CN109808254B - Composite membrane with early warning and sterilization functions and preparation method and application thereof - Google Patents
Composite membrane with early warning and sterilization functions and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite membrane with early warning and sterilization functions, and a preparation method and application thereof. The composite membrane comprises a UV protective membrane, an early warning color development membrane and a UV excitation sterilization membrane from top to bottom. According to the invention, the film rich in anthocyanin is prepared by optimizing the formula of the film solution and adopting an electrostatic spinning process, so that the release efficiency of anthocyanin can be effectively improved, and the sensitivity of the chromogenic film is improved; in addition, the prepared UV protective film can effectively inhibit the degradation of anthocyanin in the color-sensitive indicator by utilizing the fact that the potato peel residues are rich in lignin and can absorb ultraviolet light to a certain extent. The composite membrane obtained by the invention has high safety and simple manufacturing process.
Description
Technical Field
The invention relates to a composite film with early warning and sterilization functions, a preparation method and application thereof, and belongs to the field of fresh food preservation.
Background
The intelligent food packaging technology mainly comprises an indicator, a data carrier, a sensor and the like, and can monitor and indicate the change of the internal environment of the food package, so that the related quality information of the food in the storage and transportation process can be reflected in real time. Among various indicators, the color-sensitive indicator can intuitively reflect the quality change of food in real time through the color change, and has wide application prospect.
The anthocyanin is a water-soluble natural pigment widely existing in plants in the nature, the color of the aqueous solution of the anthocyanin is greatly influenced by pH, the anthocyanin turns red in a neutral environment and turns blue in an acidic environment, and therefore the anthocyanin can be applied to a color-sensitive indicator.
The prior document discloses a preparation method and application of an intelligent label for judging pork critical freshness, wherein an anthocyanin solution is added into a mixed solution of methylcellulose and polyethylene glycol-6000 under the stirring condition; removing bubbles in the solution, keeping the solution on a glass plate, drying the solution by hot air, and removing the film to obtain an indicating layer; and wrapping the indicating layer with a low-density polyethylene film to obtain the intelligent label. The intelligent label can be pasted in a package for use, and the freshness of the pork is monitored in real time according to the color change of the intelligent label; the device can also be used as a quick detection indicator card for pork freshness, and can be combined with an electronic tongue to further detect the pork freshness. However, this method has the following drawbacks: on one hand, the membrane is prepared by adopting a casting method, and the anthocyanin embedded in the methyl cellulose and polyethylene glycol-6000 matrix has low permeation efficiency, so that the sensitivity of the intelligent label is low, and therefore the electronic tongue is required to further detect the freshness of pork and verify the detection result; on the other hand, anthocyanin has instability, is greatly influenced by the surrounding environment, and is easily degraded by ultraviolet irradiation and oxidation in processing and storage environments.
Disclosure of Invention
In order to overcome the technical defects, the invention provides the composite preservative film with the functions of early warning and sterilization, which can intelligently identify the freshness of fresh meat in the storage process according to color change and has the advantages of good stability and high sensitivity; meanwhile, when the number of microorganisms in the fresh meat is found to exceed the standard, the fresh meat can be sterilized by ultraviolet light, and the composite preservative film is excited to release natural sterilizing components, so that the quality guarantee period of the fresh meat is prolonged.
The technical scheme of the invention is as follows:
a composite membrane with early warning and sterilization functions comprises a UV protective membrane, an early warning color development membrane and a UV excitation sterilization membrane from top to bottom.
The UV protection film is prepared from the following raw materials in parts by weight: 1-2 parts of polylactic acid and 20-25 parts of potato lignin extract. The UV protection film is formed on the surface of the glass plate by adopting a conventional film-making technology.
The potato lignin extract is obtained by extracting with diethyl ether, and specifically comprises the following components: drying the potato peel residues at 40-50 ℃ to constant weight, crushing and sieving to obtain potato peel residue particles; mixing the potato peel residue particles with an ether solution according to the proportion of 10-15% (W/V), stirring at room temperature for 10-12 h, filtering to remove impurities, and evaporating ether at 50-60 ℃ to obtain the potato lignin extract.
The early warning color developing film is prepared from the following raw materials in parts by weight: 25-30 parts of corn protein, 2-4 parts of anthocyanin extracting solution and 1-2 parts of guar gum. The anthocyanin extracting solution is prepared by taking purple potato peel residues as a raw material and extracting the anthocyanin in the purple potato peel residues under the ultrasonic wave assistance, wherein the extracting conditions are as follows: the material-liquid ratio is 1: 30(g/mL, extraction temperature 55 ℃, extraction time 30min, pH 1, vacuum rotary concentration at 40 ℃ to obtain the product, wherein the concentration of the product is 10-20 mg/mL.
The early warning color developing film is obtained by adopting an electrostatic spinning technology. The method comprises the following specific steps: mixing the raw materials to prepare an early warning color developing film solution, placing the solution in an injector, selecting a needle tube with the diameter of 0.08-0.09 mm, controlling the relative humidity at 60-70% at room temperature, setting the spinning speed at 0.04-0.06 mm/min, the spinning voltage at 12-14 kV, the receiving distance at 10-12 cm, the rotating speed of a receiver at medium speed, and the spinning time at 90-100 min respectively to obtain the early warning color developing film.
The UV excited sterilization film is prepared from the following raw materials in parts by weight: 0.5-1 part of gallic acid grafted chitosan solution, 1-2 parts of polyvinyl alcohol and 40-45 parts of citric acid; the gallic acid grafted chitosan solution is prepared from the following raw materials in parts by weight: 1-2 parts of chitosan, 0.5-1 part of vitamin C and H2O20.2-0.4 part of gallic acid and 1-2 parts of gallic acid.
The UV excitation sterilization film is also prepared by adopting an electrostatic spinning technology. The method comprises the following specific steps: dissolving 0.5-1% (W/V) gallic acid grafted chitosan solution and 1-2% (W/V) polyvinyl alcohol in 40-45% (W/V) citric acid solution at 90-92 ℃, stirring at 95 ℃ for 10-15 min, cooling to room temperature, and eliminating bubbles in the solution to obtain UV excited sterilization membrane solution; placing the UV excited sterilization membrane solution into an injector, selecting a needle tube with the diameter of 0.30-0.40 mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 14-18 kV, the receiving distance to be 15-18 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 40-60 min respectively to obtain the UV excited sterilization membrane.
The invention also provides a preparation method of the composite membrane with the functions of early warning and sterilization, which comprises the following steps:
(1) preparation of the UV protective film: taking potato peel residues as a raw material, and extracting a potato lignin extract; dissolving polylactic acid in trichloromethane, adding a potato lignin extract, stirring at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air, and removing the film to obtain a UV protective film;
(2) preparing an early warning color developing film: dissolving corn protein, anthocyanin extraction solution and guar gum in 80% ethanol solution, slowly stirring at room temperature, fully dissolving to obtain early warning color development membrane solution, and performing electrostatic spinning to obtain an early warning color development membrane;
(3) preparing a UV-excited sterilization film: mixing chitosan and vitamin C, H2O2Dissolving gallic acid in an acetic acid solution, and uniformly stirring at room temperature to prepare a gallic acid grafted chitosan solution; dissolving a gallic acid grafted chitosan solution and polyvinyl alcohol in a citric acid solution, uniformly stirring, cooling to room temperature, eliminating bubbles in the solution, and performing electrostatic spinning to obtain a UV excited sterilization membrane;
(4) and pressing the UV protective film, the early warning color development film and the UV excitation sterilization film in the order from top to bottom to obtain the composite film.
In the step (2), the technical parameters of the electrostatic spinning are as follows: selecting a needle tube with the diameter of 0.08-0.09 mm, controlling the relative humidity to be 60-70% at room temperature, setting the spinning speed to be 0.04-0.06 mm/min, the spinning voltage to be 12-14 kV, the receiving distance to be 10-12 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90-100 min respectively.
In the step (3), the technical parameters of the electrostatic spinning are as follows: selecting a needle tube with the diameter of 0.30-0.40 mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 14-18 kV, the receiving distance to be 15-18 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 40-60 min respectively.
As one embodiment of the present invention, a method for preparing the composite membrane includes the steps of:
(1) drying the potato peel residues at 40-50 ℃ to constant weight, crushing, sieving, mixing 10-15% (W/V) of the potato peel residue particles with an ether solution, stirring at room temperature for 10-12 h, filtering to remove impurities, and evaporating ether at 50-60 ℃ to obtain a potato lignin extract;
(2) dissolving 1-2% (W/V) polylactic acid in trichloromethane, adding 20-25% (W/V) potato lignin extract, stirring at room temperature for 15-20 min, removing bubbles in the solution, casting the solution onto a glass plate, drying with hot air at 40-45 ℃, and removing the film to obtain the UV protective film;
(3) mixing 25-30% (W/V) zein 2-4%Dissolving the anthocyanin extract solution (W/V) and 1-2% of guar gum in 80% ethanol solution, and using 0.2mol/L NaOH solution or 0.2mol/L H2SO4The pH value of the mixed solution is adjusted to 3-4 by the solution, the mixed solution is slowly stirred for 1 hour at room temperature, and a preparation solution of the early warning chromogenic membrane is obtained after the mixed solution is fully dissolved; placing the early warning color developing membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.08-0.09 mm, controlling the relative humidity to be 60-70% at room temperature, setting the spinning speed to be 0.04-0.06 mm/min, the spinning voltage to be 12-14 kV, the receiving distance to be 10-12 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90-100 min respectively to finally obtain the early warning color developing membrane.
(4) Mixing 1-2% (W/V) chitosan, 0.5-1% (W/V) vitamin C, 0.2-0.4% (W/V) H2O2Dissolving 1-2% (W/V) gallic acid in a solution containing 1-2% (W/V) acetic acid, and uniformly stirring at room temperature to prepare a gallic acid grafted chitosan solution; dissolving 0.5-1% (W/V) gallic acid grafted chitosan solution and 1-2% (W/V) polyvinyl alcohol in 40-45% (W/V) citric acid solution at 90-92 ℃, stirring for 10-15 min at 95 ℃, then cooling to room temperature, and eliminating air bubbles in the solution; placing the UV excited sterilization membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.30-0.40 mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 14-18 kV, the receiving distance to be 15-18 cm, the rotating speed of a receiver to be medium speed, and spinning time to be 40-60 min respectively to finally obtain the UV excited sterilization membrane.
(5) And laminating the UV protective film, the early warning color development film and the UV excitation sterilization film in the sequence from top to bottom to obtain the composite preservative film with the functions of early warning and sterilization.
The invention also provides the application of the composite film in fresh food packaging; preferably, the fresh food is fresh fish meat, pork, poultry meat, etc. Specifically, the obtained composite film is used as a preservative film to package fresh fish meat and is stored at the temperature of more than 0 ℃; when the composite film shows reddish purple, the fresh fish meat is placed under LED ultraviolet light and the like, the wavelength is 265-395 nm, and the irradiation intensity is 300-400 mu W/cm2The irradiation time is 3-5 min, and the gallic acid is released to the surface of the fresh fish meat by exciting the sterilization membraneThe noodle can effectively prolong the shelf life of the fresh fish.
A method for judging the quality of fresh fish meat by using a composite membrane comprises the following steps: when the composite film shows red, the fish meat is fresh meat, and the volatile basic nitrogen value of the fish meat is less than 5mg/100 g; when the color of the composite membrane is purple, the fish meat is second-time fresh meat, and the volatile basic nitrogen value of the fish meat is 5-10 mg/100 g; when the composite film shows blue or purple color, the fish meat is putrefying meat, and the volatile basic nitrogen value is more than 10mg/100 g.
The invention has the following beneficial effects:
according to the composite film, the first film on the upper surface is the UV protective film which mainly comprises lignin in the potato peel residues, so that low-intensity ultraviolet rays in processing and storage environments can be absorbed, and the early warning color developing film rich in anthocyanin is protected; the second film is an early warning color development film which mainly comprises anthocyanin and zein, is prepared by electrostatic spinning, and can accurately monitor the freshness of the fresh meat in real time according to the color change of the fresh meat; the third film is a UV excitation sterilization film, mainly comprises chitosan, gallic acid and polyvinyl alcohol, and is prepared by electrostatic spinning.
According to the invention, the film rich in anthocyanin is prepared by optimizing the formula of the film solution and adopting an electrostatic spinning process, so that the release efficiency of anthocyanin can be effectively improved, and the sensitivity of the chromogenic film is improved; in addition, the prepared UV protective film can effectively inhibit the degradation of anthocyanin in the color-sensitive indicator by utilizing the fact that the potato peel residues are rich in lignin and can absorb ultraviolet light to a certain extent. The composite membrane obtained by the invention has high safety and simple manufacturing process.
Drawings
Fig. 1 is a schematic structural diagram of a composite preservative film with early warning and sterilization functions.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a preparation of a composite film, including the following steps:
step one, drying the potato peel residues at 40 ℃ to constant weight, crushing, sieving, mixing 10 percent (W/V) of potato peel residue particles with an ether solution, stirring for 10 hours at room temperature, filtering to remove impurities, and evaporating ether at 50 ℃ to obtain the potato lignin extract.
And step two, dissolving 2% (W/V) polylactic acid in trichloromethane, then adding 20% (W/V) potato lignin extract, stirring for 20min at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air at 40 ℃, and removing the film to obtain the UV protective film.
Step three, dissolving 30% (W/V) of zein, 2-4% of anthocyanin extraction solution (W/V) and 2% of guar gum in 80% of ethanol solution, and using 0.2mol/L NaOH solution or 0.2mol/L H2SO4And (3) regulating the pH value of the mixed solution to 3, slowly stirring for 1h at room temperature, and fully dissolving to obtain the preparation solution of the early warning chromogenic membrane. Placing the preparation solution of the early warning chromogenic membrane into an injector, selecting a needle tube with the diameter of 0.08mm, controlling the relative humidity to be 60% at room temperature, setting the spinning speed to be 0.04mm/min, the spinning voltage to be 12kV, the receiving distance to be 10cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90min respectively to finally obtain the early warning chromogenic membrane.
And step four, dissolving 2% (W/V) chitosan, 0.5% (W/V) vitamin C, 0.2% (W/V) H2O2 and 2% (W/V) gallic acid in a solution containing 1% (W/V) acetic acid, and uniformly stirring at room temperature to prepare the gallic acid grafted chitosan solution. Dissolving 1% (W/V) gallic acid grafted chitosan solution and 2% (W/V) polyvinyl alcohol in 40% (W/V) citric acid solution at 90 deg.C, stirring at 95 deg.C for 10min, cooling to room temperature, and removing bubbles in the solution. Placing the UV excited sterilization membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.30mm, controlling the relative humidity to be 45% at room temperature, setting the spinning speed to be 0.25mm/min, the spinning voltage to be 14kV, the receiving distance to be 15cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 40min respectively, and finally obtaining the UV excited sterilization membrane.
And step five, laminating the UV protective film, the early warning color developing film and the UV excitation sterilization film in the sequence from top to bottom to obtain the composite preservative film with the early warning and sterilization functions. As shown in fig. 1.
Example 2
This example provides a preparation of a composite film, including the following steps:
step one, drying the potato peel residues at 50 ℃ to constant weight, crushing, sieving, mixing 12% (W/V) of the potato peel residue particles with an ether solution, stirring for 10 hours at room temperature, filtering to remove impurities, and evaporating ether at 55 ℃ to obtain the potato lignin extract.
And step two, dissolving 2% (W/V) polylactic acid in chloroform, adding 22% (W/V) potato lignin extract, stirring for 16min at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air at 42 ℃, and removing the film to obtain the UV protective film.
Step three, dissolving 26 percent (W/V) of zein, 2 percent of anthocyanin extraction solution (W/V) and 2 percent of guar gum into 80 percent of ethanol solution, and using 0.2mol/L NaOH solution or 0.2mol/L H2SO4And (3) regulating the pH value of the mixed solution to 4, slowly stirring for 1h at room temperature, and fully dissolving to obtain the preparation solution of the early warning chromogenic membrane. Placing the preparation solution of the early warning chromogenic membrane into an injector, selecting a needle tube with the diameter of 0.08mm, controlling the relative humidity to be 60% at room temperature, setting the spinning speed to be 0.06mm/min, the spinning voltage to be 12kV, the receiving distance to be 12cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90min respectively to finally obtain the early warning chromogenic membrane.
Step four, 2 percent (W/V) of chitosan, 1 percent (W/V) of vitamin C and 0.3 percent (W/V) of H2O2Dissolving 2% (W/V) gallic acid in a solution containing 2% (W/V) acetic acid, and uniformly stirring at room temperature to prepare the gallic acid grafted chitosan solution. Dissolving 0.5-1% (W/V) gallic acid grafted chitosan solution and 1% (W/V) polyvinyl alcohol in 40% (W/V) citric acid solution at 90 ℃, stirring for 10min at 95 ℃, then cooling to room temperature, and eliminating bubbles in the solution. Placing the UV excited sterilization membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.30mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 16kV, the receiving distance to be 16cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 50min respectively, and finally obtaining the UV excited sterilization membrane.
And step five, laminating the UV protective film, the early warning color developing film and the UV excitation sterilization film in the sequence from top to bottom to obtain the composite preservative film with the early warning and sterilization functions.
Example 3
This example provides a preparation of a composite film, including the following steps:
step one, drying the potato peel residues at 40 ℃ to constant weight, crushing, sieving, mixing 10% (W/V) of the potato peel residue particles with an ether solution, stirring for 10 hours at room temperature, filtering to remove impurities, and evaporating ether at 50 ℃ to obtain the potato lignin extract.
And step two, dissolving 2% (W/V) polylactic acid in chloroform, adding 22% (W/V) potato lignin extract, stirring for 17min at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air at 42 ℃, and removing the film to obtain the UV protective film.
Step three, dissolving 28% (W/V) of zein, 3% of anthocyanin extraction solution (W/V) and 2% of guar gum in 80% of ethanol solution, and using 0.2mol/L of NaOH solution or 0.2mol/L of H2SO4And (3) regulating the pH value of the mixed solution to 3-4, slowly stirring for 1h at room temperature, and fully dissolving to obtain the preparation solution of the early warning chromogenic membrane. Placing the preparation solution of the early warning chromogenic membrane into an injector, selecting a needle tube with the diameter of 0.08mm, controlling the relative humidity to be 60% at room temperature, setting the spinning speed to be 0.04mm/min, the spinning voltage to be 12kV, the receiving distance to be 10cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90min respectively to finally obtain the early warning chromogenic membrane.
Step four, 2 percent (W/V) of chitosan, 1 percent (W/V) of vitamin C and 0.2 percent (W/V) of H2O2Dissolving 2% (W/V) gallic acid in a solution containing 2% (W/V) acetic acid, and uniformly stirring at room temperature to prepare the gallic acid grafted chitosan solution. Dissolving 1% (W/V) gallic acid grafted chitosan solution and 2% (W/V) polyvinyl alcohol in 91 deg.C 42% (W/V) citric acid solution, stirring at 95 deg.C for 12min, cooling to room temperature, and removing bubbles in the solution. Placing the UV-excited sterilization membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.35mm, controlling the relative humidity at 48% at room temperature, and setting the spinning speedThe degree is 0.3mm/min, the spinning voltage is 14kV, the receiving distance is 16cm, the rotating speed of the receiver is medium speed, and the spinning time is 50min respectively, so that the UV excited sterilization film is finally obtained.
And step five, laminating the UV protective film, the early warning color developing film and the UV excitation sterilization film in the sequence from top to bottom to obtain the composite preservative film with the early warning and sterilization functions.
Control group 1A composite film (without UV protective film)
Control 1 provides a composite membrane, specifically prepared as follows:
step one, dissolving 30 percent (W/V) of zein, 4 percent of anthocyanin extraction solution (W/V) and 2 percent of guar gum in 80 percent of ethanol solution, and using 0.2mol/L NaOH solution or 0.2mol/L H2SO4And (3) regulating the pH value of the mixed solution to 3, slowly stirring for 1h at room temperature, and fully dissolving to obtain the preparation solution of the early warning chromogenic membrane. Placing the preparation solution of the early warning chromogenic membrane into an injector, selecting a needle tube with the diameter of 0.08mm, controlling the relative humidity to be 60% at room temperature, setting the spinning speed to be 0.04mm/min, the spinning voltage to be 14kV, the receiving distance to be 10cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 100min respectively to finally obtain the early warning chromogenic membrane.
Step two, 1% (W/V) chitosan, 0.5% (W/V) vitamin C and 0.2% (W/V) H2O2Dissolving 1% (W/V) gallic acid in a solution containing 2% (W/V) acetic acid, and uniformly stirring at room temperature to prepare the gallic acid grafted chitosan solution. Dissolving 0.5% (W/V) gallic acid grafted chitosan solution and 2% (W/V) polyvinyl alcohol in 42% (W/V) citric acid solution at 90 deg.C, stirring at 95 deg.C for 12min, cooling to room temperature, and removing bubbles in the solution. Placing the UV excited sterilization membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.35mm, controlling the relative humidity to be 50% at room temperature, setting the spinning speed to be 0.36mm/min, the spinning voltage to be 16kV, the receiving distance to be 16cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 50min respectively to finally obtain the UV excited sterilization membrane.
And step three, laminating the early warning color developing film and the UV excitation sterilization film in the sequence from top to bottom to obtain the composite preservative film.
Control 2A composite membrane (without UV excitation sterilization membrane)
Step one, drying the potato peel residues at 45 ℃ to constant weight, crushing, sieving, mixing 12% (W/V) of the potato peel residue particles with an ether solution, stirring for 11 hours at room temperature, filtering to remove impurities, and evaporating ether at 505 ℃ to obtain the potato lignin extract.
And step two, dissolving 1% (W/V) polylactic acid in chloroform, adding 22% (W/V) potato lignin extract, stirring for 18min at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air at 42 ℃, and removing the film to obtain the UV protective film.
Step three, dissolving 28% (W/V) of zein, 3% of anthocyanin extraction solution (W/V) and 1% of guar gum in 80% of ethanol solution, and using 0.2mol/L of NaOH solution or 0.2mol/L of H2SO4And (3) regulating the pH value of the mixed solution to 3, slowly stirring for 1h at room temperature, and fully dissolving to obtain the preparation solution of the early warning chromogenic membrane. Placing the early warning chromogenic membrane preparation solution into an injector, selecting a needle tube with the diameter of 0.08mm, controlling the relative humidity to be 65% at room temperature, setting the spinning speed to be 0.05mm/min, the spinning voltage to be 13kV, the receiving distance to be 11cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 95min respectively, and finally obtaining the early warning chromogenic membrane.
And step four, laminating the UV protective film and the early warning color development film in sequence from top to bottom to obtain the composite preservative film.
Control group 3
The control group 3 used a common plastic film as a preservative film.
Effect verification
The fresh-keeping effects of the composite films obtained in examples 1 to 3 and the composite films and plastic films obtained in comparative examples 1 to 3 were further examined.
The method comprises the steps of purchasing fresh grass carps in a supermarket, removing heads, tails, scales and internal organs after bloodletting, removing fishbones after cleaning, and wrapping fish meat which is cut into fish meat with proper size by using a preservative film. Refrigerating at 4 deg.C in refrigerator, and taking out every 4 days.
Wherein the samples treated in examples 1-3 and controls 1 and 2 showed a reddish purple color when the wrap film showed a reddish purple colorThe preservative film is placed under LED ultraviolet light and the like, the wavelength is 395nm, and the irradiation intensity is 300 mu W/cm2The irradiation time is 3 min. The total bacterial count, thiobarbituric acid value and volatile basic nitrogen value of the fish are measured and compared with the blank of the fish wrapped by a common plastic film.
Detecting items:
1. total bacterial count of fish
Weighing 10.0g fish meat in a sterile operating table, adding 90mL sterile physiological saline with concentration of 0.85%, placing in a sterilized cooking bag, beating and homogenizing for 60s, and standing at room temperature for 20 min. 1mL of the supernatant was diluted to 10-7 in 9mL of physiological saline in a gradient. Selecting 3 appropriate dilutions, mixing 1mL of the dilution with 20mL of sterilized plate count agar medium, pouring onto the plate, after the agar is solidified, turning the plate over, culturing at 30 deg.C for 72h, and repeating for 3 times. Finally, colony counting is carried out. The results are shown in Table 1.
TABLE 1 Total number of grass carp bacteria in storage period
| 2 days | 4 days | 8 days | 12 days | 16 days | |
| Example 1(log cfu/g) | 2.5±0.2 | 2.9±0.1 | 3.6±0.1 | 4.5±0.3 | 5.2±0.2 |
| Example 2(log cfu/g) | 2.2±0.1 | 2.8±0.3 | 3.4±0.2 | 4.2±0.3 | 4.8±0.2 |
| Example 3(log cfu/g) | 2.4±0.3 | 2.6±0.2 | 3.2±0.2 | 3.9±0.1 | 4.5±0.2 |
| Control group 1(log cfu/g) | 3.2±0.3 | 6.1±0.2 | 7.2±0.4 | 8.1±0.3 | 8.9±0.2 |
| Control group 2(log cfu/g) | 2.3±0.2 | 4.8±0.1 | 5.4±0.1 | 6.2±0.2 | 7.6±0.2 |
| Control group 3(log cfu/g) | 2.8±0.2 | 5.8±0.3 | 7.4±0.4 | 8.4±0.3 | 9.2±0.2 |
2. Thiobarbituric acid number
Weighing 10g of minced fish, adding 25mL of distilled water, homogenizing, adding 25mL of trichloroacetic acid (TCA) with the mass concentration of 5%, stirring uniformly, standing for 30min, filtering, taking 5mL of supernatant, and adding 5mL of 0.02mol/L TBA solution. Heating the mixed solution in 80 deg.C constant temperature water bath for 40min for color development, cooling to room temperature, and measuring absorbance at 532 nm. The results are shown in Table 2.
TABLE 2 acid value of grass carp thiobarbiturate in storage period
| 2 days | 4 days | 8 days | 12 days | 16 days | |
| Example 1(mg/kg) | 0.08±0.02 | 0.09±0.01 | 0.11±0.01 | 0.15±0.01 | 0.20±0.03 |
| Example 2(mg/kg) | 0.05±0.01 | 0.08±0.01 | 0.10±0.02 | 0.15±0.02 | 0.18±0.02 |
| Example 3(mg/kg) | 0.07±0.03 | 0.10±0.02 | 0.15±0.02 | 0.18±0.01 | 0.22±0.02 |
| Control group 1(mg/kg) | 0.06±0.03 | 0.18±0.02 | 0.26±0.04 | 0.32±0.03 | 0.45±0.04 |
| Control group 2(mg/kg) | 0.07±0.02 | 0.17±0.01 | 0.23±0.01 | 0.29±0.02 | 0.39±0.03 |
| Control group 3(mg/kg) | 0.08±0.02 | 0.15±0.01 | 0.24±0.02 | 0.39±0.01 | 0.52±0.02 |
3. Volatile basic nitrogen
Weighing 10.00g of minced fish, placing in a beaker, adding distilled water to 100mL, homogenizing, soaking for 30min, filtering, sucking 5mL of filtrate and a digestive tube, and measuring with a volatile basic nitrogen apparatus. Each set of samples was assayed in parallel 3 times. The results are shown in Table 3.
TABLE 3 storage period volatile amino nitrogen values for grass carp
| 2 days | 4 days | 8 days | 12 days | 16 days | |
| Example 1(mg/100g) | 4.8±0.5 | 7.8±0.4 | 9.5±0.2 | 12.5±0.3 | 15.3±0.8 |
| Example 2(mg/100g) | 4.2±0.4 | 6.7±0.3 | 8.5±0.3 | 11.8±0.5 | 14.6±0.9 |
| Example 3(mg/100g) | 4.5±0.3 | 7.2±0.3 | 9.3±0.5 | 12.7±0.4 | 15.9±0.7 |
| Control group 1(mg/100g) | 5.3±0.2 | 10.2±0.5 | 16.2±0.6 | 19.2±1.1 | 27.5±1.2 |
| Control group 2(mg/100g) | 4.9±0.2 | 7.5±0.4 | 11.2±0.8 | 15.6±0.6 | 22.4±1.9 |
| Control group 3(mg/100g) | 5.2±0.3 | 12.3±0.9 | 23.2±1.0 | 32.4±1.2 | 40.5±2.2 |
Through researching the quality determination of different preservative films on the storage period of the grass carp, the result shows that the storage period of the grass carp can be effectively prolonged by combining the LED ultraviolet rays with the composite preservative film prepared in the embodiment 1-3 of the invention; when the fish is in a fresh state, the volatile basic nitrogen value is less than 10mg/100 g; when the display color is purple, the fish meat is second-time fresh meat, and the volatile basic nitrogen value is 10-15 mg/100 g. When the color is blue or purple, the fish meat is putrefying meat, and the volatile basic nitrogen value is more than 15mg/100 g.
And when the composite film shows purple, the fish is placed under LED ultraviolet light with a wavelength of 395nm and an irradiation intensity of 300 μ W/cm2The irradiation time is 3min, and the preservation period of the fish can be effectively prolonged by at least 3-4 days. The control group 1 preservative film lacks a protective layer, so that the sensitivity of the color development layer is reduced, and the sterilization time is not easy to accurately grasp; the preservative film of the control group 2 lacks a sterilization layer, so that the shelf life of the fish meat cannot be effectively prolonged.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (13)
1. A composite membrane with early warning and sterilization functions is characterized by comprising a UV protective membrane, an early warning color development membrane and a UV excitation sterilization membrane from top to bottom;
the UV protection film is prepared from the following raw materials in parts by weight: 1-2 parts of polylactic acid and 20-25 parts of potato lignin extract;
the UV excited sterilization film is prepared from the following raw materials in parts by weight: 0.5-1 part of gallic acid grafted chitosan solution, 1-2 parts of polyvinyl alcohol and 40-45 parts of citric acid; the gallic acid grafted chitosan solution is prepared from the following raw materials in parts by weight: 1-2 parts of chitosan, 0.5-1 part of vitamin C and H2O20.2-0.4 part of gallic acid and 1-2 parts of gallic acid;
the early warning color developing film is prepared from the following raw materials in parts by weight: 25-30 parts of corn protein, 2-4 parts of anthocyanin extracting solution and 1-2 parts of guar gum.
2. A composite film according to claim 1 wherein said potato lignin extract is obtained by extraction with diethyl ether.
3. A composite film according to claim 2 wherein said potato lignin extract is obtained by a process comprising:
drying the potato peel residues at 40-50 ℃ to constant weight, crushing and sieving to obtain potato peel residue particles; mixing the potato peel residue particles with an ether solution according to the proportion of 10-15% (W/V), stirring at room temperature for 10-12 h, filtering to remove impurities, and evaporating ether at 50-60 ℃ to obtain the potato lignin extract.
4. The composite film of claim 1 wherein said pre-warning color developing film is obtained using an electrospinning technique.
5. The composite film of claim 4, wherein the pre-warning color-developing film is obtained by:
mixing the raw materials to prepare an early warning color developing film solution, placing the solution in an injector, selecting a needle tube with the diameter of 0.08-0.09 mm, controlling the relative humidity at 60-70% at room temperature, setting the spinning speed at 0.04-0.06 mm/min, the spinning voltage at 12-14 kV, the receiving distance at 10-12 cm, the rotating speed of a receiver at medium speed, and the spinning time at 90-100 min respectively to obtain the early warning color developing film.
6. The composite membrane of claim 1, wherein the UV activated germicidal membrane is produced using an electrospinning technique.
7. The composite film of claim 6, wherein the UV activated germicidal film is obtained by:
dissolving 0.5-1% (W/V) gallic acid grafted chitosan solution and 1-2% (W/V) polyvinyl alcohol in 40-45% (W/V) citric acid solution at 90-92 ℃, stirring at 95 ℃ for 10-15 min, cooling to room temperature, and eliminating bubbles in the solution to obtain UV excited sterilization membrane solution; placing the UV excited sterilization membrane solution into an injector, selecting a needle tube with the diameter of 0.30-0.40 mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 14-18 kV, the receiving distance to be 15-18 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 40-60 min respectively to obtain the UV excited sterilization membrane.
8. A preparation method of the composite membrane with the functions of early warning and sterilization as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) preparation of the UV protective film: taking potato peel residues as a raw material, and extracting a potato lignin extract; dissolving polylactic acid in trichloromethane, adding a potato lignin extract, stirring at room temperature, removing bubbles in the solution, casting the solution onto a glass plate, drying by hot air, and removing the film to obtain a UV protective film;
(2) preparing an early warning color developing film: dissolving corn protein, anthocyanin extraction solution and guar gum in 80% ethanol solution, slowly stirring at room temperature, fully dissolving to obtain early warning color development membrane solution, and performing electrostatic spinning to obtain an early warning color development membrane;
(3) preparing a UV-excited sterilization film: mixing chitosan and vitamin C, H2O2Dissolving gallic acid in an acetic acid solution, and uniformly stirring at room temperature to prepare a gallic acid grafted chitosan solution; dissolving a gallic acid grafted chitosan solution and polyvinyl alcohol in a citric acid solution, uniformly stirring, cooling to room temperature, eliminating bubbles in the solution, and performing electrostatic spinning to obtain a UV excited sterilization membrane;
(4) and pressing the UV protective film, the early warning color development film and the UV excitation sterilization film in the order from top to bottom to obtain the composite film.
9. The method according to claim 8, wherein in the step (2), the technical parameters of the electrostatic spinning are as follows: selecting a needle tube with the diameter of 0.08-0.09 mm, controlling the relative humidity to be 60-70% at room temperature, setting the spinning speed to be 0.04-0.06 mm/min, the spinning voltage to be 12-14 kV, the receiving distance to be 10-12 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 90-100 min respectively;
and/or in the step (3), the technical parameters of the electrostatic spinning are as follows: selecting a needle tube with the diameter of 0.30-0.40 mm, controlling the relative humidity to be 45-55% at room temperature, setting the spinning speed to be 0.25-0.45 mm/min, the spinning voltage to be 14-18 kV, the receiving distance to be 15-18 cm, the rotating speed of a receiver to be medium speed, and the spinning time to be 40-60 min respectively.
10. Use of a composite film according to any of claims 1 to 7 for packaging fresh food.
11. The use of claim 10, wherein the fresh food is fresh fish, pork, poultry.
12. Use according to claim 11, wherein the obtained composite film is used as a preservative film to package fresh fish meat and stored at a temperature above 0 ℃; when the composite film shows reddish purple, the fresh fish meat is placed under LED ultraviolet light and the like, the wavelength is 265-395 nm, and the irradiation intensity is 300-400 mu W/cm2。
13. A method for judging the meat quality of fresh fish using the composite film of any one of claims 1 to 7, comprising: when the composite film of any one of claims 1 to 7 exhibits a red color, the fish meat is fresh meat having a volatile basic nitrogen value of less than 5mg/100 g; when the color of the composite membrane is purple, the fish meat is sub-fresh meat, and the volatile basic nitrogen value of the fish meat is 5-10 mg/100 g; when the composite film shows blue or purple color, the fish meat is putrefying meat, and the volatile basic nitrogen value of the putrefying meat is more than 10mg/100 g.
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| CN111676538A (en) * | 2020-06-10 | 2020-09-18 | 合肥工业大学 | Preparation method of anthocyanin/PVA (polyvinyl alcohol) nano composite fiber |
| CN113211924B (en) * | 2020-11-27 | 2023-05-09 | 天津科技大学 | Thermal insulation packaging bag for cooling and preventing dewing of quick-frozen food |
| CN113281312B (en) * | 2021-03-31 | 2024-02-02 | 渤海大学 | Preparation method and application of ratio type fluorescence response sensing tag for salmon freshness |
| CN113211898A (en) * | 2021-05-28 | 2021-08-06 | 海南赛诺实业有限公司 | Coating film for food packaging |
| CN113234260B (en) * | 2021-06-04 | 2023-06-13 | 重庆工商大学 | Preparation method of guar gum base nano composite film |
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Application publication date: 20190528 Assignee: GUANGDONG FORUNSIKE BIOTECHNOLOGY Co.,Ltd. Assignor: Institute of Agricultural Products Processing, Chinese Academy of Agricultural Sciences (Institute of Atomic Energy Utilization, Chinese Academy of Agricultural Sciences) Contract record no.: X2023980032271 Denomination of invention: A composite membrane with early warning and sterilization functions, its preparation method and application Granted publication date: 20201229 License type: Common License Record date: 20230220 |