CN116217985A - Double-crosslinked starch-based active packaging film with interpenetrating network, and preparation method and application thereof - Google Patents

Double-crosslinked starch-based active packaging film with interpenetrating network, and preparation method and application thereof Download PDF

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CN116217985A
CN116217985A CN202211093502.4A CN202211093502A CN116217985A CN 116217985 A CN116217985 A CN 116217985A CN 202211093502 A CN202211093502 A CN 202211093502A CN 116217985 A CN116217985 A CN 116217985A
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film
carboxymethyl starch
starch
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packaging film
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CN116217985B (en
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陈龙
徐昊
金征宇
田耀旗
缪铭
彭新文
龙杰
邱超
周星
赵建伟
纪杭燕
谢正军
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention discloses a double-crosslinked starch-based active packaging film with an interpenetrating network, and a preparation method and application thereof, and belongs to the technical field of packaging material processing. The invention relates to a preparation method of a double-crosslinked starch-based active packaging film with an interpenetrating network, which adopts carboxymethyl starch, catecholamine substances, gelatin, iridoid substances, plant essential oil, a carboxyl activating agent and an alkaline environment solution as raw materials, and finally prepares the double-crosslinked starch-based active packaging film with the interpenetrating network based on the characteristics of carboxyl-amino coupling, iridoid substance self-crosslinking and catecholamine substance self-polymerization. The preparation method is simple, green, pollution-free and low in energy consumption, and the prepared starch-based active packaging film not only has ultraviolet shielding performance, but also can uniformly load plant essential oil, has excellent antibacterial performance, and has wide application prospects in the field of food packaging.

Description

Double-crosslinked starch-based active packaging film with interpenetrating network, and preparation method and application thereof
Technical Field
The invention relates to a double-crosslinked starch-based active packaging film with an interpenetrating network, and a preparation method and application thereof, and belongs to the technical field of packaging material processing.
Background
The active packaging film is a novel packaging material which has the functions of traditional packaging physical blocking and actively regulating and controlling the internal environment of food packaging. The packaging material contains active ingredients, and can inhibit the growth of food spoilage bacteria to the greatest extent and delay the nutrition oxidation loss rate of food, thereby improving the safety quality of the food and prolonging the shelf life of the food. The plant essential oil is a natural and efficient plant source antibacterial active substance which is easy to obtain and widely distributed, and can achieve efficient antibacterial effect with extremely low concentration, so that the plant essential oil has potential to be applied to the development of active packages.
However, most of the plant essential oil is insoluble in water, and the characteristic makes it difficult to uniformly disperse in the water-based packaging material, so that the active packaging material has poor mechanical properties, is easy to decompose under ultraviolet light, has poor antibacterial activity and limited effect, and is difficult to be practically applied to active packaging of foods. Moreover, the existing active packaging materials have the defects of limited long-acting antibacterial performance, high cost, nondegradability, single function, incapability of having ultraviolet shielding function while inhibiting bacteria, and the like.
Therefore, there is a need to develop a degradable active packaging film capable of uniformly loading plant essential oil, enhancing mechanical properties and having ultraviolet light shielding, and a preparation method thereof, which have important economic and social significance for prolonging the shelf life of food, improving the safety quality of food and reducing the food waste.
Disclosure of Invention
The invention aims to solve the technical problems that the existing active package essential oil containing plant essential oil is uneven in load, poor in mechanical property, limited in antibacterial effect due to the fact that the essential oil is easy to decompose after encountering light, and incapable of having ultraviolet shielding performance. Therefore, the invention provides a simple and environment-friendly double-crosslinked emulsified plant essential oil starch-based active packaging film with an interpenetrating network, and a preparation method and application thereof. The invention adopts an alkaline self-polymerization double-crosslinking synergistic homogeneous emulsification method to prepare the mechanically reinforced starch-based degradable active packaging film which has ultraviolet shielding performance and uniformly loads plant essential oil, and the method is simple, green, pollution-free and low in energy consumption. Compared with the original starch-based packaging film, the antibacterial effect of the active packaging film is improved from 0mm to 13.5mm, the ultraviolet shielding performance is improved from 32% to 100%, the active packaging film has certain transparency, meanwhile, the decomposition of plant essential oil can be effectively avoided, and the antibacterial performance of the active packaging film is maintained.
A first object of the present invention is to provide a method for preparing a double-crosslinked starch-based active packaging film having an interpenetrating network, said method comprising the steps of:
(1) Dissolving carboxymethyl starch in buffer solution, heating for gelatinization, and cooling to obtain carboxymethyl starch stock solution; then adding a carboxyl activating agent to perform an activation reaction to obtain carboxymethyl starch activating solution;
(2) Under the condition of room temperature, catecholamine-like substances are added into carboxymethyl starch activation liquid obtained in the step (1) to carry out coupling reaction, so as to obtain modified carboxymethyl starch crude solution, and supernatant is removed by centrifugation, so as to obtain modified carboxymethyl starch;
(3) Dissolving gelatin in buffer solution to prepare gelatin solution;
(4) Uniformly mixing the modified carboxymethyl starch obtained in the step (2), the gelatin liquid obtained in the step (3) and the epoxy ether terpenoid substance to form a mixed liquid;
(5) Adding plant essential oil into the mixed solution obtained in the step (4), homogenizing and emulsifying, and carrying out self-polymerization and coupling reaction under the condition of oxygen blowing or air to obtain film forming solution; the plant essential oil comprises one or more of tea tree essential oil, clove essential oil, rose essential oil or orange essential oil;
(6) Pouring the film forming liquid obtained in the step (5) into a polytetrafluoroethylene flat plate by adopting a tape casting method, drying the film to form a film, and then removing the film and balancing the film to obtain the double-crosslinked starch-based active packaging film with an interpenetrating network.
In one embodiment, the carboxyl activating agent in step (1) comprises one or more of 1-ethyl- (3-dimethylaminopropyl) carbodiimide, dicyclohexylcarbodiimide or N-hydroxysuccinimide.
In one embodiment, the mass ratio of carboxymethyl starch to carboxyl activator in step (1) is 20: 1-10:1.
In one embodiment, the catecholamine-like substance of step (2) comprises one or more of 5S cysteine dopamine, 5, 6-dihydroxyindole, L-dopamine, catecholamine, dopamine hydrochloride or dopamine.
In one embodiment, the mass ratio of the carboxymethyl starch to the catecholamine substance in the step (2) is 6:1-2:1.
In one embodiment, the mass ratio of the modified carboxymethyl starch to the gelatin in the step (4) is 3:1-1:3.
In one embodiment, the epoxy ether terpenoid of step (4) comprises one or more of geniposide, gentiopicroside, genipin, or gentisic acid.
In one embodiment, the mass ratio of the iridoid substance to the gelatin in the step (4) is 50:1-10:1.
In one embodiment, the volume ratio of the plant essential oil to the mixed solution in the step (5) is 100:1-20:1.
In one embodiment, the buffer of step (1) is phosphate buffer, having a pH of 4-7.
In one embodiment, the gelatinizing of step (1) is gelatinizing at 80-90 ℃ for 10-30 min.
In one embodiment, the buffer of step (3) is a phosphate buffer, having a pH of 7.5 to 10.
In one embodiment, the stirring rate in step (1) is 100 to 500rpm and the activation reaction time is 10 to 60 minutes.
In one embodiment, the stirring rate in step (5) is 100 to 500rpm and the coupling reaction time is 1 to 5 hours.
In one embodiment, after the supernatant is removed by centrifugation in step (2), the supernatant is centrifuged with water for a further 3 times at 8000rpm for 30min.
In one embodiment, the homogenizing time in step (5) is 1-5min and the homogenizing speed is 3000-6000rpm.
In one embodiment, the self-polymerization and coupling reaction time in step (5) is 30-180min, the temperature is 50-60 ℃, and the stirring speed in the water bath is 100-500rpm.
In one embodiment, the drying mode in the step (6) is hot air drying or vacuum drying, the drying temperature is 25-60 ℃, and the drying time is 4-48 h.
In one embodiment, the equilibrium conditions of step (6) are: the temperature is 22-37 ℃, the relative humidity is 50-80% RH, and the balancing time is 12-72 h.
The second object of the invention is to provide a double-crosslinked starch-based active packaging film with interpenetrating network, which is prepared by the preparation method.
A third object of the present invention is to provide a packaging material, a wearable material and a degradable material comprising a double cross-linked starch-based active packaging film with an interpenetrating network as described above.
A fourth object of the present invention is to provide the use of the double cross-linked starch-based active packaging film with interpenetrating network described above in the field of food, pharmaceutical, agricultural or textile products.
The invention has the beneficial effects that:
the invention is based on an alkaline self-polymerization double-crosslinking synergistic homogeneous emulsification method, and promotes modified carboxymethyl starch molecules, iridoid substances and gelatin to construct a stable double-crosslinking interpenetrating network through phenolic hydroxyl self-polymerization, hydrogen bonding and cyclic imine coupling reaction, and simultaneously, plant essential oil microdroplets are uniformly embedded in the interpenetrating network under the cooperation of the hydrogen bonding through homogeneous emulsification, so that aggregation is avoided, the dispersion uniformity of the plant essential oil in an aqueous packaging film is improved, and the efficient antibacterial performance is further favorably given to an active packaging film, and meanwhile, the ultraviolet shielding performance is given to a starch film through the formation of the double-crosslinking interpenetrating network, so that the photodecomposition and volatilization of the essential oil are further reduced, and the antibacterial performance is further improved. The prepared active packaging film is complete and continuous, has an ultraviolet shielding effect close to 100%, has certain transparency, and has antibacterial performance on escherichia coli reaching 13.5mm. The packaging film can effectively inhibit the growth of food spoilage bacteria in the package, prolong the shelf life of the food and improve the safety quality of the food, and can be used in the field of food packaging.
Drawings
FIG. 1 is a graph showing the antibacterial properties of example 1 and comparative examples 1 to 5 of the present invention;
FIG. 2 is a graph showing the UV shielding properties of the dual crosslinked starch-based active films with interpenetrating networks prepared in example 1 and comparative examples 1-3 of the present invention;
FIG. 3 is a Fourier infrared spectrum of modified carboxymethyl starch of example 1 of the present invention.
Detailed Description
The present invention is further described below with reference to examples, but embodiments of the present invention are not limited thereto.
1. Antibacterial performance test: the antibacterial performance of the protective starch-based film was tested by an agar paper diffusion method.
The method comprises the following specific steps: firstly, pouring agar into a sterilization plate to prepare an agar plate with the thickness of 4mm, then cutting a film sample into circular diaphragms with the diameter of 6mm, and placing the circular diaphragms under ultraviolet rays for sterilization for 1h; and then 100 mu L of activated bacteria liquid is uniformly coated on agar, finally, a round membrane with the thickness of 6mm is placed on the agar, and the diameter of a bacteria inhibition zone is observed and recorded after incubation for 24 hours at 37 ℃ in a biochemical incubator.
2. Ultraviolet shielding performance test: the full spectrum transmittance of the protective starch-based film was tested by spectrophotometry to evaluate its uv shielding properties.
The specific operation steps are as follows: firstly, cutting a film sample into rectangular films with the length of 35mm and the width of 8mm, then placing the prepared rectangular films in a glass cuvette, placing the cuvette in an ultraviolet-visible light spectrometer, and measuring the light transmittance of the films in the wavelength range of 200-800nm by taking the transmittance as an ordinate.
Carboxymethyl starch (AR) with substitution degree of 0.3-0.6, purchased from Shanghai Ala Biotechnology Co., ltd
Butyl essential oil, purchased from Shanghai Ala Biochemical technologies Co., ltd., refractive index 1.532, density 1.05.
Example 1 (modified carboxymethylcellulose, gelatin and genipin cross-linked emulsion)
The preparation method of the starch-based active packaging film with the interpenetrating network specifically comprises the following steps:
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 4.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Carboxyl activation: 200mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 100mg of N-hydroxysuccinimide are weighed and mixed and added into the carboxymethyl starch stock solution obtained in the step (1), and the mixture is stirred uniformly, and an activation reaction is carried out at room temperature for 30min to obtain carboxymethyl starch activation solution;
(3) Carboxymethyl starch modification: weighing 0.5g of dopamine hydrochloride, adding the dopamine hydrochloride into the carboxymethyl starch activating solution obtained in the step (2), uniformly stirring at room temperature, and performing a coupling reaction for 1 hour to obtain a modified carboxymethyl starch crude solution;
(4) Washing and centrifuging: centrifuging the modified carboxymethyl starch crude solution obtained in the step (3) at 8000rpm for 30min to remove supernatant, adding deionized water, oscillating, centrifuging at 8000rpm for 30min again, and repeating the process for 3 times to obtain modified carboxymethyl starch;
(5) Dissolving: weighing 1.5g of gelatin, placing in 100ml of PBS buffer solution with pH of 8.5, and dissolving in water bath at 50deg.C to obtain gelatin stock solution;
(6) Mixing evenly: uniformly mixing the modified carboxymethyl starch obtained in the step (4), the gelatin solution obtained in the step (5) and 50mg genipin to obtain a mixed solution;
(7) Normal temperature crosslinking synergistic emulsification: adding 2ml of clove essential oil into the mixed solution obtained in the step (6), homogenizing and emulsifying for 5min at 5000rpm by using a homogenizer, placing in a water bath kettle at 50 ℃ in the presence of oxygen blowing or air, performing self-polymerization and coupling reaction for 30min at the rotating speed of 300rpm by using a stirrer, and performing vacuum degassing to obtain a film forming solution;
(8) And (3) film preparation: pouring the film forming liquid obtained in the step (7) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the double-crosslinked starch-based active packaging film with the interpenetrating network.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. The diameter of the antibacterial ring of the film on the escherichia coli is 13.5mm, and the film has obvious antibacterial effect on the escherichia coli.
The ultraviolet shielding ability of the protective starch-based film with ultraviolet resistance and antibacterial activity prepared in this example is shown in fig. 2. It can be observed that the film has a transmittance of almost 0 to ultraviolet rays and a transmittance of 10 to 40% in the visible light region of 500 to 800, proving that the film has excellent ultraviolet shielding ability while ensuring a certain transmittance.
The product prepared in this example has UV resistance and antibacterial activityThe Fourier infrared spectrogram of the modified carboxymethyl starch in the protective starch-based film is shown in figure 3; it can be observed that the modified carboxymethyl starch has a wavelength of 1524cm compared to carboxymethyl starch -1 、1286cm -1 And 811cm -1 A new absorption peak appears at 1524cm -1 The absorption peak is mainly due to stretching vibration of-NH bond, 1286cm -1 The vibration is mainly due to the C-N bond, but is 700-900cm -1 Double peak 860cm of wavelength region -1 And 811cm -1 The modified carboxymethyl starch is proved to be successful by being related to the 1,2, 4-trisubstituted benzene structure.
Comparative example 1 (modified carboxymethyl cellulose, gelatin and genipin are not crosslinked, but emulsified)
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 4.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Carboxyl activation: weighing 200mg of EDC and 100mg of NHS, mixing and adding the mixture into the carboxymethyl starch stock solution obtained in the step (1), uniformly stirring, and performing an activation reaction at room temperature for 30min to obtain carboxymethyl starch activation solution;
(3) Carboxymethyl starch modification: weighing 0.5g of dopamine hydrochloride, adding the dopamine hydrochloride into the carboxymethyl starch activating solution obtained in the step (2), uniformly stirring at room temperature, and performing a coupling reaction for 1 hour to obtain a modified carboxymethyl starch crude solution;
(4) Washing and centrifuging: centrifuging the modified carboxymethyl starch crude solution obtained in the step (3) at 8000rpm for 30min to remove supernatant, adding deionized water, oscillating, centrifuging at 8000rpm for 30min again, and repeating the process for 3 times to obtain modified carboxymethyl starch;
(5) Dissolving: weighing 1.5g of gelatin, placing in 100ml of deionized water, and dissolving in water bath at 50 ℃ to obtain gelatin stock solution;
(6) Mixing evenly: uniformly mixing the modified carboxymethyl starch obtained in the step (4), the gelatin solution obtained in the step (5) and 50mg genipin to obtain a mixed solution;
(7) Emulsifying at normal temperature: adding 2ml of clove essential oil into the mixed solution obtained in the step (6), homogenizing and emulsifying for 5min at 5000rpm by using a homogenizer, placing in a water bath kettle at 50 ℃ in the presence of oxygen blowing or air, stirring for 30min at 300rpm by using a stirrer, and carrying out vacuum degassing to obtain a film forming solution;
(8) And (3) film preparation: pouring the film forming liquid obtained in the step (7) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the double-crosslinked starch-based active packaging film with the interpenetrating network.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. The diameter of the antibacterial ring of the film on the escherichia coli is 7.8mm, and the film has poor antibacterial effect on the escherichia coli.
The ultraviolet shielding ability of the protective starch-based film with ultraviolet resistance and antibacterial activity prepared in this example is shown in fig. 2. It was observed that the film had a transmittance of 30% for ultraviolet rays, which proved that the film had poor ultraviolet ray shielding ability.
Comparative example 2 (emulsification of carboxymethyl cellulose, gelatin, and genipin)
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 4.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Dissolving: weighing 1.5g of gelatin, placing in 100ml of PBS buffer solution with pH of 8.5, and dissolving in water bath at 50deg.C to obtain gelatin stock solution;
(3) Mixing evenly: uniformly mixing the carboxymethyl starch stock solution obtained in the step (1), the gelatin solution obtained in the step (2) and 50mg genipin to obtain a mixed solution;
(4) Normal temperature crosslinking synergistic emulsification: adding 2ml of clove essential oil into the mixed solution obtained in the step (3), homogenizing and emulsifying for 5min at 5000rpm by using a homogenizer, placing in a water bath kettle at 50 ℃ in the presence of oxygen blowing or air, performing coupling reaction for 30min at the rotating speed of 300rpm by using a stirrer, and performing vacuum degassing to obtain a film forming solution;
(5) And (3) film preparation: pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the double-crosslinked starch-based active packaging film with the interpenetrating network.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. The diameter of the antibacterial ring of the film on the escherichia coli is 4.5mm, and the film has poor antibacterial effect on the escherichia coli.
The ultraviolet shielding ability of the protective starch-based film with ultraviolet resistance and antibacterial activity prepared in this example is shown in fig. 2. It was observed that the film had a transmittance of 55% for ultraviolet rays, which proved that the film had poor ultraviolet ray shielding ability.
Comparative example 3 (emulsification of carboxymethyl cellulose and gelatin)
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 4.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Dissolving: weighing 1.5g of gelatin, placing in 100ml of PBS buffer solution with pH of 8.5, and dissolving in water bath at 50deg.C to obtain gelatin stock solution;
(3) Mixing evenly: uniformly mixing the carboxymethyl starch gelatinized liquid obtained in the step (1) with the gelatin solution obtained in the step (2) to obtain a mixed liquid;
(4) Emulsification: adding 2ml of clove essential oil into the mixed solution obtained in the step (3), homogenizing and emulsifying for 5min at 5000rpm by using a homogenizer, placing in a water bath kettle at 50 ℃ in the presence of oxygen blowing or air, stirring for 30min at 300rpm by using a stirrer, and carrying out vacuum degassing to obtain a film forming solution;
(5) And (3) film preparation: pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the starch-based active packaging film.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. It can be observed that the diameter of the inhibition zone of the membrane for escherichia coli is 6.2mm, and the inhibition effect of the membrane for escherichia coli is poor.
The ultraviolet shielding ability of the protective starch-based film with ultraviolet resistance and antibacterial activity prepared in this example is shown in fig. 2. The film has a transmittance of 68% for ultraviolet rays, and the film has extremely poor ultraviolet ray shielding ability and hardly has effective ultraviolet ray shielding ability.
Comparative example 4 (modified carboxymethyl cellulose, gelatin, and genipin cross-linked, non-emulsified)
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 4.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Carboxyl activation: weighing 200mg of EDC and 100mg of NHS, mixing and adding the mixture into the carboxymethyl starch stock solution obtained in the step (1), uniformly stirring, and performing an activation reaction at room temperature for 30min to obtain carboxymethyl starch activation solution;
(3) Carboxymethyl starch modification: weighing 0.5g of dopamine hydrochloride, adding the dopamine hydrochloride into the carboxymethyl starch activating solution obtained in the step (2), uniformly stirring at room temperature, and performing a coupling reaction for 1 hour to obtain a modified carboxymethyl starch crude solution;
(4) Washing and centrifuging: centrifuging the modified carboxymethyl starch crude solution obtained in the step (3) at 8000rpm for 30min to remove supernatant, adding deionized water, oscillating, centrifuging at 8000rpm for 30min again, and repeating the process for 3 times to obtain modified carboxymethyl starch;
(5) Dissolving: weighing 1.5g of gelatin, placing in 100ml of PBS buffer solution with pH of 8.5, and dissolving in water bath at 50deg.C to obtain gelatin stock solution;
(6) Mixing evenly: uniformly mixing the modified carboxymethyl starch obtained in the step (4), the gelatin solution obtained in the step (5) and 50mg genipin to obtain a mixed solution;
(7) Crosslinking at normal temperature: adding 2ml of clove essential oil into the mixed solution obtained in the step (6), placing the mixed solution in a water bath kettle at 50 ℃ in the presence of oxygen blowing or air, performing self-polymerization and coupling reaction for 30min at the rotating speed of 300rpm by using a stirrer, and performing vacuum degassing to obtain film forming solution;
(8) And (3) film preparation: pouring the film forming liquid obtained in the step (7) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the double-crosslinked starch-based active packaging film with the interpenetrating network.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. The diameter of the antibacterial ring of the film on the escherichia coli is 8.2mm, and the film has obvious and poor antibacterial effect on the escherichia coli.
Comparative example 5 (carboxymethyl cellulose and gelatin do not contain plant essential oils)
(1) Gelatinization: 1.5g of carboxymethyl starch is weighed and dissolved in 50ml of PBS buffer with pH of 8.5, and gelatinized for 20min at 80 ℃; then stirring and cooling to 30 ℃ to obtain carboxymethyl starch stock solution;
(2) Dissolving: weighing 1.5g of gelatin, placing in 100ml of PBS buffer solution with pH of 8.5, and dissolving in water bath at 50deg.C to obtain gelatin stock solution;
(3) Mixing evenly: uniformly mixing the carboxymethyl starch stock solution obtained in the step (1) with the gelatin solution obtained in the step (2) to obtain a film forming solution;
(4) And (3) film preparation: pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ for drying and forming a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the double-crosslinked starch-based active packaging film with the interpenetrating network.
The antimicrobial properties of the starch-based active packaging film with interpenetrating network prepared in this example are shown in fig. 1. The diameter of the antibacterial ring of the film on the escherichia coli is 0mm, and the film has no antibacterial effect on the escherichia coli.
The specific embodiments described herein are offered by way of example only, and are illustrative of the spirit and scope of the invention. Those skilled in the art to which the invention relates may make various modifications or additions to the specific embodiments described or substitutions in a similar manner without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.

Claims (10)

1. A method for preparing a double-crosslinked starch-based active packaging film with an interpenetrating network, the method comprising the steps of:
(1) Dissolving carboxymethyl starch in buffer solution, heating for gelatinization, and cooling to obtain carboxymethyl starch stock solution; then adding a carboxyl activating agent to perform an activation reaction to obtain carboxymethyl starch activating solution;
(2) Under the condition of room temperature, catecholamine-like substances are added into carboxymethyl starch activation liquid obtained in the step (1) to carry out coupling reaction, so as to obtain modified carboxymethyl starch crude solution, and supernatant is removed by centrifugation, so as to obtain modified carboxymethyl starch;
(3) Dissolving gelatin in buffer solution to prepare gelatin solution;
(4) Uniformly mixing the modified carboxymethyl starch obtained in the step (2), the gelatin liquid obtained in the step (3) and the epoxy ether terpenoid substance to form a mixed liquid;
(5) Adding plant essential oil into the mixed solution obtained in the step (4), homogenizing and emulsifying, and carrying out self-polymerization and coupling reaction under the condition of oxygen blowing or air to obtain film forming solution; the plant essential oil comprises one or more of tea tree essential oil, clove essential oil, rose essential oil or orange essential oil;
(6) Pouring the film forming liquid obtained in the step (5) into a polytetrafluoroethylene flat plate by adopting a tape casting method, drying the film to form a film, and then removing the film and balancing the film to obtain the double-crosslinked starch-based active packaging film with an interpenetrating network.
2. The method of claim 1, wherein the carboxyl activating agent in step (1) comprises one or more of 1-ethyl- (3-dimethylaminopropyl) carbodiimide, dicyclohexylcarbodiimide or N-hydroxysuccinimide.
3. The method of claim 1, wherein the catecholamine-like substance of step (2) comprises one or more of 5S cysteine dopamine, 5, 6-dihydroxyindole, L-dopamine, catecholamine, dopamine hydrochloride, or dopamine.
4. The method of claim 1, wherein the epoxy ether terpenoid of step (4) comprises one or more of geniposide, gentiopicroside, genipin, or gentian.
5. The method according to claim 1, wherein the mass ratio of the modified carboxymethyl starch to the gelatin in the step (4) is 3:1-1:3; the mass ratio of the iridoid substance to the gelatin is 50:1-10:1.
6. The method according to claim 1, wherein the mass ratio of carboxymethyl starch to carboxyl activator in step (1) is 20: 1-10:1.
7. The method according to claim 1, wherein the mass ratio of carboxymethyl starch to catecholamine substance in the step (2) is 6:1-2:1.
8. A double crosslinked starch-based active packaging film having an interpenetrating network prepared by the method of any one of claims 1 to 7.
9. A packaging material, wearable material or a degradable material comprising the dual crosslinked starch-based active packaging film with interpenetrating network of claim 8.
10. Use of the double crosslinked starch-based active packaging film with interpenetrating network according to claim 8 in the field of food, pharmaceutical, agricultural or textile products.
CN202211093502.4A 2022-09-08 2022-09-08 Double-crosslinked starch-based active packaging film with interpenetrating network, and preparation method and application thereof Active CN116217985B (en)

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CN112745535A (en) * 2020-12-30 2021-05-04 江苏大学 Preparation method of gallic acid crosslinked chitosan-gelatin active composite membrane
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