CN115466570A - Preparation method and application of silk-based coating material - Google Patents
Preparation method and application of silk-based coating material Download PDFInfo
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- CN115466570A CN115466570A CN202210518196.8A CN202210518196A CN115466570A CN 115466570 A CN115466570 A CN 115466570A CN 202210518196 A CN202210518196 A CN 202210518196A CN 115466570 A CN115466570 A CN 115466570A
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- silk
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- chlorogenic acid
- silk fibroin
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention discloses a preparation method and application of a silk-based coating material. Belongs to the field of composite materials, and comprises the following steps: dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution; 2. dialyzing the silk solution to remove salt and concentrating to obtain a silk fibroin solution; 3. adding cellulose nanocrystals and chlorogenic acid into the silk fibroin solution, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution; 4. attaching the silk fibroin mixed solution to the surface of the fruit by a solution dipping method, and forming a coating film on the surface of the fruit by a solvent evaporation method. According to the invention, hydrogen bonds are formed between the added cellulose nanocrystals and chlorogenic acid and silk fibroin, so that beta folding is induced, and the hydrophobicity and mechanical properties of the coating material can be effectively enhanced; in the method, a mixed solution of cellulose nanocrystals and chlorogenic acid is added to form a film on the surface of the fruit quickly at normal temperature; the preparation method is simple and easy to operate, low in raw material cost and convenient for industrial popularization.
Description
Technical Field
The invention belongs to the field of composite materials, relates to a preparation method and application of a silk-based antibacterial coating material, and particularly relates to a preparation method and application of a silk-based antibacterial coating material through auxiliary crosslinking of cellulose nanocrystals and chlorogenic acid.
Background
In recent years, due to public concerns about food quality and safety, preservation of fresh foods, particularly fruits, has attracted a great deal of attention. Among them, water dispersion and microbial infection are important causes of fruit decay, and water loss of fruits not only causes pericarp shrinkage, but also causes various enzyme activities to be aggravated, and fruit deterioration is accelerated. In addition, fruits placed at ambient temperature are quickly contaminated and attacked by microorganisms without some protective measures. During the growth and reproduction of the microorganisms, various enzymes are generated to destroy the cell walls of the fruits and enter the cells, so that the fruits deteriorate and rot. Therefore, the method has important significance for the production, transportation and sale of the fruits by controlling water dispersion and blocking microbial infection to slow down the deterioration speed of the fruits and prolong the shelf life of the fruits. Recently, bio-based films having biocompatibility and biodegradability have attracted much attention. Currently, polysaccharides, proteins and lipids have become the main raw materials for bio-based films. Among them, silk is a natural fiber mainly composed of proteins, and among them, silk fibroin has been used in the fields of foods, cosmetics and medical treatment because of its biodegradability, biocompatibility and excellent mechanical properties. Furthermore, studies on the edibility of silk fibroin have shown that oral administration of silk fibroin does not cause mutagenic, genotoxic, toxicological or allergic problems, and thus it can be widely used in the food industry as a safe edible protein.
However, in the preparation method of the prior art, the film material prepared from silk fibroin mostly only has basic barrier performance, and lacks the performance of resisting microbial infection. For example, chinese patent application No. 202111317066.X discloses a method for preparing silk fibroin powder, which comprises obtaining raw materials, degumming, dissolving, desalting, extracting, and drying to obtain silk fibroin powder, and preparing silk fibroin solution from the obtained silk fibroin powder, wherein the silk fibroin solution can be attached to the surface of food to form a film, thereby achieving the effect of preservation. The Chinese invention patent with the application number of 202110152222.5 discloses a method for drying and film-forming silk fibroin solution on the surface of fruits for preservation, wherein the silk fibroin solution is obtained by dissolving degummed silk by using lithium bromide, dialyzing and purifying. Chinese invention patents with application numbers of 202110152748.3 and 202110152748.3 prepare 0.1-10% silk fibroin solution which is respectively sprayed on treated large and medium-sized Chinese medicinal materials and then dried to form a film so as to finish the fresh keeping of the Chinese medicinal materials. Most of pure silk fibroin films have the problems of poor hydrophobicity, weak water vapor barrier property and the like, and in addition, the pure silk fibroin films do not have the capability of resisting microbial invasion and are not beneficial to inhibiting fruit rot. The Chinese patent with the application number of 202111468589.4 discloses a preparation method and application of a peanut leaf fiber/fibroin film, the peanut leaf fiber and fibroin are dissolved in ionic liquid, and a mixed solution is transferred to two glass sheets, so that the problem of unstable water barrier performance of a single protein film is solved by means of flow-extension film forming. However, ionic liquids are expensive and not suitable for large-scale production, and the peanut leaf fiber/fibroin film itself is not antimicrobial and is not resistant to microbial infestation of fruits. The patent with the application number of 202110439855 discloses a fibroin oxidized bacterial cellulose nano composite film and a preparation method thereof, wherein the fibroin oxidized bacterial cellulose nano composite film comprises silk fibroin, nano silver, polyvinyl alcohol and oxidized bacterial cellulose, and has antibacterial activity and can be used as a packaging material. However, the preparation process is very complicated and silver is expensive as an antibacterial agent. In addition, although the nano silver is used as a metal nano particle, the antibacterial property of the silk composite film is endowed, the addition of the nano silver can not effectively improve the hydrophobicity of the film, and the preservative film with low hydrophobicity can not effectively inhibit the water loss of fruits and can not achieve the ideal preservative effect. Therefore, the selection of a proper antibacterial agent and a preparation process are problems to be solved in the preparation method of the silk fibroin composite material.
Cellulose nanocrystals are needle-or rod-shaped celluloses of 1-100nm diameter, obtainable from cellulose by mechanical, thermochemical and biological methods, and are widely used as nanoreinforcing agents due to their high surface activity and crystallinity and excellent mechanical and thermal properties. Compared with conventional-scale cellulose, nano-scale cellulose has a higher specific surface area and more exposed hydroxyl groups, and thus, more hydrogen bonds may be formed between the hydroxyl groups of the cellulose nanocrystals and the amino or carboxyl groups of silk fibroin. Thus, the addition of cellulose nanocrystals can enhance the hydrophobicity, barrier, and mechanical properties of bio-based films, which helps to extend the shelf life of the food. However, simple or mixed biofilms can only passively protect food from environmental factors. Biofilms are also required to inhibit or retard the growth of microorganisms on food surfaces to preserve food safety and quality. Chlorogenic acid is an important bioactive dietary polyphenol, widely exists in natural plants, and has antioxidant, antibacterial, antiinflammatory and antipyretic effects. In addition, chlorogenic acid molecules have rich hydroxyl groups, and can form hydrogen bonds with polymers such as silk fibroin and cellulose nanocrystals, so that the hydrophobicity and the water vapor barrier property of the material are further enhanced. Therefore, chlorogenic acid can be used as an antibacterial agent of the edible film and also can be used as a bridge formed by hydrogen bonds between biopolymers.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a silk-based antibacterial coating material which has high hydrophobicity, low water vapor transmission rate and antibacterial property and is prepared by the auxiliary cross-linking of cellulose nanocrystals and chlorogenic acid.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the silk-based coating material comprises the following specific preparation steps:
dissolving the prepared degummed silk in a mixed solution containing calcium chloride, ethanol and water to prepare a silk solution;
step (2), dialyzing the prepared silk solution to remove salt, and concentrating to obtain a silk fibroin solution;
step (3), sequentially adding cellulose nanocrystals and chlorogenic acid into the prepared silk fibroin solution, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid;
step (4), attaching the prepared silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid to the surface of the fruit by a solution dipping method, and forming a coating film by a solution evaporation method at normal temperature; namely, the silk-based antibacterial coating material containing cellulose nanocrystals and chlorogenic acid for auxiliary crosslinking.
Further, in the step (1), the mass fractions of the silk solution prepared are as follows: 5 to 15 weight percent.
Further, in the step (2), the dialysis time is: 48-72 h, the dialysis temperature is: 4-20 ℃, and the concentration of the concentrated silk fibroin solution is as follows: 5 to 15 weight percent.
Further, in the step (3), the mass fraction of the added cellulose nanocrystals is: 0.5-7 wt%, and the mass fraction of chlorogenic acid is: 0.5 to 7 weight percent;
the ultrasonic power is as follows: 480-900 w, the dispersing time is as follows: 0.5 to 2 hours.
Further, in the step (4), in the solution evaporation method, the temperature at which the solvent is evaporated is: 5-30 ℃, and the required time is as follows: 1 to 4 hours.
Further, the silk-based antibacterial coating material prepared by any one of the preparation methods is applied to preservation of fruits and vegetables after picking.
Has the advantages that: compared with the prior art, the invention has the characteristics that: 1. hydrogen bonds are formed between the added cellulose nanocrystals and chlorogenic acid and silk fibroin to induce beta folding, so that the hydrophobicity and mechanical properties of the coating material can be effectively enhanced, and the water vapor transmission rate of the coating material is reduced; 2. chlorogenic acid as a plant active substance can be directly obtained from a large amount of plants, is renewable in source and is a good antibacterial agent; 3. the prepared coating material has good plasticity and toughness, and the stock solution can quickly form a film on the surface of the fruit at normal temperature; 4. the preparation method is simple, the cost of raw materials is low, complex chemical reaction is not needed, and the industrial popularization is facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of silk-based coating material of example 1 of the present invention;
FIG. 2 is a water vapor transmission rate histogram of example 1 of the present invention;
FIG. 3 is a water contact angle graph of example 1 of the present invention;
FIG. 4 is a graph of the antibacterial properties of a silk-based coating material of example 1 of the present invention, wherein a is a control group, b is E.coli treated in comparative example 1, c is E.coli treated in comparative example 2, d is E.coli treated in example 1, wherein e is a control group, f is Staphylococcus aureus treated in comparative example 1, g is Staphylococcus aureus treated in comparative example 2, and h is Staphylococcus aureus treated in example 1;
fig. 5 is a graph of the appearance of strawberries in different time periods within 15 days of preservation, and b is an internal image of strawberries after 15 days of preservation, according to the invention, in example 1, strawberry is selected as a model fruit;
FIG. 6 shows the decay rate of strawberries treated according to example 1 of the present invention;
FIG. 7 is the mass loss rate after treatment in example 1 of the present invention;
FIG. 8 is a flow chart of the preparation of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The preparation method of the silk-based coating material comprises the following specific preparation steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution;
step two, dialyzing the silk solution obtained in the step one to remove salt, and further concentrating to obtain a silk fibroin solution;
step three, sequentially adding cellulose nanocrystals and chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and forming a coating film on the surface of the fruit by a solvent evaporation method.
Further, in the first step, the mass fraction of the silk solution is 5-15 wt%.
Further, in the second step, the dialysis time is 48-72 h, the dialysis temperature is 4-20 ℃, and the concentration of the concentrated silk fibroin solution is 5-15 wt%.
Further, in the third step, the mass fraction of the cellulose nanocrystal is 0.5-7 wt%, the mass fraction of the chlorogenic acid is 0.5-7 wt%, the ultrasonic power is 480-900 w, and the dispersion time is 0.5-2 h. .
Furthermore, in the fourth step, the temperature required by the solvent evaporation method is 5-30 ℃, and the required time is 1-4 h.
Further, the prepared silk-based antibacterial coating material with cellulose nanocrystals and chlorogenic acid auxiliary cross-linking is applied to fruit and vegetable fresh-keeping after picking.
The preparation principle is as follows: the degumming silk is dissolved in a mixed solution of calcium chloride, ethanol and water, degumming and concentration are carried out to obtain a silk fibroin solution with a certain concentration, and hydrogen bonds are formed between the degumming silk and the silk by adding cellulose nanocrystals and chlorogenic acid and inducing a beta-folded structure of the silk, so as to obtain the silk-based coating material with high hydrophobicity, low water vapor transmission rate and enhanced mechanical property.
Example 1
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 4 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
step three, sequentially adding 1wt% of cellulose nanocrystals and 1wt% of chlorogenic acid into the mixed solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid, wherein the ultrasonic power is set to 480W, and the ultrasonic time is set to 1h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 20 ℃, and the drying time is 2 hours.
Comparative example 1
For comparison, by not performing step three in example 1, a pure silk fibroin solution was prepared; the method specifically comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 4 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
and step three, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 20 ℃, and the drying time is 2 hours.
Comparative example 2
For comparison, a cellulose nanocrystal and silk fibroin composite solution was prepared by not adding chlorogenic acid powder in step three in example 1; the method specifically comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 4 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
step three, sequentially adding 1wt% of cellulose nanocrystals into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and chlorogenic acid, wherein the ultrasonic power is set to 480W, and the ultrasonic time is set to 1h;
step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 20 ℃, and the drying time is 2 hours; as shown in FIG. 1, the SEM image of example 1 shows that there are many small particles distributed uniformly and the surface is rough.
As shown in FIG. 2, the water vapor transmission rates of comparative example 1, comparative example 2 and example 1 are shown, respectively, and the water vapor transmission rate of comparative example 1 is at most 2.235X 10 10 g -1 Pa -1 s -1 m -1 The water vapor transmission rate of example 1 was 1.246X 10 as the lowest 10 g - 1 Pa -1 s -1 m -1 This shows that the addition of cellulose nanocrystals and chlorogenic acid can effectively reduce the water vapor transmission rate of the silk-based coating material.
As shown in fig. 3, the water contact angle of comparative example 1 was 80.3 ° minimum, and the water contact angle of example 1 was 90.1 ° maximum, which indicates that the addition of cellulose nanocrystals and chlorogenic acid was effective in increasing the hydrophobicity of the coating material.
As shown in FIG. 4, it can be seen that the control group, comparative example 1 and comparative example 2 had no antibacterial activity due to the absence of chlorogenic acid as an antibacterial agent, and many colonies were formed on the plate; the silk-based coating material in example 1 successfully kills the thalli by utilizing the antibacterial ability of chlorogenic acid, so that no colony is formed on the surface of a flat plate, and the coating material is proved to have good antibacterial performance.
As shown in fig. 5, it can be seen that the degree of rotting and mildewing of the strawberries of the control group was the most severe, the degree of rotting and mildewing of the strawberries of the comparative examples 1 and 2 was reduced compared to the control group, and the strawberries of the example 1 were substantially free from rotting and mildewing; in addition, the pictures in the strawberries are visible, the color of the pulp of the control group, the comparative example 1 and the comparative example 2 is changed into dark brown, and obvious deterioration appears; while the pulp of example 1 still appeared fresh pink.
As shown in FIG. 6, the decay rate of the control group was the fastest, and the decay rate after 15 days was 70.00%; the rot rates of comparative example 1 and comparative example 2 were 33.33% and 35.00%, respectively; whereas the strawberry rot rate of example 1 was the lowest (21.67%); the results demonstrate that the addition of chlorogenic acid in example 1 makes the edible film effective in inhibiting strawberry decay and microbial invasion.
As shown in fig. 7, the strawberry of the control group had the highest weight loss (15.31%); the weight loss ratio (8.57%) of the strawberry of comparative example 2 was lower than the weight loss ratio (10.49%) of the film-packaged strawberry of comparative example 1, which indicates that the cellulose nanocrystals enhanced the barrier properties of the edible film; the weight loss of the strawberry of example 1 was the lowest (7.32%), which indicates that the strawberry of example 1 has the best barrier property and can effectively inhibit the water loss of the strawberry.
Example 2
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 8 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
step three, sequentially adding 3wt% of cellulose nanocrystals and 3wt% of chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid, wherein the ultrasonic power is set to be 600W, and the ultrasonic time is set to be 2h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 30 ℃, and the drying time is 1h.
Example 3
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 12 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
step three, sequentially adding 5wt% of cellulose nanocrystalline and 5wt% of chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystalline and the chlorogenic acid, wherein the ultrasonic power is set to be 600W, and the ultrasonic time is set to be 2h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 5 ℃, and the drying time is 4 hours.
Example 4
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 5 wt%;
step two, dialyzing the silk solution obtained in the step one at 20 ℃ for 48 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 5 wt%;
step three, sequentially adding 7wt% of cellulose nanocrystals and 7wt% of chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid, wherein the ultrasonic power is set to be 720W, and the ultrasonic time is set to be 2h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit, wherein the drying temperature is 20 ℃, and the drying time is 2 hours.
Example 5
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 4 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 10 wt%;
step three, sequentially adding 10wt% of cellulose nanocrystalline and 10wt% of chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystalline and the chlorogenic acid, wherein the ultrasonic power is set to 900W, and the ultrasonic time is set to 2h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit, wherein the drying temperature is 20 ℃, and the drying time is 2 hours.
Example 6
A preparation method of a silk-based coating material comprises the following steps:
step one, dissolving degummed silk in a mixed solution of calcium chloride, ethanol and water to prepare a silk solution with the mass fraction of 10 wt%;
step two, dialyzing the silk solution obtained in the step one at 4 ℃ for 72 hours to remove salt, and further concentrating to obtain a silk fibroin solution with the mass fraction of 20 wt%;
step three, sequentially adding 1wt% of cellulose nanocrystals and 1wt% of chlorogenic acid into the solution obtained in the step two, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid, wherein the ultrasonic power is set to be 720W, and the ultrasonic time is set to be 2h;
and step four, adhering the mixed solution obtained in the step three to the surface of the fruit by a solution dipping method, and further forming a coating film on the surface of the fruit by a solvent evaporation method, wherein the drying temperature is 20 ℃, and the drying time is 2 hours.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (6)
1. A preparation method of a silk-based coating material is characterized by comprising the following specific preparation steps:
dissolving the prepared degummed silk in a mixed solution containing calcium chloride, ethanol and water to prepare a silk solution;
step (2), dialyzing the prepared silk solution to remove salt, and concentrating to obtain a silk fibroin solution;
step (3), sequentially adding cellulose nanocrystals and chlorogenic acid into the prepared silk fibroin solution, and performing ultrasonic dispersion to obtain a silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid;
step (4), attaching the prepared silk fibroin mixed solution containing the cellulose nanocrystals and the chlorogenic acid to the surface of the fruit by a solution dipping method, and forming a coating film by a solution evaporation method at normal temperature; namely, the silk-based antibacterial coating material containing cellulose nanocrystals and chlorogenic acid for auxiliary crosslinking.
2. The method for preparing silk-based coating material according to claim 1,
in the step (1), the mass fraction of the silk solution is as follows: 5 to 15 weight percent.
3. The method for preparing silk-based coating material according to claim 1,
in step (2), the dialysis time is: 48-72 h, the dialysis temperature is: 4-20 ℃, and the concentration of the concentrated silk fibroin solution is as follows: 5 to 15 weight percent.
4. The method for preparing silk-based coating material according to claim 1,
in the step (3), the mass fraction of the added cellulose nanocrystals is as follows: 0.5-7 wt%, and the mass fraction of chlorogenic acid is: 0.5 to 7 weight percent;
the ultrasonic power is as follows: 480-900 w, the dispersing time is as follows: 0.5 to 2 hours.
5. The method for preparing silk-based coating material according to claim 1,
in the step (4), in the solution evaporation method, the temperature at which the solvent is evaporated is: 5-30 ℃, and the required time is as follows: 1 to 4 hours.
6. Use of the silk-based coating material prepared by the preparation method according to any one of claims 1 to 5 for the preservation of fruits and vegetables after picking.
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| CN106928729A (en) * | 2017-03-27 | 2017-07-07 | 广西科技大学 | A kind of nanometer silver antimicrobial regenerated silk fibroin material and preparation method thereof |
| CN111575829A (en) * | 2020-07-01 | 2020-08-25 | 深圳千维生态纺织有限公司 | Fibroin-containing fiber and preparation method thereof |
| CN112300292A (en) * | 2020-11-20 | 2021-02-02 | 江苏科技大学 | Preparation method of chlorogenic acid modified cellulose antibacterial material based on natural active ingredients |
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| CN106928729A (en) * | 2017-03-27 | 2017-07-07 | 广西科技大学 | A kind of nanometer silver antimicrobial regenerated silk fibroin material and preparation method thereof |
| CN111575829A (en) * | 2020-07-01 | 2020-08-25 | 深圳千维生态纺织有限公司 | Fibroin-containing fiber and preparation method thereof |
| CN112300292A (en) * | 2020-11-20 | 2021-02-02 | 江苏科技大学 | Preparation method of chlorogenic acid modified cellulose antibacterial material based on natural active ingredients |
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