CN114044996A - Preparation and use methods of pH-sensitive intelligent active packaging film for chilled fresh multi-wave mutton - Google Patents

Preparation and use methods of pH-sensitive intelligent active packaging film for chilled fresh multi-wave mutton Download PDF

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CN114044996A
CN114044996A CN202111116250.8A CN202111116250A CN114044996A CN 114044996 A CN114044996 A CN 114044996A CN 202111116250 A CN202111116250 A CN 202111116250A CN 114044996 A CN114044996 A CN 114044996A
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mutton
pigment
packaging film
chitosan
polyvinyl alcohol
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宋丽军
于鑫淼
张丽
赵岩
王平
廖月梅
武杰
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Bengbu College
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Bengbu College
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041Optical brightening agents, organic pigments
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545Six-membered rings

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Abstract

The invention belongs to the technical field of food preservation, and discloses preparation of a pH sensitive intelligent active packaging film for cold-fresh Duan mutton. According to the pH sensitive intelligent active packaging film prepared by adopting the lycium ruthenicum pigment, after meat is packaged, the freshness of the meat in the package can be judged through the color change of the film, the pH response to the meat is sensitive, all the raw materials are degradable materials, the mechanical performance required by food packaging can be met, and the capacities of oxidation resistance, odor adsorption, pigment protection, bacteriostasis and the like of mutton are further enhanced by adding tea polyphenol inside, so that the purpose of prolonging the shelf life is achieved.

Description

Preparation and use methods of pH-sensitive intelligent active packaging film for chilled fresh multi-wave mutton
Technical Field
The invention belongs to the technical field of food preservation, and particularly relates to a pH-sensitive intelligent packaging film for cold-fresh multi-wave mutton and a preparation and use method thereof.
Background
The Wulang sheep is a good meat and fat dual-purpose sheep variety bred by hybridization of Afghanistan Wahagi fat rump sheep and local native breeding sheep in Xinjiang, China, is a good local small livestock variety which is mainly protected and widely popularized, is named due to wide distribution in the Wulang river basin, is also called Maigai sheep because the core producing area of the sheep is in Kashi Magai county, is continuously supported by science and technology in recent years, and is good in variety Dulang sheep bred on the original basis by the modern genetic breeding technology and has good characters such as high polyembryony performance, good stress resistance, strong disease resistance, early maturity, perennial estrus and the like, so that the Wulang sheep becomes a good variety for lamb production.
Therefore, the pH-sensitive intelligent active packaging film applied to the cold fresh multi-wave mutton is provided, and the intelligent expression of the pH-sensitive intelligent active packaging film is that the freshness of the mutton can be indicated through the color change of the film; the activity shows that has antioxidant activity, slows down lipid oxidation rate, prolongs the cold bright unrestrained mutton shelf life that many waves, and this membrane mainly utilizes novel degradable material polyvinyl alcohol (PVA) as the base stock, compares with traditional material, and novel material performance is more outstanding, and is more environmental protection, and the natural material chitosan of addition, tea polyphenol ubiquitous in nature can produce in a large amount. The chitosan has good film forming property and compatibility, the tea polyphenol can improve the stability of the pigment in the film, the glycerol is a high polymer material auxiliary agent, the glycerol is added into a film forming matrix material, the mechanical property, the stability, the processability and the like of the material are improved, and the functional substance of the Lycium ruthenicum Murr pigment is added, so that the coloring reaction can be carried out on the pigment and gas generated by putrefaction in meat food, and the freshness and the edibility of the food are judged according to the visual change of color; by adopting the raw material scheme and the preparation method, the obtained pH-sensitive intelligent active packaging film can fully utilize the synergistic effect of the excellent properties of the raw materials, has good fresh-keeping effect and oxidation resistance on the materials, and slows down the fat oxidation speed of the cold fresh unrestrained mutton.
Disclosure of Invention
The invention aims to solve the problems, and provides a preparation method and a use method of a pH-sensitive intelligent active packaging film applied to cold fresh unrestrained mutton.
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the pH sensitive intelligent packaging film for the chilled fresh unrestrained mutton comprises the steps of lycium ruthenicum pigment freeze-dried powder, chitosan mixed solution, polyvinyl alcohol solution and tea polyphenol powder, wherein the chilled fresh unrestrained mutton pH sensitive intelligent active packaging film is prepared by adopting solution through tape casting and drying, and the specific operation steps are as follows:
(1) drying Lycium ruthenicum Murr raw material in a vacuum freeze dryer, pulverizing into powder with an ultrafine pulverizer, extracting pigment from the raw material powder with ethanol under ultrasonic assistance, centrifuging to remove impurities, collecting supernatant, evaporating for concentration, and vacuum freeze drying the concentrate to obtain Lycium ruthenicum Murr pigment freeze-dried powder;
(2) mixing polyvinyl alcohol with distilled water, dissolving the mixture by magnetic stirring in a water bath, and cooling the mixture for later use after the polyvinyl alcohol is completely dissolved to prepare a polyvinyl alcohol solution;
(3) uniformly mixing chitosan and acetic acid solution to prepare chitosan solution, adding sodium tripolyphosphate solution, magnetically stirring at room temperature, ultrasonically defoaming, and placing in a refrigerator for later use to prepare chitosan mixed solution;
(4) mixing cleaned tea leaves with high-concentration ethanol, then carrying out ultrasonic extraction, filtering, evaporating and concentrating a solid-liquid mixture prepared by production, extracting the obtained material twice with chloroform and ethyl acetate, evaporating and recovering ester from the extracted material to obtain relatively wet crude tea polyphenol, and freeze-drying and purifying the crude tea polyphenol to finally prepare high-purity dry tea polyphenol powder;
compared with the traditional extraction method, the method has the advantages of low extraction temperature, reduction of time required by extraction, improvement of extraction efficiency, prevention of the condition of overoxidation of tea polyphenol during specific preparation, high recovery rate, low oxidation extra loss, high efficiency, energy consumption saving and the like, avoids the use of toxic solvents, and has low extraction process cost, remarkable comprehensive economic benefit and good industrial popularization value.
(5) Adding a chitosan solution and glycerol into a polyvinyl alcohol solution, uniformly mixing, adding lycium ruthenicum pigment freeze-dried powder, standing for thirty minutes after primary stirring is finished, manually adding tea polyphenol while intermittently stirring, and then performing magnetic stirring, centrifugal impurity removal and ultrasonic degassing to prepare a lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution;
(6) and pouring the prepared lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution into a self-made glass mold, drying by hot air, and taking down the mold to obtain the pH sensitive intelligent active packaging film.
As a preferred technical scheme of the invention, the drying environment of the lycium ruthenicum raw material in the step (1) is that the temperature is less than or equal to minus 50 ℃, the vacuum degree is less than or equal to 30Pa and the time is 12 hours;
sieving the raw material powder by a 40-mesh sieve;
the extraction time of the pigment is 45min by using 60% ethanol solution;
the pigment extracting solution centrifugation impurity removal conditions are as follows: 4000rpm, 10 min;
the pigment extracting solution evaporation and concentration conditions are as follows: 50 ℃ at 60 rpm;
the pigment extraction concentrated solution is subjected to vacuum freeze drying: the temperature is less than or equal to minus 50 ℃, the vacuum degree is less than or equal to 30Pa, and the time is 48 hours.
As a preferable technical scheme of the invention, in the step (2), the chitosan is CAS #9012-76-4BR deacetylation degree of 90%, and sodium tripolyphosphate is used as a food additive;
the feeding mass ratio of the chitosan to the sodium tripolyphosphate to the glacial acetic acid is 0.3 g: 0.04 g: 1g of a compound;
the mixing conditions of the chitosan mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the time is 30 min;
the ultrasonic defoaming condition of the chitosan mixed solution is as follows: 30 min;
the preferred glacial acetic acid has a mass concentration of 1% after being dispersed in water;
the preferred sodium tripolyphosphate is dispersed in water at a mass concentration of 1%.
In a preferable embodiment of the invention, in the step (3), the molecular weight of the polyvinyl alcohol is 1750 ± 50;
the mass concentration of the polyvinyl alcohol dispersed in water is 5%;
the polyvinyl alcohol dissolving condition is as follows: the water bath temperature is 90 ℃, the magnetic stirring speed is 1000rpm, and the magnetic stirring time is 2 h.
As a preferred technical scheme of the invention, in the step (4), the ethanol content in the high-concentration ethanol is 75-85%, the high-purity dried tea polyphenol powder is wholly pure white particles, the drying treatment environment of the crude tea polyphenol is 70 ℃, and the time is 2 hours.
As a preferred technical scheme of the invention, in the step (5), the lycium ruthenicum pigment is a pigment extract;
the feeding mass ratio of the chitosan solution to the polyvinyl alcohol solution to the glycerol is as follows: 0.3 g: 100 g: 1.5 g;
the mass ratio of the lycium ruthenicum pigment freeze-dried powder to the polyvinyl alcohol to the tea polyphenol to the glycerin to the chitosan is (1-3) g: 5 g: 0.3 g: 1.5 g: 0.0009 g;
the dissolving conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the mixing time is 30 min;
the conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution for centrifugal impurity removal are as follows: 4000rpm, 10 min;
the ultrasonic defoaming condition of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution is as follows: and (3) 30 min.
In a preferred embodiment of the present invention, in the step (6), the film drying conditions are: the film solution is spread to a thickness of 2mm, the hot air drying temperature is 50 ℃, and the time is 8 hours.
This patent has still provided the pH sensitive intelligent packaging film application method for the unrestrained mutton of cold bright many, and this pH sensitive intelligent active packaging film of the unrestrained mutton of cold bright many concrete application method is:
(1) shearing the size of the thin film according to the size of the volume of the cold fresh multi-wave mutton for later use;
(2) wrapping the top of a preservation box filled with the cold fresh multi-wave mutton by using the prepared pH sensitive intelligent active packaging film, leaving a little gap between the mutton and the pH sensitive intelligent active packaging film, and ensuring that the film and the preservation film are completely sealed;
(3) and (3) storing the cold fresh Wulang mutton processed in the step (2) in an environment of 0-4 ℃.
As a preferred technical scheme of the invention, the thickness of the preservative film for preserving the chilled and fresh unrestrained mutton in the step (1) of the specific use method is 0.2 mm.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the lycium ruthenicum pigment to prepare the pH sensitive intelligent active packaging film, meat can be judged for freshness by film color change after being packaged, the film is sensitive to pH reaction of the meat, all the raw materials are degradable materials, mechanical properties required by food packaging can be met, the oxidation resistance, odor adsorption, pigment protection, bacteriostasis and other capabilities of mutton can be further enhanced by adding tea polyphenol inside, the tea polyphenol has obvious inhibition effect on some common food such as staphylococcus, escherichia coli and bacillus subtilis, and simultaneously has good odor adsorption capability, so that the invention can play a good deodorization effect, has a protection effect on the pigment in the food, can play a role of natural pigment, can prevent food from discoloring, and can inhibit the formation and accumulation of nitrite, the materials are mixed together to be made into a corresponding protective film structure, so that the purpose of prolonging the shelf life can be achieved;
according to the invention, polyvinyl alcohol is used as a main raw material, and the prepared product has the advantages of good comprehensive performance, excellent mechanical property, good pigment stability, oxidation resistance, biodegradability and high environmental friendliness.
Firstly, forming a complete network structure by adopting a polyvinyl alcohol solution; then, the chitosan solution is adopted, so that the stability of the three-dimensional network structure is further improved, and the stability of the lycium ruthenicum pigment added in the film is more excellent;
the pH sensitive intelligent active packaging film applied to the cold fresh multi-wave mutton can reduce the oxidation rate of the cold fresh multi-wave mutton and the proliferation of harmful microorganisms in the package.
In conclusion, compared with the prior art, the pH-sensitive intelligent active packaging film for the cold fresh unrestrained mutton and the preparation and use methods thereof provided by the invention have the advantages that by adopting safe, nontoxic, biodegradable and good antibacterial effect biomacromolecules as materials and compounding the biomacromolecules with good pH sensitivity, a safe, nontoxic and economical packaging film is developed, and the shelf life of the cold fresh unrestrained mutton stored at 4 +/-1 ℃ can be effectively prolonged; the invention has good antibacterial and fresh-keeping performance; on the other hand, the contact between the raw meat and the outside air is isolated, and the storage stability of the raw meat is also improved; because the pH sensitive intelligent active packaging film has biodegradability, the degradation products of the main raw material polyvinyl alcohol in the invention are water and carbon dioxide, and the packaging film is an environment-friendly packaging material, and can not cause white pollution after being discarded like a preservative film or a preservative bag made of traditional chemical polymer materials.
Drawings
FIG. 1 is a schematic process flow diagram of a pH sensitive smart active packaging film according to the present invention;
FIG. 2 is a table showing the index of spoilage of chilled and deep-fried mutton in different packages according to the present invention;
FIG. 3 is a schematic diagram showing a comparison of different packaged chilled fresh mutton examples according to the present invention;
FIG. 4 is a schematic diagram illustrating the appearance evaluation of a pH sensitive smart active packaging film in accordance with the present invention;
FIG. 5 is a schematic illustration of the opacity of a pH-sensitive smart active packaging film of the present invention;
FIG. 6 is a graph showing the oxidation resistance comparison of the pH sensitive smart active packaging film of the present invention;
FIG. 7 is a schematic diagram showing the comparison of mechanical properties (tensile strength, elongation at break) of the pH-sensitive smart active packaging film of the present invention
FIG. 8 is a schematic diagram showing the comparison of pH values of different packaged chilled fresh mutton;
FIG. 9 is a graph showing the comparison of the volatile basic nitrogen content of different packaged chilled fresh Dolange mutton according to the present invention;
FIG. 10 is a graph showing the acidity/oxidation coefficient comparison of different packaged chilled red mutton;
FIG. 11 is a schematic diagram showing the comparison of malondialdehyde content in different packaged chilled fresh Dolang mutton according to the present invention;
FIG. 12 is a schematic diagram showing the comparison of the total number of colonies of the chilled red mutton with different packages according to the present invention;
FIG. 13 is a schematic diagram showing the change of the total color difference of the pH-sensitive intelligent active packaging film during the storage period of the chilled fresh unrestrained mutton;
FIG. 14 is a schematic view of a correlation analysis according to the present invention;
FIG. 15 is a Fourier infrared spectrum of a pH sensitive smart active packaging film of the present invention;
FIG. 16 is a schematic X-ray diffraction diagram of a pH sensitive smart active packaging film in accordance with the present invention;
FIG. 17 is a schematic view of a scanning electron microscope of a pH-sensitive intelligent active packaging film according to the present invention;
FIG. 18 is a schematic diagram of thermogravimetric analysis of the pH sensitive smart active packaging film of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a first aspect, as shown in fig. 1 to 3, the invention provides a preparation method of a pH-sensitive intelligent packaging film for chilled fresh bazaar mutton, which comprises lycium ruthenicum pigment freeze-dried powder, a chitosan mixed solution, a polyvinyl alcohol solution and tea polyphenol powder, wherein the pH-sensitive intelligent active packaging film for chilled fresh bazaar mutton is prepared by adopting solution through tape casting and drying, and the specific operation steps are as follows:
(1) drying Lycium ruthenicum Murr raw material in a vacuum freeze dryer, pulverizing into powder with an ultrafine pulverizer, extracting pigment from the raw material powder with ethanol under ultrasonic assistance, centrifuging to remove impurities, collecting supernatant, evaporating for concentration, and vacuum freeze drying the concentrate to obtain Lycium ruthenicum Murr pigment freeze-dried powder;
(2) mixing polyvinyl alcohol with distilled water, dissolving the mixture by magnetic stirring in a water bath, and cooling the mixture for later use after the polyvinyl alcohol is completely dissolved to prepare a polyvinyl alcohol solution;
(3) uniformly mixing chitosan and acetic acid solution to prepare chitosan solution, adding sodium tripolyphosphate solution, magnetically stirring at room temperature, ultrasonically defoaming, and placing in a refrigerator for later use to prepare chitosan mixed solution;
(4) mixing cleaned tea leaves with high-concentration ethanol, then carrying out ultrasonic extraction, filtering, evaporating and concentrating a solid-liquid mixture prepared by production, extracting the obtained material twice with chloroform and ethyl acetate, evaporating and recovering ester from the extracted material to obtain relatively wet crude tea polyphenol, drying and purifying the crude tea polyphenol to finally prepare high-purity dry tea polyphenol powder;
(5) adding a chitosan solution and glycerol into a polyvinyl alcohol solution, uniformly mixing, adding lycium ruthenicum pigment freeze-dried powder, standing for thirty minutes after primary stirring is finished, manually adding tea polyphenol while intermittently stirring, and then performing magnetic stirring, centrifugal impurity removal and ultrasonic degassing to prepare a lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution;
(6) pouring the prepared lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution into a self-made glass mold, drying by hot air, and taking down the mold to prepare the pH sensitive intelligent active packaging film;
wherein, the vacuum freeze drying conditions of the lycium ruthenicum raw material in the step (1) are that the temperature is less than or equal to minus 50 ℃, the vacuum degree is less than or equal to 30Pa and 12 hours;
sieving the raw material powder by a 40-mesh sieve;
the extraction time of the pigment is 45min by using 60% ethanol solution;
the pigment extracting solution centrifugation impurity removal conditions are as follows: 4000rpm, 10 min;
the pigment extracting solution evaporation and concentration conditions are as follows: 50 ℃ at 60 rpm;
the pigment extraction concentrated solution is subjected to vacuum freeze drying: the temperature is less than or equal to minus 50 ℃, the vacuum degree is less than or equal to 30Pa, and the time is 48 hours.
Wherein in the step (2), the chitosan is CAS #9012-76-4BR deacetylation degree of 90%, and the sodium tripolyphosphate is used as a food additive;
the feeding mass ratio of the chitosan to the sodium tripolyphosphate to the glacial acetic acid is 0.3 g: 0.04 g: 1g of a compound;
the mixing conditions of the chitosan mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the time is 30 min;
the ultrasonic defoaming condition of the chitosan mixed solution is as follows: 30 min;
the preferred glacial acetic acid has a mass concentration of 1% after being dispersed in water;
the preferred sodium tripolyphosphate is dispersed in water at a mass concentration of 1%.
Wherein in the step (3), the molecular weight of the polyvinyl alcohol is 1750 +/-50;
the mass concentration of the polyvinyl alcohol dispersed in water is 5%;
the polyvinyl alcohol dissolving condition is as follows: the water bath temperature is 90 ℃, the magnetic stirring speed is 1000rpm, and the dissolving time is 2 h.
Wherein, in the step (4), the ethanol content in the high-concentration ethanol is 75-85%, the high-purity dried tea polyphenol powder is wholly pure white particles, the drying treatment environment of the crude tea polyphenol is 70 ℃, and the time is 2 hours.
Wherein in the step (5), the lycium ruthenicum pigment is a pigment extract;
the feeding mass ratio of the chitosan solution to the polyvinyl alcohol solution to the glycerol is as follows: 0.3 g: 100 g: 1.5 g;
the mass ratio of the lycium ruthenicum pigment freeze-dried powder to the polyvinyl alcohol to the tea polyphenol to the glycerin to the chitosan is (1-3) g: 5 g: 0.3 g: 1.5 g: 0.0009 g;
the dissolving conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the mixing time is 30 min;
the conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution for centrifugal impurity removal are as follows: 4000rpm, 10 min;
the ultrasonic defoaming condition of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution is as follows: and (3) 30 min.
In the step (6), the film drying conditions are as follows: the film solution is spread to a thickness of 2mm, the hot air drying temperature is 50 ℃, and the time is 8 hours.
In a second aspect, the pH-sensitive intelligent active packaging film applied to the cold fresh multi-wave mutton prepared by the method is provided.
In a third aspect, a pH-sensitive intelligent active packaging film applied to cold fresh unrestrained mutton is provided, and the pH-sensitive intelligent active packaging film at least comprises polyvinyl alcohol, chitosan, glycerol, glacial acetic acid, tea polyphenol, sodium tripolyphosphate and lycium ruthenicum pigment.
In a fourth aspect, the method provides a use method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton, and the specific use method of the pH-sensitive intelligent active packaging film for the chilled fresh unrestrained mutton comprises the following steps:
(1) shearing the size of the thin film according to the size of the volume of the cold fresh multi-wave mutton for later use;
(2) packaging the prepared pH sensitive intelligent active packaging film on the top of a chilled fresh multi-wave mutton preservative box, leaving a little gap between the mutton and the pH sensitive intelligent active packaging film, and ensuring that the film and the preservative film are completely sealed;
(3) and (3) storing the cold fresh Wulang mutton processed in the step (2) in an environment of 0-4 ℃.
Wherein, the thickness of the preservative film for preserving the chilled fresh Dulang mutton in the step (1) of the specific use method is 0.2 mm.
In addition, compared with the prior art, the pH sensitive intelligent packaging film for the cold fresh pluronic mutton and the preparation and use methods thereof provided by the invention have the advantages that the safe, nontoxic, biodegradable and good antibacterial effect biomacromolecules are adopted as materials and are compounded with the pigment with good pH sensitivity, so that the safe, nontoxic and economical packaging film for the cold fresh pluronic mutton can be developed, and the shelf life of the cold fresh pluronic mutton stored at 4 +/-1 ℃ can be effectively prolonged.
The invention has good tensile strength, elongation at break and light transmittance, and also has good antibacterial and fresh-keeping properties; the storage time of the cold fresh multi-wave mutton at 4 +/-1 ℃ can be effectively prolonged, the color of the packaging film can be visually changed from purple (fresh) to blue (putrefaction), in addition, the pH sensitive intelligent active packaging film has biodegradability, and degradation products of polyvinyl alcohol serving as a main raw material in the invention are water and carbon dioxide, so that the pH sensitive intelligent active packaging film is an environment-friendly packaging material, and the condition that the pH sensitive intelligent active packaging film is discarded to cause white pollution is avoided unlike a preservative film or a preservative bag made of a traditional chemical polymer material.
FIG. 4 is a comparison of colors exhibited by pH sensitive smart active packaging films with different proportions of Lycium ruthenicum pigment added; the film added with the amount of 1% is light purple, the color of the film gradually deepens along with the increase of the adding concentration, and the color of the film added with the amount of 3% is dark purple.
FIG. 5 is a graph showing opacity comparison of pH-sensitive smart active packaging films with different proportions of Lycium ruthenicum pigment added; the film with the addition amount of 1% is light purple, the color of the film is gradually deepened along with the increase of the addition concentration, and the opacity is increased; the film is more favorable for blocking ultraviolet penetration compared with a control film, the performance is very excellent for food packaging materials, and in addition, the oxidation, color change and nutrient loss caused by light to food are more easily blocked.
FIG. 6 is a graph showing the oxidation resistance of pH-sensitive smart active packaging films with different proportions of Lycium ruthenicum pigment added; food oxidation is a chain reaction that produces free radicals that lead to a reduction in food quality, and the antioxidant capacity of food packaging can be explained by the scavenging rate of DPPH free radicals.
As can be seen from FIG. 6, as DPPH radical scavenging rate of Lycium ruthenicum pigment concentration sample increases from 79.8% to 88.1%, the control membrane also has weak DPPH radical scavenging activity with a scavenging rate of 22.2%, because chitosan contains free amino groups which can scavenge DPPH radical, generate stable free radical and hydrogen ion, i.e. form ammonium (NH)3+) In addition, the clearance rate of the film to DPPH is sequentially increased along with the increase of the pigment concentration of lycium ruthenicum, the film containing lycium ruthenicum pigment has good DPPH free radical scavenging activity, and the results preliminarily show that the pH sensitive intelligent active packaging film containing lycium ruthenicum pigment has the effect of effectively delaying the occurrence of oxidation reaction.
FIG. 7 is a graph comparing the mechanical properties (tensile strength, elongation at break) of pH-sensitive smart active packaging films with different proportions of Lycium ruthenicum pigment; the tensile strength is the maximum stress when the sample breaks under the action of tensile force, the elongation at break is the percentage of the original length of the elongation when the sample is broken, and the toughness of the film is generally evaluated according to the tensile strength, and the magnitude of the elongation at break is used for measuring whether the plastic belongs to a ductile material or a brittle material.
As can be seen from fig. 7, compared with the blank film, the pH-sensitive intelligent active film added with the lycium ruthenicum pigment has tensile strength improved by about 10%, and the tensile strength is greater than 30MPa, but the change of the concentration of the lycium ruthenicum pigment has little influence on the tensile strength, the elongation at break is slightly reduced with the increase of the concentration of the lycium ruthenicum pigment, and is reduced from 269% to 176%.
FIG. 8 is a graph showing the trend of the pH of mutton during storage of cold fresh multi-wave mutton for samples and controls; the pH is positively correlated with the degree of fat oxidation, which is one of the important indexes for evaluating the freshness of meat, after an animal is slaughtered, the phenomenon that the blood circulation stops occurs, at the moment, the cell metabolic process is blocked, fatty acid in tissues is oxidized, at the moment, the mutton is subjected to acid discharge, the pH value of the meat at the initial storage stage is 6.57, after 0-4 days after slaughter, glycogen in the mutton is subjected to glycolysis and generates lactic acid to release glucose under the influence of external environmental factors and the action of a self-source enzyme, the pH value of the meat is slowly reduced until a control product reaches a minimum value of 5.82 at the 4 th day, a sample reaches a minimum value of 5.84, at the moment, under the action of microorganisms and autolytic enzyme, protein is degraded into polypeptide, amino acid and other substances are generated, muscle fibers are dissolved and broken, the meat is tender, and begins to deteriorate and go bad along with the continuous increase of time, during the period, volatile nitrogen-containing compounds which are alkaline are generated, so that the pH value is gradually increased, when the storage time is 25 days, the comparison pH value reaches 7.52, the amplification is 1.7, the pH value of a sample is 6.89, the amplification is only 1.05, and in the storage process of 25 days, the pH value of a sample group is always lower than that of the comparison group, which shows that compared with a common packaging film, the intelligent active film packaging can obviously reduce the decay rate of the multi-wave mutton;
according to the reference standard, the mutton is fresh meat with pH of 5.8-6.2, the mutton is sub-fresh meat with pH of 6.3-6.6 and the rotten meat with pH of more than 6.7, the mutton wrapped by the common preservative film (contrast) reaches the rotten standard with pH of more than 6.7 at the 11 th day, and the mutton wrapped by the pH sensitive intelligent active packaging film (sample) reaches the rotten standard with pH of more than 6.7 at the 22 th day, the pH sensitive intelligent active packaging film is proved to prolong the storage time of the mutton from 10 days to 21 days at the 4 ℃ condition;
FIG. 9 shows the variation of volatile basic nitrogen (TVB-N) content of mutton during storage of chilled fresh unrestrained mutton for the samples and controls; TVB-N means that in the putrefaction process of animal food, protein is decomposed to generate alkaline nitrogen-containing substances such as ammonia, amines and the like due to the action of enzyme and bacteria, and the substances have volatility, and the higher the content of the substances is, the more amino acids are destroyed, particularly methionine and tyrosine, so that the nutritional value is greatly influenced, and the TVB-N is a main index reflecting the freshness of meat;
as can be seen from fig. 9: the TVB-N content of the sample and the reference substance is gradually increased along with the prolonging of the storage time; the increase amplitude of the TVB-N content of the sample is obviously lower than that of the control product, when the storage time is 25 days, the TVB-N content of the control product reaches 66.73mg/100g, the increase is 66.5mg/100g, the TVB-N content of the sample is 22.33mg/100g, the increase is only 22.1mg/100g, and in the 25-day storage process, the TVB-N content of the sample group is always lower than that of the control group; according to the national standard (GB5009.228-2016), the TVB-N value of mutton less than 15mg/100g is defined as fresh meat, 15-20mg/100g as sub-fresh meat, and more than 20mg/100g as putrid meat, which shows that the smart active film package can significantly reduce the putrefaction rate of the unrestrained mutton compared with the common packaging film.
FIG. 10 shows the trend of the acidity/oxidation coefficient of the chilled and fresh mutton samples and the control samples during storage; the acidity/oxidation coefficient, namely the ratio of the pH value to the oxidation force of the meat, is an indicator of the freshness of the mutton;
as can be seen from fig. 10: the acidity/oxidation coefficient of the sample and the reference shows a trend of increasing and then decreasing with the prolonging of the storage time, but the change range of the acidity/oxidation coefficient of the sample is obviously lower than that of the reference. This is because the protein of mutton is decomposed by the action of microorganisms during storage to generate amine substances, which leads to the reduction of acidity of the mutton, so that the acidity oxidation value is in a general descending trend, which is consistent with the result of pH change of the sample in FIG. 8; when the storage time is 25 days, the acidity/oxidation coefficient of the reference substance is reduced to 0.01, the reduction amplitude is 0.39, the acidity/oxidation coefficient of the sample is reduced to 0.15, the reduction amplitude is only 0.25, and the acidity/oxidation coefficient of the sample group is always higher than that of the reference group in the 25-day storage process, which shows that compared with a common packaging film, the intelligent active film packaging can obviously reduce the lipid oxidation rate of the pluronic and has obvious effect of inhibiting the fat oxidation of the chilled pluronic.
FIG. 11 is the variation trend of Malondialdehyde (MDA) content during storage of sample and reference cold fresh Dolang mutton; MDA is a secondary product of lipid oxidation and is in direct proportion to the oxidation degree of fat, and is one of important indexes for evaluating the freshness degree of meat;
as can be seen from fig. 11: along with the extension of the storage time, the MDA content of the sample and the MDA content of the reference product are gradually increased, but the MDA content of the sample is obviously lower than that of the reference product, when the storage time is 25 days, the MDA content of the reference product reaches 1.18, the amplification is 1.02, the MDA content of the sample is 0.61, the amplification is only 0.45, and in the 25-day storage process, the MDA of the sample group is always lower than that of the reference group, which shows that compared with a common packaging film, the intelligent active film packaging can obviously reduce the lipid oxidation rate of the pluronic mutton and has an obvious effect of inhibiting the fat oxidation of the chilled fresh pluronic mutton.
FIG. 12 is the variation trend of the total number of colonies in the storage process of the sample and the reference product of the chilled fresh multi-wave mutton; the total colony number measurement is used for judging the bacterial contamination degree and the sanitation quality of food, and is one of important indexes for evaluating the freshness degree of meat, the meat quality and the total colony number are in an inverse proportional relation, and the freshness evaluation standard of the cold fresh meat is as follows: first grade freshness<5log10CFU/g, secondary freshness: 5-7log10CFU/g, spoiled meat>7 log10CFU/g;
As can be seen from fig. 12: the total number of colonies of the sample and the control product gradually increases along with the prolonging of the storage time, but the increase range of the total number of the colonies of the sample is obviously lower than that of the control product, and when the storage time is 25 days, the total number of the colonies of the control product reaches 11.21 logs10CFU/g, with an amplification of 8.48log10CFU/g, total colony count of sample 7.09 log10CFU/g, the amplification is only 4.35log10CFU/g, and in 25 days storage process, the total number of sample group bacterial colony is always less than the control group, shows that compare in ordinary packaging film, the rotten fungus proliferation rate of unrestrained mutton can be obviously reduced to intelligent active membrane packing, and is showing to inhibiting the rotten effect of cold fresh unrestrained mutton.
FIG. 13 is a graph of the change in the total color difference (Δ E) of pH sensitive smart active packaging films during storage of mutton; research shows that the difference is visible by naked eyes when the delta E is more than 3.5, as can be seen from figure 9, the delta E reaches 4.48 at 3 days, the color difference of the film is obvious, multiple freshness indexes of the sample reach the putrefaction standard at 25 days of storage, and the delta E is 28.21 at the moment, which is enough to be recognized by naked eyes of a non-professional person, and the volatile biogenic amine is released when mutton is degenerated, so that the gas composition in the space around the mutton is alkaline, the gas alkalinity in the space is increased along with the increase of the storage time, the generated volatile biogenic amine (trimethylamine, cadaverine, putrescine and the like) is more along with the increase of the storage time of the mutton, the pH value in the environment is increased, and the color of the pH-sensitive intelligent active packaging film loaded with the lycium ruthenicum pigment is changed.
FIG. 14 is a graph showing the correlation between the total color difference Δ E of the pH-sensitive intelligent active thin film and the pH, volatile basic nitrogen, total bacterial count, acidity/oxidation coefficient of the chilled fresh unrestrained mutton;
as can be seen from fig. 14, the total color difference Δ E of the intelligent active thin film has a strong correlation with the pH, the volatile basic nitrogen, the total number of colonies, and the acidity/oxidation coefficient of the chilled fresh unrestrained mutton; the acidity/oxidation coefficient shows strong negative correlation, which indicates that the freshness of the chilled and unrestrained mutton can be represented by the color change of the film.
FIG. 15 is a comparison graph of Fourier Infrared Spectroscopy (FTIR) of different addition ratios of pH sensitive type intelligent active packaging film Lycium ruthenicum pigment; the three graphs provided in fig. 15 are, in order from top to bottom: the infrared spectrum of the Fourier comparison graph of the pH sensitive intelligent active packaging film, the blank-pH sensitive intelligent active packaging film-Fourier infrared spectrogram and the BWP-1.5-pH sensitive intelligent active packaging film-Fourier infrared spectrogram can effectively reflect the crosslinking condition among compounds;
as shown in FIG. 15, 3263.72cm-1The wider peak is the stretching vibration peak of O-H bond, and the chitosan-containing composite membrane is 3263.72cm-1The peak intensity is high because of the simultaneous existence of multiple absorption peaks superposed by the stretching vibration of N-H bond, and after the lycium ruthenicum pigment is added, the absorption peaks obviously shift to high wave number, which is in contact with the phenolic hydroxyl structure in the extractRelated (hydrogen bonding), 2938.07cm-1is-CH2Vibration absorption peak of (8), 1632.51cm-1Corresponding to the stretching vibration of the ketone C ═ O bond in Lycium ruthenicum Murr pigment, 1653.46cm-1(stretching vibration of amide I, C ═ O bond) and 1565.98cm-1(bending vibration of amide II, N-H bond) is a characteristic peak of chitosan, 1653.46cm-1The bending vibration peak corresponding to 0-H bond in polyvinyl alcohol (PVA) is added with Lycium ruthenicum Murr pigment, and the composite membrane 1550--1The obvious enhancement and shift of the absorption peak are caused by the vibration of C ═ C bond, which indicates that intermolecular force exists between lycium ruthenicum pigment and the polymer, partial bond energy is enhanced, and the mechanical property of the film is changed, probably because the ortho-position substitution occurs on the aromatic ring, and the results indicate that: the lycium ruthenicum pigment has good compatibility with a film forming substrate, the film performance can be changed due to intermolecular force, and the chemical components are not influenced.
FIG. 16 is a comparison graph of X-ray diffraction (XRD) of different addition ratios of pH sensitive type intelligent active packaging film Lycium ruthenicum pigment; in FIG. 16, the map is blank, BWP-3%, BWP-2.5%, BWP-2%, BWP-1.5%, BWP-1% from top to bottom;
as can be seen from fig. 16, the XRD diffraction patterns of the composite films prepared with different lycium ruthenicum pigment contents have substantially the same trend, and compared with the blank film, as the content of lycium ruthenicum pigment increases, the XRD diffraction peak intensity of the composite film decreases and the position of the diffraction peak also changes, which indicates that cross-linking occurs between film-forming substances, and such a result is consistent with the infrared spectrum result in fig. 15, and in addition, the addition of lycium ruthenicum pigment also indicates that the cross-linking structure of chitosan and polyvinyl alcohol is destroyed and the chitosan and the lycium ruthenicum pigment are cross-linked, thereby increasing the pigment stability.
FIG. 17 is a scanning electron microscope comparison graph of a pH-sensitive intelligent active packaging film with Lycium ruthenicum Murr pigment added and a blank film; fig. 17 is a sectional view of the blank-pH sensitive smart active packaging film and a sectional view of the BWP-1.5-pH sensitive smart active packaging film, respectively, from left to right;
as shown in fig. 17, the left blank film has a smooth cross section, uniform and dense components, and no particle structure or pore structure, indicating that chitosan is well compatible with polyvinyl alcohol (PVA), and the BWP-1.5-pH sensitive smart active packaging film has a flat cross section with a few pores, and has a rough cross section and an irregular pore structure compared to the blank film, and it is likely that the extract of lycium ruthenicum pigment destroys the continuous structure of the chitosan polyvinyl alcohol matrix, so that the pigment is tightly bonded to the film, indicating that the stability of the pigment of the pH sensitive smart active packaging film loaded with lycium ruthenicum pigment is good.
FIG. 18 is a thermogravimetric analysis (TG-DTG) comparison of pH sensitive smart active packaging film with Lycium ruthenicum pigment added and a blank film; the upper and lower diagrams are respectively blank-pH sensitive intelligent active packaging film-TG-TDG and BWP-1.5-pH sensitive intelligent active packaging film-TG-TDG, a thermogravimetric analyzer is adopted to measure the thermal stability of the films, as shown in FIG. 18, the thermal degradation mainly occurs at 160 ℃ and 320 ℃, the thermal degradation process of the pH sensitive intelligent active packaging film is divided into three main stages, and the first stage is mainly related to water volatilization; the second stage is carried out at 480 ℃ of 160-; in the third stage, the change is stable at 480-700 ℃, and the residual mass approaches 10 percent, which indicates that the pH sensitive intelligent active packaging film has stronger thermal degradation;
the blank film is shown in FIG. 18, the mass change is obvious at the temperature of 180-280 ℃ and the residual mass at the temperature of 797.8 ℃ is 1.92 percent, the film loaded with Lycium ruthenicum pigment is shown in FIG. 17, the mass change is obvious at the temperature of 180-330 ℃ and the residual mass at the temperature of 797.9 ℃ is 10.42 percent; it can be seen that lycium ruthenicum pigment improved the thermal stability of the film but the residual mass was slightly increased, probably due to the formation of a stable structure between lycium ruthenicum pigment and chitosan-polyvinyl alcohol, thus improving the thermal stability of the film and partial residues, which is consistent with the infrared spectroscopy results.
It should be noted that the control data line is composed of a line and an inverted triangle, and the sample data line is composed of a line and a regular triangle, both of which can be seen in the graphic area on the graph.
Example one
(1) Freeze-drying Lycium ruthenicum Murr raw material at temperature of-50 deg.C and vacuum degree of 30Pa for 12 hr, pulverizing into powder with an ultrafine pulverizer, sieving with 40 mesh sieve, ultrasonic extracting with 60% ethanol for 45min, centrifuging at 4000rpm for 10min to remove impurities, collecting supernatant, evaporating and concentrating at 50 deg.C, freeze-drying the concentrated solution at temperature of-50 deg.C and vacuum degree of 30Pa for 48 hr to obtain Lycium ruthenicum Murr pigment lyophilized powder;
(2) uniformly mixing 0.3g of chitosan and 100mL of 1% (w/v) acetic acid solution to prepare 0.3% (w/v) chitosan solution, adding 4mL of 1% (w/v) sodium tripolyphosphate solution, stirring at room temperature (1000rpm) for 30min, ultrasonically defoaming for 30min, and placing in a refrigerator for later use to prepare 0.3% (w/v) chitosan solution;
(3) mixing 5g of polyvinyl alcohol with 95mL of distilled water, heating and stirring (90 ℃, 1000rpm) for 2h, and cooling for later use after the polyvinyl alcohol is completely dissolved to prepare a 5% (w/v) polyvinyl alcohol solution;
(4) the preparation of tea polyphenol adopts ultrasonic extraction method treatment, 20g of tea leaves are mixed with 15g of high-concentration ethanol, then the tea polyphenol is extracted by ultrasonic wave assistance, the optimal conditions are 70 ℃, 80% ethanol is used under 100W ultrasonic radiation according to the material-liquid ratio of 1: extracting for 20min for 10min to obtain high content of tea polyphenols, and preventing tea polyphenols from being solidified and maintaining high quality;
(5) adding 6mL of 0.3% (w/v) chitosan solution and 1.5g of glycerol into 100mL of polyvinyl alcohol solution, uniformly mixing, adding 1.5g of lycium ruthenicum pigment freeze-dried powder, standing for 30min after primary stirring, manually adding 8g of tea polyphenol while intermittently stirring, wherein the specific adding time is 20% every five minutes until the treatment is finished, stirring for 30min at room temperature, centrifuging, taking supernatant, and performing ultrasonic degassing for 30min to obtain a lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution;
(6) pouring the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution into a self-made glass mold, flattening the solution to be 2mm in thickness, drying the solution by hot air at 50 ℃ for 12h, and taking the solution down from the mold to obtain the pH sensitive intelligent active packaging film.
With specific reference to fig. 1-3, we conclude that:
sample preparation: cutting fresh mutton, wherein the volume of cut mutton is as follows: packaging the mutton in a ratio of 0.9:1, sealing the top of the packaging box by using a pH sensitive intelligent active packaging film, wherein as shown in figure 1, the difference between a control group and a sample is not great before the first five days of mutton, but the five days are divided into two parts, wherein the pH change of the control area and the pH change of the sample group are basically consistent from the first day to the second day, and the sample group line is positioned above the control group line from the third day to the fifth day; after five days, the pH value of the control group is obviously different from the pH value of the sample group and is influenced by picture display, the upper end line is a control group line, and the lower end line is a sample group line;
comparison: cutting fresh mutton, wherein the volume of cut mutton is as follows: packaging the packaging box according to the volume ratio of 0.9:1, and sealing the top of the packaging box by using a common preservative film;
and (4) conclusion: the pH sensitive intelligent active packaging film can effectively prolong the storage time of the cold fresh multi-wave mutton at the temperature of 4 +/-1 ℃.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The pH sensitive intelligent packaging film for the chilled fresh unrestrained mutton is prepared by the following raw materials of lycium ruthenicum pigment freeze-dried powder, chitosan mixed solution, polyvinyl alcohol solution and tea polyphenol powder, and the pH sensitive intelligent active packaging film for the chilled fresh unrestrained mutton is prepared by adopting solution through tape casting and drying, and has the specific operation steps of:
(1) drying Lycium ruthenicum Murr raw material in a vacuum freezer, pulverizing into powder with an ultrafine pulverizer, extracting pigment from the raw material powder with ethanol under the assistance of ultrasound, centrifuging to remove impurities, collecting supernatant, evaporating for concentration, and vacuum freeze-drying the concentrate to obtain Lycium ruthenicum Murr pigment lyophilized powder;
(2) mixing polyvinyl alcohol with distilled water, dissolving the mixture by magnetic stirring in a water bath, and cooling the mixture for later use after the polyvinyl alcohol is completely dissolved to prepare a polyvinyl alcohol solution;
(3) uniformly mixing chitosan and acetic acid solution to prepare chitosan solution, adding sodium tripolyphosphate solution, magnetically stirring at room temperature, ultrasonically defoaming, and placing in a refrigerator for later use to prepare chitosan mixed solution;
(4) mixing cleaned tea leaves with high-concentration ethanol, then carrying out ultrasonic extraction, filtering, evaporating and concentrating a solid-liquid mixture prepared by production, extracting the obtained material twice with chloroform and ethyl acetate, evaporating and recovering ester from the extracted material to obtain relatively wet crude tea polyphenol, drying and purifying the crude tea polyphenol to finally prepare high-purity dry tea polyphenol powder;
(5) adding a chitosan solution and glycerol into a polyvinyl alcohol solution, uniformly mixing, adding lycium ruthenicum pigment freeze-dried powder, standing for thirty minutes after primary stirring is finished, manually adding tea polyphenol while intermittently stirring, and then performing magnetic stirring, centrifugal impurity removal and ultrasonic degassing to prepare a lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution;
(6) and pouring the prepared lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution into a self-made glass mold, drying by hot air, and taking down the mold to obtain the pH sensitive intelligent active packaging film.
2. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (1), the drying environment of the lycium ruthenicum raw material is at the temperature of less than or equal to-50 ℃, the vacuum degree of less than or equal to 30Pa and 12 hours;
sieving the raw material powder by a 40-mesh sieve;
the extraction time of the pigment is 45min by using 60% ethanol solution;
the pigment extracting solution centrifugation impurity removal conditions are as follows: 4000rpm, 10 min;
the pigment extracting solution evaporation and concentration conditions are as follows: 50 ℃ at 60 rpm;
the pigment extraction concentrated solution is subjected to vacuum freeze drying: the temperature is less than or equal to minus 50 ℃, the vacuum degree is less than or equal to 30Pa, and the time is 48 hours.
3. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (2), the chitosan is CAS #9012-76-4BR deacetylation degree of 90%, and sodium tripolyphosphate is used as a food additive;
the feeding mass ratio of the chitosan to the sodium tripolyphosphate to the glacial acetic acid is 0.3 g: 0.04 g: 1g of a compound;
the mixing conditions of the chitosan mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the time is 30 min;
the ultrasonic defoaming condition of the chitosan mixed solution is as follows: 30 min;
the preferred glacial acetic acid has a mass concentration of 1% after being dispersed in water;
the preferred sodium tripolyphosphate is dispersed in water at a mass concentration of 1%.
4. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (3), the molecular weight of the polyvinyl alcohol is 1750 +/-50;
the mass concentration of the polyvinyl alcohol dispersed in water is 5%;
the polyvinyl alcohol dissolving condition is as follows: the water bath temperature is 90 ℃, the magnetic stirring speed is 1000rpm, and the dissolving time is 2 h.
5. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (4), the ethanol content in the high-concentration ethanol is 75-85%, the high-purity dried tea polyphenol powder is wholly pure white particles, the drying treatment environment of the crude tea polyphenol is 70 ℃, and the time is 2 hours.
6. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (5), the lycium ruthenicum pigment is a pigment extract;
the feeding mass ratio of the chitosan solution to the polyvinyl alcohol solution to the glycerol is as follows: 0.3 g: 100 g: 1.5 g;
the mass ratio of the lycium ruthenicum pigment freeze-dried powder to the polyvinyl alcohol to the tea polyphenol to the glycerin to the chitosan is (1-3) g: 5 g: 0.3 g: 1.5 g: 0.0009 g;
the dissolving conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution are as follows: the magnetic stirring speed is 1000rpm, and the mixing time is 30 min;
the conditions of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution for centrifugal impurity removal are as follows: 4000rpm, 10 min;
the ultrasonic defoaming condition of the lycium ruthenicum pigment-polyvinyl alcohol-chitosan-tea polyphenol mixed solution is as follows: and (3) 30 min.
7. The preparation method of the pH-sensitive intelligent packaging film for the chilled fresh unrestrained mutton according to claim 1, which is characterized by comprising the following steps: in the step (6), the film drying conditions are as follows: the film-making solution is spread to a thickness of 2mm, the hot air drying temperature is 50 ℃, and the time is 8 hours.
8. A use method of a pH sensitive intelligent packaging film for chilled fresh unrestrained mutton is characterized in that the use method of the pH sensitive intelligent active packaging film for chilled fresh unrestrained mutton comprises the following steps:
(1) shearing the size of the thin film according to the size of the volume of the cold fresh multi-wave mutton for later use;
(2) wrapping the top of a preservation box filled with the cold fresh multi-wave mutton by using the prepared pH sensitive intelligent active packaging film, leaving a little gap between the mutton and the pH sensitive intelligent active packaging film, and ensuring that the film and the preservation film are completely sealed;
(3) and (3) storing the cold fresh Wulang mutton processed in the step (2) in an environment of 0-4 ℃.
9. The use method of the cold fresh multi-wave mutton pH sensitive intelligent active packaging film according to claim 8, characterized in that: the specific use method comprises the step (1) that the thickness of the preservative film for preserving the chilled and fresh unrestrained mutton is 0.2 mm.
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