to claim 1, wherein the mass concentration of the gelatin solution is 0.5 to 5wt%; agNO 3 The mass of the gelatin is 0.1-1% of the mass of the gelatin; the mass concentration of the carboxymethyl chitosan in the carboxymethyl chitosan solution is 0.5-5wt%; the mass concentration of the graphene oxide in the graphene oxide solution is 0.5-3mg/mL; the concentration of the triphosphate in the triphosphate solution is 0.5-3mg/mL.
4. The process according to claim 1, wherein the mass concentration of the gelatin solution is 0.5 to 3wt%; agNO 3 The mass of the gelatin is 0.1-0.5% of the mass of the gelatin; the mass concentration of the carboxymethyl chitosan in the carboxymethyl chitosan solution is 0.5 to 3 weight percent; the mass concentration of the graphene oxide in the graphene oxide solution is 0.5-1.5mg/mL; the concentration of the triphosphate in the triphosphate solution is 0.5-1.5mg/mL.
5. The preparation method according to claim 1, wherein the mass concentration of graphene oxide in the graphene oxide solution is 1mg/mL; the concentration of triphosphate in the triphosphate solution was 1mg/mL.
6. The preparation method according to claim 1, wherein the volume ratio of the carboxymethyl chitosan solution, the graphene oxide solution and the triphosphate solution is 50:50:1.
7. the application of the degradable antibacterial film prepared by the preparation method according to any one of claims 1 to 6 is characterized in that the degradable antibacterial film is used as an antibacterial packaging material or a sustained-release drug-loading material in the fields of food or medicine.
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