CN113004559B - Active gelatin-based edible film and preparation and application methods thereof - Google Patents

Active gelatin-based edible film and preparation and application methods thereof Download PDF

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CN113004559B
CN113004559B CN202110248712.5A CN202110248712A CN113004559B CN 113004559 B CN113004559 B CN 113004559B CN 202110248712 A CN202110248712 A CN 202110248712A CN 113004559 B CN113004559 B CN 113004559B
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gelatin
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CN113004559A (en
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葛黎明
徐锦芳
陈沁菲
李德富
穆畅道
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Sichuan University
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Abstract

The invention discloses an active gelatin-based edible film and a preparation method and an application method thereof. Wherein the preparation method of the active gelatin-based edible film comprises the following steps: mixing the water solution of dialdehyde cellulose nanocrystal with an oil solution of an antibacterial and/or antioxidant active ingredient, and homogenizing and ultrasonically treating the obtained mixed solution to obtain a Pickering emulsion loaded with the active ingredient; and (3) uniformly mixing the Pickering emulsion loaded with the active ingredients, a gelatin aqueous solution and a plasticizer to obtain a film forming solution, and then forming a film. The active gelatin-based edible film obtained by the invention has edibility, good mechanical property, water resistance, ultraviolet barrier property and antibacterial and antioxidant activity.

Description

Active gelatin-based edible film and preparation and application methods thereof
Technical Field
The invention relates to the technical field of gelatin-based edible films.
Background
Gelatin is a product obtained by partial hydrolysis of natural collagen in animal tissues, has abundant surface active groups, is widely available and low in cost, can be obtained from renewable resources such as agricultural industry, marine waste and byproducts, and is widely applied to different fields such as food, medicine, daily chemicals and the like. Researchers have found that gelatin, when used to prepare an active edible film that maintains the flavor and quality of food products, has the advantages of ease of use, natural non-toxicity, excellent film forming properties, good biodegradability, and good barrier properties to gases, oxygen, and lipids at low or moderate relative humidity.
The edible gelatin film is a protein film, has strong hydrophilicity, and can bring antibacterial and antioxidant activities after the introduced hydrophobic or volatile natural active ingredients are fixed by a method of encapsulation or emulsification and the like. The traditional emulsion used in the emulsification method mostly contains a surfactant with certain toxicity as an emulsifier, and cannot be applied to the field of food additives or food packaging films; moreover, the emulsion prepared by emulsifying the surfactant has poor stability, is easy to aggregate and adsorb in the preparation and storage processes, and even gradually migrates to the surface layer, so that the structure of the gelatin-based film is not uniform, and the physical and chemical properties of the film are influenced.
Unlike the traditional emulsion emulsification method, the Pickering emulsion method is considered to be a more potential method, and the emulsifier used in the method is solid particles with water-oil amphipathy, and the solid particles can form a thicker and complex solid interface layer between oil and water in the emulsion in the emulsification process, so that oil drops are fixed through a three-dimensional mechanism. On the other hand, the active gelatin-based film in the prior art generally has the problems of insufficient mechanical properties, poor water resistance, poor ultraviolet barrier property and the like, and the application range is extremely limited.
Disclosure of Invention
The invention aims to provide a gelatin-based edible film which has edibility, good mechanical property, water resistance, ultraviolet barrier property and antibacterial and antioxidant activity, and a preparation method and an application method thereof.
The invention firstly discloses the following technical scheme:
a method of making an edible film based on activated gelatin, comprising:
mixing the water solution of dialdehyde cellulose nanocrystal with an oil solution of an antibacterial and/or antioxidant active ingredient, and homogenizing and ultrasonically treating the obtained mixed solution to obtain a Pickering emulsion loaded with the active ingredient;
uniformly mixing the Pickering emulsion loaded with the active ingredients, a gelatin aqueous solution and a plasticizer to obtain a film forming solution, and then forming a film to obtain the active gelatin-based edible film;
wherein the content of the dialdehyde cellulose nanocrystals in the water solution of the dialdehyde cellulose nanocrystals is 0.05-2wt%, and the content of the active ingredients in the oil solution of the active ingredients is 0.1-5 wt%; the mass ratio of the Pickering emulsion loaded with the active ingredients to the gelatin water solution and the plasticizer is 100 (0.2-4) to 0.8; the solute concentration of the gelatin water solution is 2-6 wt%.
In the above embodiment, the oily solution of the active ingredient is a solution obtained by dissolving the active ingredient in an oily solvent.
According to some preferred embodiments of the present invention, the plasticizer is selected from one or more of sorbitol, glycerol, propylene glycol, mannitol, monoglycerides, hydrogenated castor oil, epoxidized soybean oil, coconut oil, hydrogenated lanolin, maltitol, more preferably from glycerol.
According to some preferred embodiments of the present invention, the obtaining of the dialdehyde cellulose nanocrystals comprises:
hydrolyzing cellulose at constant temperature of 30-50 deg.C by acid to obtain cellulose nanocrystal;
under an acidic condition, adding sodium periodate into the aqueous solution of the cellulose nanocrystals, and carrying out a light-shielding oxidation reaction at a reaction temperature of 35-60 ℃ to obtain the dialdehyde cellulose nanocrystals.
According to some preferred embodiments of the invention, the acid is selected from a sulfuric acid solution having a concentration of 40-65wt% by mass.
According to some preferred embodiments of the present invention, the mass ratio of the cellulose to the sulfuric acid solution is (2-6): 50-200.
According to some preferred embodiments of the invention, the acidic condition is pH 2-4.
According to some preferred embodiments of the present invention, the shear rotation speed of the homogenization treatment is 8000-14000 rpm.
According to some preferred embodiments of the present invention, the time of the homogenization treatment is 2 to 10 min.
According to some preferred embodiments of the present invention, the sonication power is 200-600W.
According to some preferred embodiments of the invention, the time of the sonication is 2-6 min.
According to some preferred embodiments of the present invention, the active ingredient is selected from one or more of dihydromyricetin, quercetin, curcumin, prunella flavones, naringenin, luteolin, allicin, apigenin, linalool and anisidine.
According to some preferred embodiments of the invention, the oil solvent is selected from vegetable oils.
According to some preferred embodiments of the present invention, the oil solvent is selected from one or more of soybean oil, corn oil, peanut oil, olive oil, linseed oil, rapeseed oil, sesame oil, cottonseed oil and sunflower seed oil.
The present invention further provides a novel active gelatin-based edible film, which is prepared by the above preparation method.
In the active gelatin-based edible film, firstly, dialdehyde cellulose nanocrystals are used for stabilizing Pickering emulsion to encapsulate oil-soluble active substances, then the Pickering emulsion loaded with the active substances is uniformly introduced into a gelatin matrix, and aldehyde groups of the dialdehyde cellulose nanocrystals and amino groups of gelatin are subjected to Schiff base reaction to chemically crosslink and modify the gelatin to prepare the gelatin-based edible film with excellent ultraviolet blocking performance, good water resistance, higher mechanical strength and stronger antibacterial and antioxidant activity.
The invention further provides application of the active gelatin-based edible film prepared by the preparation method in a packaging material.
Preferably, the use comprises using the active gelatin-based edible film as a food or pharmaceutical packaging material.
The invention has the following beneficial effects:
the preparation method comprises the steps of taking Dialdehyde Cellulose Nanocrystals (DCNC) as a solid particle stabilizer, preparing a Pickering emulsion loaded with active ingredients by an ultrasonic-homogeneous combined emulsification method, and introducing the Pickering emulsion into a gelatin matrix to prepare an active gelatin-based edible film, wherein the DCNC is distributed on an oil-water interface of the Pickering emulsion, while active substances are effectively encapsulated in the Pickering emulsion, the gelatin film is modified by chemical crosslinking through Schiff base reaction between aldehyde groups in molecules and amino groups of gelatin molecules, and in addition, the DCNC with nanometer size is distributed in a continuous phase of a mixed system and can physically fill the gelatin matrix. The gelatin-based edible film obtained by the synergistic effect of the components has excellent physicochemical property and biological or medicinal activity.
In the preparation method, the Pickering emulsion with stable biological macromolecular solid particles has the advantages of environmental friendliness, safety, nontoxicity, good long-term stability, high loading capacity, controllable release of active substances and the like, the Dialdehyde Cellulose Nanocrystal (DCNC) is a rod-shaped biological macromolecular nanoparticle and has the advantages of high mechanical strength, high surface area ratio and high length-diameter ratio, abundant aldehyde groups on the surface and the like, and the subsequent application and development are facilitated.
In some preferred embodiments, the DCNC is prepared by acid hydrolysis and sodium periodate oxidation processes, wherein sodium periodate can specifically oxidize ortho-position hydroxyl groups in CNC molecules into aldehyde groups, further, Cellulose Nanocrystals (CNC) with different size distributions can be obtained by adjusting the reaction time, temperature and concentration of cellulose hydrolysis by sulfuric acid, and DCNC with different aldehyde group contents can be obtained by adjusting the addition amount of sodium periodate.
In some preferred embodiments, the preparation method of the invention prepares a stable Pickering emulsion loaded with active substances by regulating and controlling oil-water ratio, DCNC concentration, DCNC aldehyde group content, homogeneous rotation speed and ultrasonic power; and finally, introducing the Pickering emulsion into a gelatin matrix to prepare the active gelatin-based edible film.
The preparation method of the invention takes the natural biomass which has huge reserves in the nature and can be regenerated as the raw material, and the obtained product can be used as a substitute of petroleum-based synthetic plastics, thereby effectively relieving the pressure of resources and environment.
The active gelatin-based edible film obtained by the invention has good water resistance, higher mechanical strength, excellent ultraviolet blocking performance, good controllable biodegradability and stronger antibacterial and antioxidant activity, can effectively prevent the packaged objects from being polluted by harmful microorganisms and the lipid from being oxidized, keeps the packaged objects safe, and has application advantages in the fields of food and medicine packaging materials.
Drawings
Fig. 1 is a SEM comparison of the active gelatin-based edible film obtained in example 1.
Fig. 2 is a graph showing the results of uv-vis transmittance test of the activated gelatin-based edible film obtained in example 1.
Fig. 3 is a graph showing the results of a water contact angle test of the edible film based on activated gelatin obtained in example 1.
Fig. 4 is a graph showing the results of an equilibrium swelling degree test of the active gelatin-based edible film obtained in example 1.
FIG. 5 is a graph showing ABTS of the activated gelatin-based edible film obtained in example 1+Kinetics of radical clearance over time.
Detailed Description
According to the technical scheme of the invention, one specific implementation mode comprises the following steps:
(1) dispersing 2-6 parts by mass of cellulose in 50-200 parts by mass of sulfuric acid solution with the mass concentration of 40-65wt%, reacting in water bath at 30-50 ℃ for 2-24 h, and then washing and dialyzing to obtain Cellulose Nanocrystal (CNC) water solution;
(2) adding sodium periodate into a CNC aqueous solution according to the mass ratio of the CNC to the sodium periodate of 1 (0.5-4), adjusting the pH of a reaction solution to 2-4, reacting for 2-8 h at 35-60 ℃ in a dark place, then carrying out centrifugal washing and dialysis to obtain a Dialdehyde Cellulose Nanocrystal (DCNC) aqueous solution;
(3) mixing a DCNC water solution with the mass concentration of 0.05-2wt% with an active ingredient oil solution with the mass concentration of 0.1-5wt%, homogenizing at the speed of 8000-14000rpm for 2-10min, and then carrying out ultrasonic treatment at the ultrasonic power of 200-600W for 2-6min to obtain a Pickering emulsion loaded with active ingredients;
(4) gelatin aqueous solution with the mass concentration of 2-6wt%, the obtained Pickering emulsion loaded with active ingredients and a plasticizer are mixed according to the mass ratio of 100: (0.2-4):0.8, uniformly mixing to obtain a film forming solution, pouring the film forming solution into a die, and drying at 25-40 ℃ to prepare the active gelatin-based edible film;
wherein the active ingredient is preferably one or more of dihydromyricetin, quercetin, curcumin, prunella vulgaris flavone, naringenin, luteolin, garlicin, apigenin, linalool and anisylene.
Wherein, the oil solvent of the active ingredient oil solution is preferably vegetable oil, more preferably one or more of soybean oil, corn oil, peanut oil, olive oil, linseed oil, rapeseed oil, sesame oil, cottonseed oil and sunflower seed oil.
The above specific embodiment is a preferred embodiment of the present invention. The inventors have surprisingly found that some edible films based on active gelatin with better performance can be obtained under the reaction time, temperature and concentration of the sulfuric acid hydrolysis cellulose, the addition amount of sodium periodate, oxidation time, pH, vegetable oil type, oil-water ratio, DCNC concentration, DCNC aldehyde group content, homogenizing rotation speed, ultrasonic power and the proportion of emulsion, gelatin and plasticizer in the film.
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
Example 1
Preparing the active gelatin-based edible film by:
preparation of Dialdehyde Cellulose Nanocrystals (DCNC):
adding 4.5 parts by mass of cellulose into 135 parts by mass of a 60 wt% sulfuric acid solution, reacting in a 45 ℃ water bath for 2.5 hours, centrifuging and washing for 4 times, dialyzing for 3 days to obtain a Cellulose Nanocrystalline (CNC) aqueous solution, adding sodium periodate into the CNC aqueous solution according to the mass ratio of the CNC to the sodium periodate of 1:1.5, adjusting the pH of the reaction solution to be 3, reacting at 40 ℃ in a dark place for 4 hours, centrifuging and washing for 3 times, and dialyzing for 3 days to obtain DCNC;
preparation of Pickering emulsion:
comparing the size distribution, stability and active ingredient release rate results of the prepared emulsion, determining that a DCNC water solution with the mass concentration of 1.5% is used as a water phase, a dihydromyricetin oil solution with the mass concentration of 2% is used as an oil phase to obtain a mixed solution, homogenizing the mixed solution at 14000rpm for 2min, and performing ultrasonic treatment at 200W for 2min to prepare a Pickering emulsion loaded with active ingredients;
preparation of an active gelatin-based edible film:
uniformly mixing a gelatin aqueous solution with the mass concentration of 3%, the obtained Pickering emulsion and glycerol according to the proportion in the table 1, pouring the mixture into a mould, and drying at 40 ℃ to prepare a plurality of gelatin-based edible film samples with antibacterial and antioxidant activities.
TABLE 1 gelatin, Pickering emulsion and Glycerol ratios and samples obtained
Sample (I) Gelatin (g) Emulsion (g) Glycerol (g)
GCD-0 1 0 0.2
GCD-10 0.9 0.1 0.2
GCD-20 0.8 0.2 0.2
GCD-30 0.7 0.3 0.2
GCD-50 0.5 0.5 0.2
Performing SEM representation on the surface and the cross section of the active gelatin-based edible film sample to obtain an SEM image shown in the attached figure 1; it can be seen that the Pickering emulsion is uniformly distributed in the active gelatin-based edible film.
Samples of the above-described reactive gelatin-based edible film were tested for uv-vis transmission according to ASTM standard method D1746-92. The results are shown in fig. 2, and it can be seen that, with the increase of the Pickering emulsion content, the active gelatin-based edible film maintains higher visible light transmittance, and simultaneously, the transmittance within the range of 200-400 nm is obviously reduced, and shows good ultraviolet barrier property,
performing water contact angle and equilibrium swelling degree tests on the active gelatin-based edible film sample to show the water resistance, wherein the water contact angle test result is measured by an optical contact angle measuring instrument DSA25, and measuring the static water contact angle on the surface of the gelatin-based film in the air, as shown in figure 3; the equilibrium swelling degree is obtained by measuring the mass ratio of the completely dried film after fully swelling for 24h, and as shown in figure 4, it can be seen that the obtained active gelatin-based edible film has a larger water contact angle and a lower equilibrium swelling degree, indicating that the active gelatin-based edible film has stronger water resistance.
ABTS was performed on the above-mentioned active gelatin-based edible film sample+Free radical scavenging test, 10mg of the film sample was added to the ABTS solution with absorbance of 0.7, and the ratio of absorbance change within 30min was determined and calculated, as shown in fig. 5, it can be seen that the activated gelatin-based edible film added with Pickering emulsion was paired with ABTS+The clearance rate of free radicals is high, which shows that the antioxidant activity of the antioxidant is excellent. And with the increase of the content of Pickering emulsion, the gelatin-based edible film pair ABTS+The clearance of free radicals was increased, that is, in the above examples, the gelatin-based edible film having a Pickering emulsion content of 0.5 parts by mass had the highest pair ABTS+Clearance of free radicals.
Example 2
Preparing the active gelatin-based edible film by:
preparing DCNC:
dispersing 3 parts by mass of cellulose in 80 parts by mass of sulfuric acid solution with the mass concentration of 65wt%, carrying out water bath reaction at 50 ℃ for 8 hours, centrifuging and washing for 3 times, dialyzing for 2 days to obtain a CNC aqueous solution, adding sodium periodate into the CNC aqueous solution according to the mass ratio of the CNC to the sodium periodate of 1:1, adjusting the pH of the reaction solution to be 3.5, carrying out light-shielding reaction at 40 ℃ for 5 hours, centrifuging and washing for 4 times, and dialyzing for 2 days to obtain DCNC;
preparation of Pickering emulsion:
taking a DCNC water solution with the mass concentration of 0.08% as a water phase and a naringenin oil solution with the mass concentration of 1.5% as an oil phase, homogenizing at 8000rpm for 7min, and then carrying out ultrasonic treatment at 100W for 1min to prepare a Pickering emulsion loaded with active substances;
preparation of an active gelatin-based edible film:
gelatin water solution with the mass concentration of 5%, Pickering emulsion and glycerol are mixed according to the mass ratio of 100: (0.4-1.5): 0.8, pouring the mixture into a mould, and drying the mixture at 25 ℃ to prepare the gelatin-based edible film with the antibacterial and antioxidant activity.
Example 3
Preparing the active gelatin-based edible film by:
preparing DCNC:
dispersing 6 parts by mass of cellulose in 150 parts by mass of sulfuric acid solution with the mass concentration of 50 wt%, carrying out water bath reaction at 37 ℃ for 12 hours, carrying out centrifugal washing for 3 times, dialyzing for 3 days to obtain a CNC aqueous solution, adding sodium periodate into the CNC aqueous solution according to the mass ratio of 1:2 of the CNC to the sodium periodate, adjusting the pH of the reaction solution to 3, carrying out light-shielding reaction at 40 ℃ for 3.5 hours, carrying out centrifugal washing for 5 times, and dialyzing for 3 days to obtain DCNC;
preparation of Pickering emulsion:
taking a DCNC aqueous solution with the mass concentration of 1.2% as a water phase and a curcumine oil solution with the mass concentration of 4% as an oil phase, homogenizing at 11000rpm for 6min, and then carrying out ultrasonic treatment at 250W for 5min to prepare a Pickering emulsion loaded with active substances;
preparation of an active gelatin-based edible film:
gelatin water solution with the mass concentration of 2.4%, Pickering emulsion and glycerol are mixed according to the mass ratio of 100: (0.6-1.8): 0.8, pouring the mixture into a mould, and drying the mixture at 30 ℃ to prepare the gelatin-based edible film with the antibacterial and antioxidant activity.
The gelatin-based edible films obtained in examples 2 and 3 also have good antibacterial and antioxidant activity, and excellent mechanical properties, water resistance and ultraviolet barrier properties.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (11)

1. The preparation method of the active gelatin-based edible film is characterized by comprising the following steps: the method comprises the following steps:
mixing the water solution of dialdehyde cellulose nanocrystal with an oil solution of an antibacterial and/or antioxidant active ingredient, and homogenizing and ultrasonically treating the obtained mixed solution to obtain a Pickering emulsion loaded with the active ingredient;
uniformly mixing the Pickering emulsion loaded with the active ingredients, a gelatin aqueous solution and a plasticizer to obtain a film forming solution, and then forming a film to obtain the active gelatin-based edible film;
wherein the content of the dialdehyde cellulose nanocrystals in the water solution of the dialdehyde cellulose nanocrystals is 0.05-2wt%, and the content of the active ingredients in the oil solution of the active ingredients is 0.1-5 wt%; the mass ratio of the Pickering emulsion loaded with the active ingredients to the gelatin water solution and the plasticizer is 100 (0.2-4) to 0.8; the solute concentration of the gelatin water solution is 2-6 wt%.
2. The method of claim 1, wherein: the obtaining of the dialdehyde cellulose nanocrystal comprises:
hydrolyzing cellulose at constant temperature of 30-50 deg.C by acid to obtain cellulose nanocrystal;
under an acidic condition, adding sodium periodate into the aqueous solution of the cellulose nanocrystals, and carrying out a light-shielding oxidation reaction at a reaction temperature of 35-60 ℃ to obtain the dialdehyde cellulose nanocrystals.
3. The method of claim 2, wherein: the acid is selected from a sulfuric acid solution with the mass percentage concentration of 40-65 wt%.
4. The production method according to claim 3, characterized in that: the mass ratio of the cellulose to the sulfuric acid solution is (2-6) to (50-200).
5. The method of claim 2, wherein: the acidic condition is pH = 2-4.
6. The method of claim 1, wherein: the shearing rotating speed of the homogenization treatment is 8000-; and/or the ultrasonic power of the ultrasonic treatment is 200-600W, and/or the time of the ultrasonic treatment is 2-6 min.
7. The method of claim 1, wherein: the plasticizer is selected from one or more of sorbitol, glycerol, propylene glycol, mannitol, monoglyceride, hydrogenated castor oil, epoxidized soybean oil, coconut oil, hydrogenated lanolin, maltitol, and/or the active ingredient is selected from one or more of dihydromyricetin, quercetin, curcumin, prunella flavone, naringenin, luteolin, allicin, apigenin, linalool, and anisene.
8. The method of claim 1, wherein: in the oil solution of the active ingredient, the oil solvent is selected from vegetable oils.
9. The method of claim 8, wherein: the oil solvent is selected from one or more of soybean oil, corn oil, peanut oil, olive oil, linseed oil, rapeseed oil, sesame oil, cottonseed oil and sunflower seed oil.
10. An edible film made by the method of any one of claims 1-9 and based on activated gelatin.
11. Use of an edible film based on activated gelatin prepared by the preparation process according to any one of claims 1 to 9 in a packaging material.
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