CN114316379A - Degradable antibacterial antioxidant film and preparation method thereof - Google Patents

Degradable antibacterial antioxidant film and preparation method thereof Download PDF

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CN114316379A
CN114316379A CN202210030835.6A CN202210030835A CN114316379A CN 114316379 A CN114316379 A CN 114316379A CN 202210030835 A CN202210030835 A CN 202210030835A CN 114316379 A CN114316379 A CN 114316379A
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volatile oil
solution
zein
film
homogenizing
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CN114316379B (en
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明良山
李哲
刘红宁
江晓霞
董子舒
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Jiangxi University of Traditional Chinese Medicine
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Abstract

The invention discloses a degradable antibacterial antioxidant film and a preparation method thereof, relating to the technical field of preservative films, wherein the degradable antibacterial antioxidant film is prepared from the following raw materials in percentage by weight: the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is (0.8-1.2): (0.8-1.2): (0.8-1.2): (0.4-0.6); the preparation method of the degradable antibacterial antioxidant film comprises the following steps of S1: preparing volatile oil: s2: preparation of chitosan solution and zein solution: s3: embedding volatile oil with zein; s4: preparing a film: by adopting the biodegradable zein solution and the chitosan as the base materials of the film, the environmental problems of white pollution caused by discarding the traditional film, air pollution caused by burning and the like are solved, and the antibacterial and antioxidant functions of the film are enhanced by adopting the volatile oil, so that the food spoilage and rancidity are delayed.

Description

Degradable antibacterial antioxidant film and preparation method thereof
Technical Field
The invention relates to the technical field of preservative films, in particular to a degradable antibacterial antioxidant film and a preparation method thereof.
Background
The food safety problem is always a major global sanitary problem, which directly concerns the life health of people and is also a hot topic of social attention at home and abroad. With the improvement of water quality of people's life, people pay more and more attention to the safety of stored food, and the research on food preservation technology is a hot problem of research in recent years. The food preservative film preservation technology is concerned more and more, the traditional preservative film is often made of petroleum products such as polyethylene and polyvinyl alcohol, and due to the characteristic of difficult degradation, the traditional preservative film is easy to cause environmental problems such as white pollution, and in addition, the incineration of the film can release a large amount of carbon dioxide gas, and the greenhouse effect of the earth can be aggravated to a certain extent. In this respect, the development of novel degradable preservative films is gradually becoming the development direction of preservative films. The petroleum-based preservative film still accounts for the major market at present, and the main defects of the petroleum-based preservative film are easy environmental pollution and lack of functionality. At present, the research and development of novel film materials and film functionality are rapid, but the problems of single function, complex production and preparation process and the like generally exist.
The volatile oil is an oily liquid with volatility distilled with water vapor, has special fragrance, and is mainly present in plants of Labiatae, Umbelliferae, Compositae, Rutaceae, Zingiberaceae, etc. The essential oil mainly comprises aliphatic compounds, aromatic compounds and the like, has strong biological activities such as antibiosis, antioxidation and the like, and is widely used in the fields of medicines, foods and the like. Meanwhile, essential oils are considered to be generally safe and have been widely added to foods and medicines.
However, volatile oil has the characteristics of instability, volatility and the like, is sensitive to light, heat and air, is volatile after long-term exposure, is oxidized and deteriorated, and the like, so that related effects and functions are lost, and the application of the volatile oil is limited. Therefore, in order to increase the stability of the volatile oil, a certain technical means, such as inclusion, emulsification, encapsulation and the like, is adopted to stabilize the volatile oil in a carrier material, so as to realize the activity and the action of the volatile oil.
Based on the attention on environment and food safety at home and abroad, although volatile oil is reported to be integrated into the degradable film, the existing integrated antibacterial degradable film has complex process and needs a plurality of working procedures; or adding the volatile oil directly into the film. The cost is too high due to the complex process, the volatile oil is directly added into the film, and the volatile oil is easy to volatilize in the subsequent drying process of the film due to the heat instability of the volatile oil; volatile oils volatilize, resulting in unsmooth, even perforated film surfaces, which limits the application of the film.
Disclosure of Invention
In view of the above, the present invention provides a degradable antibacterial and antioxidant thin film and a preparation method thereof, aiming at the defects existing in the prior art, wherein the degradable antibacterial and antioxidant thin film adopts a biologically regenerated and degradable zein solution and chitosan as base materials of the thin film, so as to solve the environmental problems of 'white pollution' caused by discarding the traditional thin film and air pollution caused by burning; the volatile oil is adopted to enhance the antibacterial and antioxidant functions of the film, and the food spoilage and rancidity are delayed.
In order to achieve the purpose, the invention adopts the following technical scheme:
a degradable antibacterial antioxidant film is prepared from the following raw materials in percentage by weight: the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is (0.8-1.2): (0.8-1.2): (0.8-1.2): (0.4-0.6).
As a preferred embodiment: the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is 1: 1: 1: 0.6.
as a preferred embodiment: the volatile oil is elsholtzia splendens.
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: putting the medicinal materials containing the volatile oil into a volatile oil extractor, adding 6-10 times of water by weight, and heating, distilling and extracting for 2-8 h; stopping heating to obtain water layer and volatile oil layer, respectively, adding desiccant into volatile oil layer, dehydrating and drying to obtain volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into acetic acid solution, stirring to form transparent chitosan solution, centrifuging and filtering insoluble substances, and taking the upper layer chitosan solution for later use; dissolving zein in ethanol solution, stirring to form transparent zein solution, centrifuging and filtering insoluble substances, and taking upper zein solution for later use;
s3: embedding volatile oil with zein;
s4: preparing a film: adding chitosan and glycerol solution into the product obtained after the volatile oil is embedded in the S3 zein, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; pouring the film forming solution into a culture dish, carrying out vacuum degassing on the film forming solution in the culture dish, and drying for 36 hours in a drying oven at the temperature of 30-50 ℃ to obtain the film.
As a preferred embodiment: and the zein embedded volatile oil in the S3 is formed into nano-emulsion embedded volatile oil or nano-particle embedded volatile oil.
As a preferred embodiment: the specific steps for forming the nanoemulsion embedded volatile oil are as follows: dropwise adding the upper-layer zein solution obtained in the step S2 into ultrapure water, homogenizing while dropwise adding, and separating out zein nanoparticles from the zein solution; and (4) adding the volatile oil obtained in the step (S1) into the zein nanoparticles, dripping while homogenizing, and adsorbing the zein nanoparticles on the surfaces of the volatile oil droplets to form the nanoemulsion embedded volatile oil.
As a preferred embodiment: the homogenizing rotation speed is 10000rpm-15000rpm, the homogenizing time is 5min-30min, and the weight ratio of the volatile oil to the zein nanoparticles is 0-1.5.
As a preferred embodiment: the specific steps for forming the nanoparticle embedded volatile oil are as follows: adding the volatile oil obtained in the step S1 into the upper-layer corn protein solution obtained in the step S2, wherein the weight ratio of the volatile oil to the corn protein solution is 0-1.5, homogenizing while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the corn protein solution are fully dissolved to form a uniform solution; dripping the solution into ultrapure water while homogenizing at 13000rpm for 5-30 min to obtain volatile oil and zein insoluble in water, and precipitating nanoparticles to obtain nanoparticle-embedded volatile oil.
As a preferred embodiment: the mass concentration of the acetic acid solution in the S2 is 1% -5%, the mass concentration of the chitosan solution is 1% -5%, the volume concentration of the ethanol solution is 70% -90%, and the mass concentration of the formed corn protein solution is 1% -5%.
As a preferred embodiment: and the drying agent in the S1 is anhydrous sodium sulfate or anhydrous calcium sulfate.
Compared with the prior art, the invention has the obvious advantages and beneficial effects that:
1. the film is made of a biologically regenerated and degradable corn protein solution and chitosan, so that the environmental problems of white pollution caused by discarding the traditional film, air pollution caused by burning and the like are solved, and meanwhile, the safety of the packaging material is greatly improved;
2. the volatile oil is adopted to enhance the antibacterial and antioxidant functions of the film, delay food spoilage and rancidity and solve the problems of food safety and food waste to a certain extent;
3. the preparation method provided by the invention overcomes the technical problem of complex production process of the degradable antibacterial antioxidant film in the prior art; meanwhile, the problem that volatile oil is directly added into the film in the prior art and is easy to volatilize in the subsequent drying process of the film due to the heat instability of the volatile oil is solved; the degradable antibacterial antioxidant film provided by the invention has the advantages of smooth surface, high tensile strength and better antibacterial antioxidant effect.
To more clearly illustrate the structural features and effects of the present invention, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Drawings
FIG. 1 is a graph showing the change of transmittance with wavelength of films obtained in examples 1 to 6 of the present invention and a comparative example;
FIG. 2 is a scanning electron microscope image of the surface topography of a comparative example film of the present invention;
FIG. 3 is a scanning electron micrograph of a broken cross section of a comparative example film of the present invention;
FIG. 4 is a scanning electron microscope image of the surface topography of the film of example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the surface topography of the film of example 2 of the present invention;
FIG. 6 is a SEM of a broken cross section of a film in example 2 of the present invention;
FIG. 7 is a scanning electron microscope image of the surface topography of the film of example 3 of the present invention;
FIG. 8 is a scanning electron microscope image of the surface topography of the film of example 4 of the present invention;
FIG. 9 is a scanning electron microscope image of the surface topography of the thin film of example 5 in accordance with the present invention;
FIG. 10 is a SEM of a broken cross section of a thin film of example 5 of the present invention;
FIG. 11 is a scanning electron microscope image of the surface topography of the film of example 6 of the present invention;
FIG. 12 is a graph showing the results of oxidation resistance of the films obtained in examples 1 to 6 of the present invention and comparative example.
Detailed Description
As shown in fig. 1 to 12, the invention provides a degradable antibacterial antioxidant film, which is prepared from the following raw materials in percentage by weight: the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is (0.8-1.2): (0.8-1.2): (0.8-1.2): (0.4-0.6).
The weight ratio of the chitosan to the zein to the volatile oil to the glycerol is 1: 1: 1: 0.6.
the volatile oil is elsholtzia splendens.
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: putting the medicinal materials containing the volatile oil into a volatile oil extractor, adding 6-10 times of water by weight, and heating, distilling and extracting for 2-8 h; stopping heating to obtain water layer and volatile oil layer, respectively, adding desiccant into volatile oil layer, dehydrating and drying to obtain volatile oil; wherein, the drying agent is anhydrous sodium sulfate or anhydrous calcium sulfate;
s2: preparation of chitosan solution and zein solution: adding chitosan into acetic acid solution, stirring to form transparent chitosan solution, centrifuging and filtering insoluble substances, and taking the upper layer chitosan solution for later use; dissolving zein in ethanol solution, stirring to form transparent zein solution, centrifuging and filtering insoluble substances, and taking upper zein solution for later use; wherein, the mass concentration of the acetic acid solution is 1 to 5 percent, the mass concentration of the chitosan solution is 1 to 5 percent, the volume concentration of the ethanol solution is 70 to 90 percent, and the mass concentration of the zein solution is 1 to 5 percent.
S3: embedding volatile oil with zein;
s3, embedding the volatile oil with zein to form nano-emulsion embedded volatile oil, which comprises the following steps: dropwise adding the upper-layer zein solution obtained in the step S2 into ultrapure water, homogenizing while dropwise adding, and separating out zein nanoparticles from the zein solution; adding the volatile oil obtained in the step S1 into the zein nanoparticles, wherein the weight ratio of the volatile oil to the zein nanoparticles is 0-1.5; homogenizing while dripping, adsorbing zein nanoparticles on the surface of volatile oil droplet to form nanoemulsion embedded volatile oil, wherein the homogenizing speed is 10000rpm-15000rpm, and the homogenizing time is 5min-30 min.
S3, the corn protein embedding volatile oil forms nanoparticle embedding volatile oil, and the specific steps of forming the nanoparticle embedding volatile oil are as follows: adding the volatile oil obtained in the step S1 into the upper-layer corn protein solution obtained in the step S2, wherein the weight ratio of the volatile oil to the corn protein solution is 0-1.5, homogenizing while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the corn protein solution are fully dissolved to form a uniform solution; dripping the solution into ultrapure water while homogenizing at 13000rpm for 5-30 min to obtain volatile oil and zein insoluble in water, and precipitating nanoparticles to obtain nanoparticle-embedded volatile oil.
S4: preparing a film: adding chitosan and glycerol solution into the product obtained after the volatile oil is embedded in the S3 zein, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; pouring the film forming solution into a culture dish, carrying out vacuum degassing on the film forming solution in the culture dish, and drying for 36 hours in a drying oven at the temperature of 30-50 ℃ to obtain the film.
Example 1
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nano-emulsion embedded volatile oil: dripping the upper-layer corn protein solution obtained from 30mLS2 into 120mL of ultrapure water, and homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5min, and the corn protein solution is separated out corn protein nanoparticles; and (4) adding the volatile oil obtained in the step (S1) into the zein nanoparticles, wherein the weight ratio of the volatile oil to the zein is 0.5, homogenizing is carried out while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the zein nanoparticles are adsorbed on the surfaces of the volatile oil droplets to form the nanoemulsion embedded volatile oil.
S4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoemulsion embedded volatile oil formed in S3, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Example 2
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nano-emulsion embedded volatile oil: dripping the upper-layer corn protein solution obtained from 30mLS2 into 120mL of ultrapure water, and homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5min, and the corn protein solution is separated out corn protein nanoparticles; and (4) adding the volatile oil obtained in the step (S1) into the zein nanoparticles, wherein the weight ratio of the volatile oil to the zein is 1, homogenizing is carried out while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the zein nanoparticles are adsorbed on the surfaces of the volatile oil droplets to form the nanoemulsion embedded volatile oil.
S4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoemulsion embedded volatile oil formed in S3, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Example 3
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nano-emulsion embedded volatile oil: dripping the upper-layer corn protein solution obtained from 30mLS2 into 120mL of ultrapure water, and homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5min, and the corn protein solution is separated out corn protein nanoparticles; and (4) adding the volatile oil obtained in the step (S1) into the zein nanoparticles, wherein the weight ratio of the volatile oil to the zein is 1.5, homogenizing is carried out while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the zein nanoparticles are adsorbed on the surfaces of the volatile oil droplets to form the nanoemulsion embedded volatile oil.
S4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoemulsion embedded volatile oil formed in S3, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Example 4
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nanoparticle embedded volatile oil: adding the volatile oil obtained from 30mLS1 into the upper layer zein solution obtained from S2, wherein the weight ratio of the volatile oil to the zein solution is 0.5, homogenizing while dripping, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the zein solution are fully dissolved to form a uniform solution; dripping the solution into 120mL of ultrapure water, homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5, and the volatile oil and the zein are both insoluble in water and precipitate nanoparticles to form nanoparticle-embedded volatile oil.
S4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoparticle-embedded volatile oil formed in S3, and homogenizing at 13000rpm for 5min to obtain a film-forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Example 5
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nanoparticle embedded volatile oil: adding the volatile oil obtained from 30mLS1 into the upper layer zein solution obtained from S2, wherein the weight ratio of the volatile oil to the zein solution is 1, homogenizing while dripping, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the zein solution are fully dissolved to form a uniform solution; dripping the solution into 120mL of ultrapure water, homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5, and the volatile oil and the zein are both insoluble in water and precipitate nanoparticles to form nanoparticle-embedded volatile oil.
S4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoparticle-embedded volatile oil formed in S3, and homogenizing at 13000rpm for 5min to obtain a film-forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Example 6
The preparation method of the degradable antibacterial antioxidant film comprises the following steps:
s1: preparing volatile oil: taking elsholtzia splendens, putting into a volatile oil extractor, adding 8 times of water, distilling and extracting for 5h, stopping heating to obtain a water layer and a volatile oil layer respectively, adding anhydrous sodium sulfate or anhydrous calcium sulfate into the volatile oil layer, dehydrating and drying to obtain elsholtzia splendens volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s3: preparing the nanoparticle embedded volatile oil: adding the volatile oil obtained from 30mLS1 into the upper layer zein solution obtained from S2, wherein the weight ratio of the volatile oil to the zein solution is 1.5, homogenizing while dripping, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the zein solution are fully dissolved to form a uniform solution; dripping the solution into 120mL of ultrapure water, homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5, and the volatile oil and the zein are both insoluble in water and precipitate nanoparticles to form nanoparticle-embedded volatile oil;
s4: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoparticle-embedded volatile oil formed in S3, and homogenizing at 13000rpm for 5min to obtain a film-forming solution; and pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the volatile oil embedded film.
Comparative example
The preparation method of the blank film without carrying the volatile oil of the embodiment comprises the following steps:
s1: preparation of chitosan solution and zein solution: adding chitosan into an acetic acid solution with the mass concentration of 1%, stirring to form a transparent chitosan solution with the mass fraction of 1%, centrifugally filtering insoluble substances, and taking the upper-layer chitosan solution for later use; dissolving zein in 90% ethanol solution, stirring to obtain transparent zein solution with mass concentration of 5%, centrifuging, filtering to remove insoluble substance, and collecting upper zein solution;
s2: and (3) nanoparticle precipitation: dripping 30mLS1 to obtain upper layer zein solution into 120mL of ultrapure water, homogenizing while dripping, wherein the homogenizing rotating speed is 13000rpm, the homogenizing time is 5, zein is insoluble in water and nanoparticles are separated out;
s3: preparing a film: adding 150mL of chitosan and 0.9g of glycerol solution into the nanoparticles precipitated in the S2, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; pouring 80g of the film forming solution into a plastic culture dish with the diameter of 11cm, carrying out vacuum degassing on the film forming solution in the culture dish, drying for 36h in a drying oven at 40 ℃, and demoulding to obtain the blank film without the volatile oil.
Effect example 1
Nanoparticle and nanoemulsion particle size distribution test:
the size of the particle diameter, particle size dispersion and potential value of the film in examples 1 to 6 and comparative example were analyzed using a malvern particle size analyzer; the results of the present invention on the particle size, particle size distribution and potential value of the thin films obtained in examples 1 to 6 and comparative example are shown in the following table 1;
TABLE 1 results of particle size, particle size dispersibility and potential value of film
Figure 688809DEST_PATH_IMAGE001
And (4) analyzing results:
as can be seen from the data in Table 1: the particle diameters of the films in the examples 1-6 and the comparative example are all nano-scale, and the potential value of the film is between 40.8mV and 59.8mV, so that the film can exist stably; in the films prepared by embedding the volatile oil by using the nano-emulsion in the examples 1-3, the particle size of the films is slowly increased along with the increase of the weight ratio of the volatile oil to the zein solution; examples 4-6 films prepared by embedding volatile oil with nanoparticles, the particle size of the films increased significantly as the weight ratio of volatile oil to zein solution increased; the thin films prepared by embedding the volatile oil with the nano-emulsion in examples 1-3 have higher potential values than the thin films prepared by embedding the volatile oil with the nano-particles in examples 4-6 when the weight ratio of the volatile oil to the zein solution is the same.
Effect example 2
And (3) light transmittance test:
the light transmittance of the films obtained in examples 1 to 6 and comparative example was measured in a wavelength range of 200nm to 800nm using an ultraviolet-visible spectrophotometer (UV-2600, Shimadzu, Japan), and the results are shown in FIG. 1;
and (4) analyzing results:
as can be seen from fig. 1: the light transmittance of the films prepared in examples 1 to 6 and comparative example was increased in order as the wavelength was increased; when the wavelength is within the range of 300nm-800nm, the blank film without the volatile oil prepared by the comparative example has the highest light transmittance, and the light transmittance is 37 percent; the film prepared in example 6, which had the lowest light transmittance, had a light transmittance of 16%; in examples 1-3, the light transmittance of the film prepared by embedding the volatile oil in the nanoemulsion is increased in a small range and fluctuates little along with the increase of the wavelength; in examples 4-6, the light transmittance of the film prepared by embedding the volatile oil with the nanoparticles is increased in a large range and fluctuates greatly along with the increase of the wavelength; the higher the light transmittance is, the lower the light blocking efficiency is, and the easier the light penetrates through the film; the film has certain light-blocking effect.
Effect example 3
And (3) water vapor permeability test:
taking seven centrifuge tubes with the same specification, and placing 1.0g of anhydrous calcium chloride in each centrifuge tube without a cover; the films obtained in examples 1 to 6 and comparative example were fixed to the top of seven centrifugal tubes one by one, and the mass m was recorded1(ii) a Placing the centrifuge tube in a drier containing saturated NaCl solution, placing the drier in 25 deg.C environment, standing for 2 days, and calculating total water absorption m2The Water Vapor Permeability (WVP) is calculated as follows:
Figure 560950DEST_PATH_IMAGE002
in the formula: delta W is the mass gain (m)2-m1) (ii) a t is time (h); x is the film thickness (mm); a is the effective area (m) of the film2) (ii) a Δ P is a saturated vapor pressure (Pa); the results of the membrane water vapor permeability test are shown in Table 2;
TABLE 2 film Water vapor Permeability test results
Figure 819893DEST_PATH_IMAGE003
And (4) analyzing results:
as can be seen from the data in Table 2: the water permeability of the volatile oil-embedded films prepared in examples 1-6 was lower than that of the comparative hollow white film; examples 1-3 films prepared with the nanoemulsion embedded volatile oil had lower water permeability than the films prepared with the nanoparticle embedded volatile oil in examples 4-6; with the increase of the addition amount of the volatile oil, the water permeability of the film is firstly reduced and then increased, and when the weight ratio of the volatile oil to the zein of the film prepared by embedding the volatile oil in the nanoemulsion is 1 in the example 2, the water permeability of the film is the lowest, and the barrier effect on water vapor is the best.
Effect example 4
And (3) mechanical strength test:
to determine the mechanical properties of the film, the force required to tear the film strip was determined by a texture analyzer (ta.xt plus, Stable Micro systems, uk); firstly, the film is cut into sheets (20 × 20 mm), the probe adopts SMS P/5s, the speed used in the measurement process is 1 mm/s, the mechanical property of the film is represented by Tensile Strength (TS) and elongation at break (EAB%), each film sample prepared in examples 1-6 and comparative example is measured for 3 times, and the average value is taken; the TS (tensile Strength) and EAB (elongation at Break) calculation formulas are as follows:
Figure 574222DEST_PATH_IMAGE004
in the formula: f (N) is the maximum force at which the film breaks; a (mm 2) is the film cross-sectional area;
Figure 514497DEST_PATH_IMAGE005
in the formula: d is the distance (mm) traveled by the probe to rupture the membrane when it contacts the membrane, and R is the radius of the hole supporting the membrane and also the radius (mm) of the membrane in contact with the probe.
The tensile strength and elongation at break results for the films are shown in table 3;
TABLE 3 tensile Strength and elongation at Break of the film
Figure 303461DEST_PATH_IMAGE006
And (4) analyzing results:
as can be seen from the data in Table 3: the films prepared by embedding the volatile oil in the examples 1-6 have tensile strength which is improved by nearly 200% compared with that of the blank film in proportion; the elongation at break is also enhanced, and the film prepared by embedding the volatile oil in the nano-emulsion in the examples 1-3 has higher toughness, the tensile strength of the film is between 0.88N/mm and 1.04N/mm, and the elongation at break is between 38.43 and 69.67 percent; with the increase of the content of the added volatile oil, the tensile strength and the elongation at break are increased firstly and then reach the plateau stage or are reduced, in the film prepared by embedding the volatile oil by adopting the nanoemulsion in the embodiment 2, when the weight ratio of the volatile oil to the zein is 1, the tensile strength of the film is 1.02N/mm, and the elongation at break is 69.67%; examples 4-6 films prepared by embedding volatile oil with nanoparticles have tensile strength of 0.26N/mm-1.02N/mm and elongation at break of 14.18% -58.88%, in example 5, the weight ratio of volatile oil to zein is 1.0, and the tensile strength and elongation at break are 1.07 and 58.88 respectively; for the film, the larger the tensile strength is, the better the tensile strength is, and the elongation at break is moderate and optimum, so that the film prepared by embedding the volatile oil by using the nanoemulsion is better than the film prepared by embedding the volatile oil by using the nanoparticle, and the film prepared by embedding the volatile oil by using the nanoemulsion in example 2 has the weight ratio of the volatile oil to the zein of 1, and has the optimal mechanical strength.
Effect example 5
And (3) scanning electron microscope test:
the surface appearance of the films of examples 1-6 and comparative example was observed by a scanning electron microscope (Quanta 250, FEI company, czech), and the cross-sectional structure of the films prepared in examples 2, 5 and comparative example, which naturally fractured after being frozen into brittle by liquid nitrogen, was observed by a scanning electron microscope; before measurement, each sample was sputter plated with gold to increase conductivity, and the film samples were imaged at 15 kV accelerating voltage; the scanning electron microscope results are shown in FIGS. 2-11;
and (4) analyzing results:
as can be seen from fig. 2-11: the films prepared from examples 1-6 with embedded volatile oil had a smoother surface than the comparative blank film, and the films prepared from examples 2 and 5 had flatter broken sections than the comparative film.
Effect example 6
Thickness determination test:
the thickness of the film was measured by a hand-held digital display micrometer screw (san Ding Corp., China) with an accuracy of 0.001 mm, and when the films of examples 1-6 and comparative examples were measured, 3 thickness values were randomly taken at different positions of the film, and the measurement was repeated 3 times, and the results were averaged, and the results of the thickness measurement are shown in Table 4;
table 4 shows the results of the measurement of the film thickness
Figure 936568DEST_PATH_IMAGE007
And (4) analyzing results:
as can be seen from Table 4: the films obtained in examples 1 to 6 had an average thickness of 0.1 mm.
Effect example 7
And (3) antioxidant test:
antioxidant activity of the film was determined by clearance of 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radicals: respectively weighing 20.0 mg of the film samples in the examples 1-6 and the comparative example, dissolving the film samples in 10 mL of methanol, and soaking the film samples for 24h at room temperature; filtering the soak solution by a filter head (0.22 mu m), and then transferring 2 mL of 2, 2-diphenyl-1-picrylhydrazine to mix with 1 mL of methanol; then, the mixed solution is vortexed on a vortexing shaking instrument for 3 min, and is reacted for 30min in a dark place; and finally, measuring the absorbance of the sample at 517 nm by using an ultraviolet spectrophotometer, and calculating the ability of the sample to remove DPPH free radicals.
Figure 443772DEST_PATH_IMAGE008
In the formula: a. the0The absorbance value of a DPPH methanol blank solution at 517 nm is obtained; a is absorbance value of different sample solutions at 517 nm, and the antioxidant activity result is shown in figure 12, in figure 12 (a) is volatile oil (concentration is 175.4 μ g/mL); (b) comparative example film; (c) example 1 film; (d) example 2 film; (e) example 3 film; (f) example 4 film; (g) example 5 film; (h) example 6 film.
And (4) analyzing results:
as can be seen from fig. 12: the anti-oxidant activity of the films prepared in examples 1-6 was stronger than that of the blank film of the comparative example, and FIG. 12 shows that in examples 1-3, the anti-oxidant activity of the films increased as the content of volatile oil increased; FIG. 12 shows that in examples 4-6, the antioxidant activity of the film increased first and then decreased as the volatile oil content increased; example 3 the film prepared by embedding the volatile oil by the nano-emulsion has the strongest antioxidant activity when the weight ratio of the volatile oil to the zein is 1.5; the antioxidant activity of the film is as follows: example 3> example 5> example 2> example 6> example 4> example 1> comparative example, however, the antioxidant activities of example 2 and example 3 are not very different, and the film of example 2 is selected by considering the amount of the added volatile oil and the like.
Effect example 8
And (3) antibacterial test:
the antibacterial effect of different films on staphylococcus aureus and escherichia coli is measured by adopting a diffusion method, the staphylococcus aureus and the escherichia coli are respectively inoculated on a nutrient agar culture medium by using a sterilized coating rod on an ultra-clean workbench, the films of examples 1 to 6 and a comparative example are respectively cut into small disks with the diameter of 10mm and then are attached to a bacteria-containing plane, and after culture and culture are carried out at 37 ℃ for 24 hours, the diameter of an antibacterial ring is measured, and the result is shown in table 5;
TABLE 5 measurement results of the diameter of the zone of inhibition of the film
Figure 922158DEST_PATH_IMAGE009
And (4) analyzing results:
from the data in table 5, it can be seen that: evaluating the bacteriostatic effect of the film according to the diameter of the bacteriostatic circle, wherein the larger the diameter is, the better the bacteriostatic effect is; the films prepared after the volatile oil is embedded in the films of the examples 1 to 6 have stronger antibacterial capacity; the blank film prepared by the comparative example does not show antibacterial activity, and after the volatile oil is embedded, the film shows the capability of resisting staphylococcus aureus and escherichia coli; examples 1-3 films prepared by embedding volatile oil in nanoemulsion have an overall greater antibacterial effect than examples 4-6 films prepared by embedding volatile oil in nanoparticles; in examples 1-3, the anti-staphylococcus aureus and anti-escherichia coli capability of the film is enhanced along with the increase of the content of the volatile oil, and the film prepared in example 3 has the strongest antibacterial capability; in examples 4-6, the antibacterial activity of the film increased with the increase of the volatile oil and then tended to be stable, and the film prepared in example 5 had the strongest antibacterial activity but still weaker than the film of example 2 in which the weight ratio of the volatile oil to the zein was also 1; considering the comprehensive cost and the like, the preferred embodiment 2 is that the weight ratio of the volatile oil to the zein is 1, and the film prepared by embedding the volatile oil by the nano-emulsion has stronger mechanical property and physicochemical property and also has excellent antibacterial and antioxidant properties.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the technical scope of the present invention.

Claims (10)

1. A degradable antibacterial antioxidant film, which is characterized in that; the material is prepared from the following raw materials in percentage by weight: the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is (0.8-1.2): (0.8-1.2): (0.8-1.2): (0.4-0.6).
2. The degradable antibacterial and antioxidant thin film according to claim 1, wherein; the weight ratio of the chitosan to the zein to the volatile oil to the glycerol is 1: 1: 1: 0.6.
3. the degradable antibacterial and antioxidant thin film according to claim 2, wherein; the volatile oil is elsholtzia splendens.
4. A method for preparing the degradable antibacterial and antioxidant film as claimed in any one of claims 1 to 3, wherein; the method comprises the following steps:
s1: preparing volatile oil: putting the medicinal materials containing the volatile oil into a volatile oil extractor, adding 6-10 times of water by weight, and heating, distilling and extracting for 2-8 h; stopping heating to obtain water layer and volatile oil layer, respectively, adding desiccant into volatile oil layer, dehydrating and drying to obtain volatile oil;
s2: preparation of chitosan solution and zein solution: adding chitosan into acetic acid solution, stirring to form transparent chitosan solution, centrifuging and filtering insoluble substances, and taking the upper layer chitosan solution for later use; dissolving zein in ethanol solution, stirring to form transparent zein solution, centrifuging and filtering insoluble substances, and taking upper zein solution for later use;
s3: embedding volatile oil with zein;
s4: preparing a film: adding chitosan and glycerol solution into the product obtained after the volatile oil is embedded in the S3 zein, and homogenizing for 5min at the rotation speed of 13000rpm to obtain a film forming solution; pouring the film forming solution into a culture dish, carrying out vacuum degassing on the film forming solution in the culture dish, and drying for 36 hours in a drying oven at the temperature of 30-50 ℃ to obtain the film.
5. The method for preparing the degradable antibacterial and antioxidant film according to claim 4, wherein; and the zein embedded volatile oil in the S3 is formed into nano-emulsion embedded volatile oil or nano-particle embedded volatile oil.
6. The method for preparing the degradable antibacterial and antioxidant film according to claim 5, wherein; the specific steps for forming the nanoemulsion embedded volatile oil are as follows: dropwise adding the upper-layer zein solution obtained in the step S2 into ultrapure water, homogenizing while dropwise adding, and separating out zein nanoparticles from the zein solution; and (4) adding the volatile oil obtained in the step (S1) into the zein nanoparticles, dripping while homogenizing, and adsorbing the zein nanoparticles on the surfaces of the volatile oil droplets to form the nanoemulsion embedded volatile oil.
7. The method for preparing the degradable antibacterial and antioxidant film according to claim 6, wherein; the homogenizing rotation speed is 10000rpm-15000rpm, the homogenizing time is 5min-30min, and the weight ratio of the volatile oil to the zein nanoparticles is 0-1.5.
8. The method for preparing the degradable antibacterial and antioxidant film according to claim 5, wherein; the specific steps for forming the nanoparticle embedded volatile oil are as follows: adding the volatile oil obtained in the step S1 into the upper-layer corn protein solution obtained in the step S2, wherein the weight ratio of the volatile oil to the corn protein solution is 0-1.5, homogenizing while dropwise adding, the homogenizing rotating speed is 13000rpm, the homogenizing time is 15min, and the volatile oil and the corn protein solution are fully dissolved to form a uniform solution; dripping the solution into ultrapure water while homogenizing at 13000rpm for 5-30 min, wherein the volatile oil and zein are insoluble in water and precipitate nanoparticles to form nanoparticle-embedded volatile oil.
9. The method for preparing the degradable antibacterial and antioxidant film according to claim 4, wherein; the mass concentration of the acetic acid solution in the S2 is 1% -5%, the mass concentration of the chitosan solution is 1% -5%, the volume concentration of the ethanol solution is 70% -90%, and the mass concentration of the formed corn protein solution is 1% -5%.
10. The method for preparing the degradable antibacterial and antioxidant film according to claim 4, wherein; and the drying agent in the S1 is anhydrous sodium sulfate or anhydrous calcium sulfate.
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CN107141518A (en) * 2017-06-07 2017-09-08 安徽中盛食用油科技有限公司 A kind of edibility antibacterial film for wrapping up tea-seed oil and preparation method thereof
CN110771772A (en) * 2019-11-11 2020-02-11 扬州冶春食品生产配送股份有限公司 Nano composite emulsified essential oil coating film and preparation method and application thereof
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CN107141518A (en) * 2017-06-07 2017-09-08 安徽中盛食用油科技有限公司 A kind of edibility antibacterial film for wrapping up tea-seed oil and preparation method thereof
CN110771772A (en) * 2019-11-11 2020-02-11 扬州冶春食品生产配送股份有限公司 Nano composite emulsified essential oil coating film and preparation method and application thereof
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