CN114371163A - Preparation method of MOFs (metal-organic frameworks) anthocyanin-loaded functional partitioned freshness indication film - Google Patents
Preparation method of MOFs (metal-organic frameworks) anthocyanin-loaded functional partitioned freshness indication film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
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- 238000002791 soaking Methods 0.000 claims description 4
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- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 4
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/775—Indicator and selective membrane
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Abstract
The invention belongs to the technical field of food packaging, and particularly relates to a preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film. The functional partitioned freshness indicating membrane loaded with the anthocyanin by MOFs is obtained by uniformly mixing a metal-organic framework material loaded with the anthocyanin, a natural antibacterial substance and a polymer and then carrying out partitioned electrostatic spinning; the hydrophobic antibacterial layer is obtained by mixing acetone, N-dimethylformamide, polyvinylidene fluoride and natural antibacterial materials and then carrying out partition electrostatic spinning; in the spinning process, the antibacterial area and the indication area are functionally partitioned according to the functional characteristics and the action positions of the antibacterial area and the indication area in the package, the freshness indication area and the hydrophobic antibacterial area are respectively electrospun, and finally a double-layer film integrating the indication area film and the antibacterial area film is obtained, so that the mutual influence of the functional areas is reduced to the maximum extent, and the functional characteristics of corresponding materials are exerted to the maximum extent; can effectively improve the accuracy of freshness indication and has the function of bacteriostasis.
Description
Technical Field
The invention belongs to the technical field of food packaging, and particularly relates to a preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film.
Background
Along with the improvement of science and technology and the improvement of living standard, the requirements of people on food nutrition, health and safety are gradually increased. Chilled fresh meat refers to raw fresh meat which is quickly cooled after slaughtered livestock carcasses, the central temperature of the meat is reduced to 0-4 ℃ within 24 hours, and the meat is always kept within the range of 0-4 ℃ in subsequent processing, circulation and sale processes. Although chilled meat can be stored at a low temperature throughout the supply chain from production to sale, it is still subject to spoilage due to microbial growth and proliferation, lipid oxidation, and the like, resulting in a decrease in freshness. The life span on a regular meat package does not accurately express its freshness. Therefore, the design of the intelligent package with the functions of monitoring, detecting, recording, tracking and communicating is of great significance. The food freshness indicating film is a hot spot direction, can provide related food quality information through color change, is simple and convenient, has low price and has good application prospect.
The food freshness indicator film is generally composed of two parts, one is a pH indicator which reacts with metabolites that chemically react during storage of the food to produce a corresponding color change; the other part is a degradable polymer for immobilizing the indicator. Commonly used polymers are polysaccharides, lipids and proteins, which are generally more hydrophilic. Meat itself contains higher moisture, and more water vapor is usually generated in the storage process, so that the environmental humidity in the package is higher, the hydrophilic polymer material swells, the integrity of the film is damaged, the pH indicator leaks, and the stability and reliability of the indicator in the freshness indicating process are affected. This is a big problem faced in the field of indicating the freshness of food at present. Meanwhile, the existing food freshness indicating films all carry multiple functions in the same area, so that multiple bioactive components carried by the indicating films are mutually influenced and even mutually inhibited, and cannot exert the functions to the maximum extent, and the application of the food freshness indicating films with the functional partitions in the field of food packaging is not reported yet.
Most of the pH indicators commonly used in current freshness indicating packages are anthocyanins, which have a pH sensitive group in their structure. During the putrefaction process of high protein food such as meat, etc., substances containing nitrogen, amine, ammonia, alcohols, sulfur and the like are generated, so that the pH value in the environment is changed, anthocyanin senses the pH change in the environment, the molecular structure is changed, and the color change is shown, so that the acidity and alkalinity of the environment can be qualitatively indicated, and the freshness of the meat can be judged. However, the anthocyanin is unstable in chemical structure, is sensitive to external factors such as temperature, illumination and the like, and can generate color change under the influence of the factors such as temperature, illumination and the like, so that the indicating result deviation of the food freshness indicating film is large. Therefore, the improvement of the stability of the anthocyanin has important significance for the practical application of the food freshness indicating film.
Disclosure of Invention
The invention aims to solve the technical problems that a film-forming base material and anthocyanin of the existing food freshness indicating film are unstable in chemical structure, bioactive components are easy to gather, multiple functions in the same area of a packaging film are disordered and the like, and provides a preparation method of a high-stability anthocyanin-based functional partition type freshness indicating package. The preparation method of the functional partition type freshness indicating package adopts an electrostatic spinning technology, so that the reaction specific surface area of the film is effectively improved, the exposed sites of active ingredients are increased, the aggregation of the active ingredients is avoided, and the biological safety is improved. And in the spinning process, the antibacterial area and the indication area are subjected to functional partitioning according to the functional characteristics and the action positions of the antibacterial area and the indication area in the package, and the freshness indication area and the comfortable antibacterial area are respectively electrospun. The freshness indication area adopts anthocyanin embedded by MOFs nano materials as a high-stability pH indicator, so that the light and heat stability of the anthocyanin is effectively improved; meanwhile, the porous structure of the MOFs effectively increases active exposure sites, so that the reaction is more sensitive. The hydrophobic antibacterial area adopts super-hydrophobic polymers as film forming base materials and is added with natural antibacterial materials with broad-spectrum antibacterial bioactivity, so that the hydrophobic property is improved and the antibacterial function is endowed. The hydrophobic antibacterial area and the freshness indicating area are divided, so that the function of the bioactive components is exerted to the maximum extent.
The present invention achieves the above technical objects by the following technical means.
A preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film comprises the following steps:
(1) preparing MOFs materials;
dissolving gamma-cyclodextrin and potassium hydroxide in ultrapure water, performing ultrasonic treatment until the gamma-cyclodextrin and the potassium hydroxide are completely dissolved, filtering by using an organic microporous filter membrane to obtain a filtrate, mixing the filtrate with methanol A, and heating in a constant-temperature water bath until turbid liquid is clear; adding polyethylene glycol and methanol B into the obtained clear solution, forming a precipitate A at room temperature, washing the precipitate A with methanol C and ethanol respectively, finally centrifuging to obtain a precipitate B, soaking the precipitate B in dichloromethane for a period of time, centrifuging and vacuum-drying overnight to obtain a product, namely the gamma-CD-MOFs nano-particles;
further, the dosage ratio of the gamma-cyclodextrin, the potassium hydroxide and the ultrapure water in the step (1) is 1.3-3.48 g: 0.45-1.2 g: 20-50 mL; the volume ratio of the filtrate to the methanol A is 1: 1; the temperature of the constant-temperature water bath is 35 ℃, and the heating time is 2 h.
Further, the volume ratio of the clear solution in the step (1) to the polyethylene glycol to the methanol B is 4:1: 1; the dosage ratio of the sediment A to the methanol C to the ethanol is 1 g: 1-2 mL: 12 mL; the dosage ratio of the precipitate B to the dichloromethane is 1 g: 2-3 mL.
Further, the rotating speed of the centrifugation in the step (1) is 1800r/min, and the centrifugation time is 10 min; the duration of the soaking period is 70-75 h.
(2) Encapsulation of anthocyanins in a metal organic framework;
dissolving gamma-CD-MOFs nano particles and anthocyanin in methanol, magnetically stirring uniformly in the dark, centrifuging the obtained mixed solution, collecting precipitate, adding methanol, ultrasonically dissolving to remove unencapsulated anthocyanin, centrifuging again, and vacuum-drying the precipitate in the dark overnight to obtain gamma-CD-MOF loaded with anthocyanin;
further, the dosage ratio of the anthocyanin, the gamma-CD-MOF and the methanol in the step (2) is 1.16-2.9 g: 1.75-4.4 g: 10 mL.
Further, the mass ratio of the precipitate in the step (2) to the methanol is 1: 1; the centrifugal speed is 1800r/min, and the centrifugal time is 10 min; the vacuum drying temperature was 50 ℃.
(3) Preparation of the electrospinning solution
Preparing a hydrophobic antibacterial layer solution: firstly, mixing acetone and N, N-dimethylformamide solution, then adding polyvinylidene fluoride, adding a natural antibacterial material, blending, sealing, and stirring until the natural antibacterial material is completely dissolved to obtain a mixed solution which is an antibacterial hydrophobic layer solution;
preparing a freshness indicating layer solution: dissolving sodium alginate and polyvinyl alcohol in an aqueous solution, adding the gamma-CD-MOF nano particles loaded with anthocyanin into a sodium alginate/polyvinyl alcohol polymer solution under the action of ultrasound, sealing, and ultrasonically stirring until the gamma-CD-MOF nano particles are completely dissolved to obtain a mixed solution, namely a freshness indicating layer solution.
Further, the dosage ratio of the polyvinylidene fluoride, the acetone and the N, N-dimethylformamide solution in the step (3) is 2.5-3.25 g: 10mL of: 15 mL; the mass of the natural antibacterial material is 5-13% of that of polyvinylidene fluoride; the natural antibacterial material has broad-spectrum antibacterial activity; the natural antibacterial material is any one or combination of more of vanillin, carvacrol, eugenol, thymol and carvacrol.
Further, the dosage ratio of the sodium alginate, the polyvinyl alcohol and the aqueous solution in the step (3) is 0.1-0.4 g: 2-2.4 g: 10 mL; the mass of the gamma-CD-MOF nano particles loaded with the anthocyanin in the solution is 1% -5% of the total mass of the sodium alginate and the polyvinyl alcohol.
(4) Preparation of function partition type freshness indicating film
And taking the hydrophobic antibacterial layer solution and the freshness indicating layer solution as spinning solutions, and performing partition spinning by adopting an electrostatic spinning technology.
Firstly, electrospinning a hydrophobic antibacterial outer layer solution containing a natural antibacterial agent onto a collecting roller by an electrostatic spinning technology, wherein a spray head is fixed in the spinning process, a receiving roller rotates to receive spinning until a spinning film is formed on the surface of the receiving roller, and the obtained spinning film is a hydrophobic antibacterial layer film; after electrostatic spinning of the hydrophobic antibacterial layer film is finished, spinning the freshness indicating layer solution in a specific area in the hydrophobic antibacterial layer film by an electrostatic spinning technology, stopping rotation of the collecting roller at the moment, enabling the spray head to move in a reciprocating manner, and enabling a film area obtained by reciprocating movement of the spray head to be the freshness indicating area film; after the electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partitioned freshness indicating film.
Further, the electrostatic spinning technical condition parameters of the hydrophobic antibacterial layer film in the step (4) are as follows: the voltage applied by a high-voltage power supply is 12-17 kV, the receiving distance is 10-20 cm, the solution advancing speed is 0.5-0.8 mL/h, the spinning temperature is 15-30 ℃, and the rotating speed of a collecting roller is 70 r/min.
Further, the technical condition parameters of the electrostatic spinning of the freshness indicating layer film in the step (4) are as follows: the voltage applied by a high-voltage power supply is 25-35 kV, the receiving distance is 10-20 cm, the solution advancing speed is 0.1-0.3 mL/h, the spinning temperature is 25-40 ℃, and the relative humidity is 20-30%.
In order to better represent the freshness indication and the antibacterial capability of the functional partition type freshness indication package based on the high-stability anthocyanin on meat products, the freshness and the antibacterial activity of pork are determined, and the specific steps are as follows:
(1) monitoring pork freshness
The fiber film sample is pasted inside the aseptic packaging box and stored together with the meat product; during the storage process of the pork, protein contained in the pork is decomposed into peptide and amino acid under the action of microorganisms, and then further decomposed into lower amine and ammonia gas, so that the pH value of the storage environment is gradually increased, the color of the fiber membrane is changed, and the color difference is more obvious when the storage time of the meat product is longer; and (3) measuring the volatile basic nitrogen value of the sample at regular intervals by using an automatic Kjeldahl azotometer, recording the color change of the fiber membrane, analyzing and obtaining the color difference value, and establishing a correlation with the volatile basic nitrogen of the meat product, so that the freshness of the meat product is judged according to the color change, and visual detection is realized.
(2) Determination of the bacteriostatic efficacy
Activating strains: the experimental strain is taken out from a refrigerator at 4 ℃, inoculated in a fresh slant culture medium for constant temperature culture and subcultured for 2 generations.
Measuring the bacteriostatic effect of the nanofiber membrane: diluting activated staphylococcus aureus and escherichia coli strains by using sterile normal saline, sucking 10uL of bacterial liquid, adding the bacterial liquid into a plate culture medium, uniformly coating, putting a sterilized nanofiber wafer punched by a punching machine into a culture dish, and using a nanofiber membrane without antibacterial substances as a blank control. Culturing at 37 deg.C for 24h, measuring the diameter of inhibition zone, and comparing the inhibition effect on different bacteria.
The invention has the advantages of
1. The functional partitioned freshness indicating membrane loaded with the anthocyanin by MOFs is obtained by uniformly mixing a metal-organic framework material loaded with the anthocyanin, a natural antibacterial substance and a polymer and then carrying out partitioned electrostatic spinning. In the spinning process, the antibacterial area and the indication area are functionally partitioned according to the functional characteristics and the action positions of the antibacterial area and the indication area in the package, the freshness indication area and the hydrophobic antibacterial area are respectively electrospun, the influence between the functional areas is reduced to the maximum extent, and the functional characteristics of corresponding materials are exerted to the maximum extent.
2. The indication area designed by the invention adopts anthocyanin embedded in MOFs as a high-stability pH indicator, the MOFs is a nano material consisting of an organic connector and a metal cluster which are connected through coordination bonds, the nano material is organized in space to generate a cavity with a regular size, a unique structure can be adjusted according to different functions, and the anthocyanin is embedded in the cyclodextrin MOFs nano material to form a compound by utilizing the characteristics of porosity, biocompatibility, biodegradability and the like of the MOFs nano material. Compared with other MOFs nano materials, the cyclodextrin MOFs selected by the invention is safer when being applied to food packaging. Compared with natural anthocyanin, the formed compound has obviously improved light and heat stability under alkaline conditions, and the research of applying MOFs compound anthocyanin package to freshness indication package is not available. Meanwhile, the proportion range of the compound formed by the MOFs material and the anthocyanin is limited, and the compound synthesized in the proportion range is characterized by a plurality of methods, so that the anthocyanin exists in pores of the MOFs, the crystallinity of the MOFs is not influenced, and the accuracy of freshness indication can be effectively improved.
3. The nano-level fiber structure designed by electrostatic spinning has a large specific surface area, is endowed with distinctive small-size effect and surface effect, can increase the active exposure sites of antibacterial components and pH indicators in a package, effectively improves the reaction sensitivity, effectively avoids the problem of nano-material aggregation caused by the traditional film forming method, and improves the biological safety.
Drawings
FIG. 1 is a schematic view of a spinning process using electrospinning in the method of the present invention.
FIG. 2 is a scanning electron micrograph of a freshness indicating film of the present invention; wherein A is an antibacterial area diagram; b is an indication area diagram.
FIG. 3 is a graph of the stability of the freshness indicating film prepared in example 1 at 4 ℃ and 25 ℃.
FIG. 4 is a graph of the color change of the fiber film prepared in example 1 versus the volatile salt-based nitrogen value of pork.
FIG. 5 is a graph showing the bacteriostatic effects of the fibrous membrane prepared in example 2 on Escherichia coli and Staphylococcus aureus.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Example 1:
a preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film comprises the following steps:
(1) preparing MOFs materials;
1.3g of gamma-cyclodextrin and 0.45g of potassium hydroxide were dissolved in 20mL of ultrapure water, then sonicated until completely dissolved, the resulting solution was filtered, the resulting solution was mixed with 20mL of methanol, and heated in a constant temperature water bath until the turbid liquid was clear. To the resulting clear solution was added 2mL of polyethylene glycol and 2mL of methanol. Precipitates formed rapidly at room temperature and were washed with methanol and ethanol, respectively. A precipitate was obtained, which was soaked in dichloromethane for three days, then centrifuged and vacuum dried overnight to give crystalline γ -CD-MOFs nanoparticles.
(2) Encapsulation of anthocyanins in a metal organic framework;
1.75g of crystalline gamma-CD-MOFs and 1.16g of anthocyanidin were dissolved in 10mL of methanol and stirred magnetically in the dark. After centrifugation, the precipitate was collected and washed with methanol to remove the non-encapsulated anthocyanins. Finally, the anthocyanin-loaded gamma-CD-MOF was obtained by vacuum drying overnight in the dark.
(3) Preparing an electrostatic spinning solution;
preparing a hydrophobic antibacterial layer solution: dissolving 3g of polyvinylidene fluoride in 25ml of acetone-N, N-dimethylformamide solution (volume ratio is 2:3), adding 0.15g of vanillin, blending, sealing and stirring until the mixture is completely dissolved.
Preparing a freshness indicating layer solution: dissolving 0.4g of sodium alginate and 2.4g of polyvinyl alcohol in 10mL of aqueous solution, adding 0.05g of anthocyanin-loaded gamma-CD-MOF nanoparticles into the sodium alginate/polyvinyl alcohol polymer solution under the ultrasonic action, sealing, and ultrasonically stirring until the nanoparticles are completely dissolved.
(4) Preparing a fiber membrane;
firstly, electro-spinning hydrophobic antibacterial outer layer solution (5mL) containing natural antibacterial agent onto a collecting roller rotating at high speed by an electrostatic spinning technology, fixing a spray head in the spinning process, and rotating the receiving roller to receive spinning until a spinning film is formed on the surface of the receiving roller, wherein the obtained spinning film is the hydrophobic antibacterial layer film;
then, spinning a freshness indicating layer solution (5mL) containing gamma-CD-MOF nanoparticles loaded with anthocyanin into a specific area in the hydrophobic antibacterial layer film, stopping the rotation of the collecting roller at the moment, and reciprocating the spray head to obtain a film area, namely a freshness indicating area film, obtained by reciprocating the spray head; after electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partition type freshness indicating film; the corresponding technical condition parameters of the electrostatic spinning of the freshness indicating layer film are as follows: the voltage applied by a high-voltage power supply is 30kV, the receiving distance is 10cm, the solution advancing speed is 0.1mL/h, the spinning temperature is 35 ℃, and the relative humidity is 20%; the parameters of the electrostatic spinning technical condition of the hydrophobic antibacterial layer film are as follows: the voltage applied by a high-voltage power supply is 13kV, the receiving distance is 10cm, the solution advancing speed is 0.6mL/h, the spinning temperature is 20 ℃, and the relative humidity is not required; after the electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partitioned freshness indicating film. FIG. 2 shows the structure of the electrospun film by electron microscopy.
In order to better characterize the freshness indicating capability of the antibacterial freshness indicating film on meat products, the detection steps are as follows:
determination of pork freshness indication function by fiber membrane
Put 20g pork into aseptic packaging box. The nanofiber membrane sample was attached inside the space at the top of the box and the untested film served as a control. The package was stored at 25 ℃.
Record the delta E value of the film sample every 12h and record the color change of the film.
And thirdly, measuring the TVB-N level of the pork sample by adopting an automatic Kjeldahl method in national standard. 10g of pork was mixed with 75mL of water, and then the mixture was homogenized using a homogenizer and dipped for 30 min. The standard solution is hydrochloric acid standard titration solution (0.1000mol/L), an automatic nitrogen analyzer with automatic reagent adding and waste discharging functions is used, the automatic waste discharging, automatic alkali adding and automatic water adding functions are closed, and the alkali adding and water adding volume is set to be 0 mL. The boric acid receiver addition was set at 30 mL. The distillation time was set at 180 s. And (3) adopting a nitrogen determinator for judging the end point in an automatic potentiometric titration mode, and setting the pH value of the titration end point to be 4.65. 1g of magnesium oxide was added to the distillation tube containing the treated sample, which was immediately connected to the distiller, and the measurement was started as described above. The content of TVB-N in pork every 12 hours was measured. As shown in fig. 4, it is apparent that the change of the color of the nanofiber membrane, i.e., the Δ E value, is significant and has a high linear relationship with the change of the volatile basic nitrogen of pork with the increase of the storage time of pork. The pork does not exceed the national standard (15mg/100g) in the first 48 hours, the meat quality is in a fresh state, and the color change of the fiber membrane is not obvious at the moment; when the volatile basic nitrogen in the pork is about to reach the threshold value within 60h, the color of the film is changed into purple, and an early warning signal can be provided for a consumer; after 60h, as the pork gradually goes putrefactive, the color of the nanofiber membrane changes from blue to purple and green, and at the moment, the volatile basic nitrogen of the corresponding pork indicates that the pork is putrefactive and inedible. It can be seen that the nanofiber membrane can effectively indicate the freshness of pork.
Example 2:
a preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film comprises the following steps:
(1) preparing MOFs materials;
3.2g of gamma-cyclodextrin and 1.2g of potassium hydroxide were dissolved in 20ml of ultrapure water and then sonicated until completely dissolved. The resulting solution was filtered using an organic filter membrane, mixed with methanol and heated in a constant temperature water bath until the turbid liquid was clear. Polyethylene glycol and methanol were added to the resulting clear solution. Precipitates formed rapidly at room temperature and were washed with methanol and ethanol, respectively. A precipitate was obtained, which was soaked in dichloromethane for three days, then centrifuged and vacuum dried overnight to give crystalline γ -CD-MOFs nanoparticles.
(2) Encapsulation of anthocyanins in a metal organic framework;
4.4g of crystalline γ -CD-MOFs and 2.9g of anthocyanidin were dissolved in 10mL of methanol and stirred magnetically in the dark. After centrifugation, the precipitate was collected and washed twice with methanol to remove the unencapsulated anthocyanins. Finally, the anthocyanin-loaded gamma-CD-MOF was obtained by vacuum drying overnight in the dark.
(3) Preparing an electrostatic spinning solution;
preparing a hydrophobic antibacterial layer solution: dissolving 2.5g of polyvinylidene fluoride in 25ml of acetone-N, N-dimethylformamide solution (volume ratio is 2:3), adding 0.30g of vanillin for blending, sealing, stirring until the vanillin is completely dissolved to obtain a mixed solution, namely the antibacterial hydrophobic layer solution;
preparing a freshness indicating layer solution: dissolving 0.2g of sodium alginate and 2.0g of polyvinyl alcohol in an aqueous solution, adding 0.1g of anthocyanin-loaded gamma-CD-MOF nanoparticles into a sodium alginate/polyvinyl alcohol polymer solution under the action of ultrasound, sealing, and ultrasonically stirring until the sodium alginate/polyvinyl alcohol polymer solution is completely dissolved.
(4) Preparing a fiber membrane;
firstly, electro-spinning hydrophobic antibacterial outer layer solution (5mL) containing natural antibacterial agent onto a collecting roller rotating at high speed by an electrostatic spinning technology, fixing a spray head in the spinning process, and rotating the receiving roller to receive spinning until a spinning film is formed on the surface of the receiving roller, wherein the obtained spinning film is the hydrophobic antibacterial layer film;
then, spinning a freshness indicating layer solution (5mL) containing gamma-CD-MOF nanoparticles loaded with anthocyanin into a specific area in the hydrophobic antibacterial layer film, stopping the rotation of the collecting roller at the moment, and reciprocating the spray head to obtain a film area, namely a freshness indicating area film, obtained by reciprocating the spray head; after electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partition type freshness indicating film; the corresponding technical condition parameters of the electrostatic spinning of the freshness indicating layer film are as follows: the voltage applied by a high-voltage power supply is 25kV, the receiving distance is 10cm, the solution advancing speed is 0.1mL/h, the spinning temperature is 25 ℃, and the relative humidity is 20%; the parameters of the electrostatic spinning technical condition of the hydrophobic antibacterial layer film are as follows: the voltage applied by a high-voltage power supply is 12kV, the receiving distance is 10cm, the solution advancing rate is 0.5mL/h, the spinning temperature is 15 ℃, the relative humidity is not required, and after the electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partition type freshness indicating film.
In order to better characterize the antibacterial ability of the antibacterial freshness indicating film, the detection steps are as follows:
determination of bacteriostatic efficacy of fiber membranes:
activating strains: and (3) taking out the staphylococcus aureus and the escherichia coli from a refrigerator at 4 ℃, inoculating the staphylococcus aureus and the escherichia coli into a fresh slant culture medium, culturing at constant temperature for 24h at 37 ℃, and carrying out passage 2.
Measuring the bacteriostatic effect of the nanofiber membrane: diluting activated Staphylococcus aureus and Escherichia coli strain with sterile normal saline to obtain a product with bacteria content of 107～108cuf/mL, absorbing 10uL of bacterial liquid, adding into a plate culture medium, uniformly coating, placing the sterilized nanofiber wafer punched by a punching machine into a culture dish, and using the nanofiber membrane without vanillin as a blank control. Culturing at 37 deg.C for 24h, measuring the diameter of inhibition zone, and comparing the inhibition effect on different bacteria.
The result is shown in figure 5, and research results show that the prepared nanofiber membrane has obvious antibacterial efficacy on escherichia coli and staphylococcus aureus, and the diameters of inhibition zones of the nanofiber membrane on the escherichia coli and the staphylococcus aureus are respectively 14mm and 8mm through measurement, so that different bacteria inhibition effects of vanillin on different strains are shown, and compared with other strains, the vanillin has a better antibacterial effect on the escherichia coli. Namely, the bacteriostatic effect on gram negative bacteria is obviously stronger than that on gram positive bacteria. The antibacterial effect of the nanofiber membrane can effectively reduce the proliferation of microorganisms during the preservation of meat products and prolong the shelf life of the meat products.
Example 3:
a preparation method of a MOFs anthocyanin-loaded functional partitioned freshness indicating film comprises the following steps:
(1) preparing MOFs materials;
1.86g of gamma-cyclodextrin was dissolved in 50ml of ultrapure water with 0.64g of potassium hydroxide, followed by sonication until complete dissolution. The resulting solution was filtered using an organic filter membrane, mixed with methanol and heated in a constant temperature water bath until the turbid liquid was clear. Polyethylene glycol and methanol were added to the resulting clear solution. Precipitates formed rapidly at room temperature and were washed with methanol and ethanol, respectively. A precipitate was obtained, which was soaked in dichloromethane for three days, then centrifuged and vacuum dried overnight to give crystalline γ -CD-MOFs nanoparticles.
(2) Encapsulation of anthocyanins in a metal organic framework;
2.5g of crystalline gamma-CD-MOFs and 1.7g of anthocyanidin were dissolved in methanol and stirred magnetically in the dark. After centrifugation, the precipitate was collected and washed twice with methanol to remove the unencapsulated anthocyanins. Finally, the anthocyanin-loaded gamma-CD-MOF was obtained by vacuum drying overnight in the dark.
(3) Preparing an electrostatic spinning solution;
preparing a hydrophobic antibacterial layer solution: dissolving 3.25g of polyvinylidene fluoride in 25ml of acetone-N, N-dimethylformamide solution (volume ratio is 2:3), adding 0.45g of vanillin for blending, sealing, stirring until the vanillin is completely dissolved to obtain a mixed solution, namely the antibacterial hydrophobic layer solution;
preparing a freshness indicating layer solution: dissolving 0.1g of sodium alginate and 2.4g of polyvinyl alcohol in an aqueous solution, adding 0.15g of anthocyanin-loaded gamma-CD-MOF nanoparticles into a sodium alginate/polyvinyl alcohol polymer solution under the action of ultrasound, sealing, and ultrasonically stirring until the sodium alginate/polyvinyl alcohol polymer solution is completely dissolved.
(4) Preparing a fiber membrane;
firstly, electro-spinning hydrophobic antibacterial outer layer solution (5mL) containing natural antibacterial agent onto a collecting roller rotating at high speed by an electrostatic spinning technology, fixing a spray head in the spinning process, and rotating the receiving roller to receive spinning until a spinning film is formed on the surface of the receiving roller, wherein the obtained spinning film is the hydrophobic antibacterial layer film;
then, spinning a freshness indicating layer solution (5mL) containing gamma-CD-MOF nanoparticles loaded with anthocyanin into a specific area in the hydrophobic antibacterial layer film, stopping the rotation of the collecting roller at the moment, and reciprocating the spray head to obtain a film area, namely a freshness indicating area film, obtained by reciprocating the spray head; after electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partition type freshness indicating film; the corresponding technical condition parameters of the electrostatic spinning of the freshness indicating layer film are as follows: aiming at the indicating inner layer, the voltage applied by a high-voltage power supply is 35kV, the receiving distance is 20cm, the solution advancing speed is 0.3mL/h, the spinning temperature is 40 ℃, and the relative humidity is 30%; the parameters of the electrostatic spinning technical condition of the hydrophobic antibacterial layer film are as follows: the voltage applied by a high-voltage power supply is 17kV, the receiving distance is 20cm, the solution advancing speed is 0.8mL/h, the spinning temperature is 30 ℃, and the relative humidity is not required. After the electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partitioned freshness indicating film.
In order to better characterize the freshness indicating capability of the antibacterial freshness indicating film on meat products, the detection steps are as follows:
sensitivity test of the indication area to ammonia:
80mL of aqueous ammonia (8mmol/L) was put into a 500mL Erlenmeyer flask, and a fiber membrane (20 mm. times.20 mm) containing the indicated region was suspended at a liquid level of 10mm, and image information was recorded every 5min for 60min using a camera. As the reaction time increased, the color of the freshness-indicating film gradually changed from blue to purple and finally to green, indicating that ammonia gas causes a change in the color of the freshness-indicating film. Then, the freshness indicating film which is subjected to the ammonia gas sensitivity test is placed on a bottle mouth filled with an acidic solution, and the color of the freshness indicating film is gradually changed from green to original blue under the action of acidic steam. Fresh meat and aquatic products produce ammonia and biogenic amines (cadaverine, putrescine, trimethylamine, etc.) upon spoilage, and these substances have been shown to be indicative of spoilage of meat and aquatic products.
During the putrefaction process of the fresh meat and the aquatic products, the freshness indicating film gradually changes from the initial blue color to the purple color and finally to the green color, so the freshness indicating film has the potential of indicating the freshness of the fresh meat and the aquatic products in real time.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. A preparation method of a MOFs anthocyanin-loaded functional partition type freshness indicating film is characterized by comprising the following steps:
(1) dissolving gamma-cyclodextrin and potassium hydroxide in ultrapure water, performing ultrasonic treatment until the gamma-cyclodextrin and the potassium hydroxide are completely dissolved, filtering by using an organic microporous filter membrane to obtain a filtrate, mixing the filtrate with methanol A, and heating in a constant-temperature water bath until turbid liquid is clear; adding polyethylene glycol and methanol B into the obtained clear solution, forming a precipitate A at room temperature, washing the precipitate A with methanol C and ethanol respectively, finally centrifuging to obtain a precipitate B, soaking the precipitate B in dichloromethane for a period of time, centrifuging and vacuum-drying overnight to obtain a product, namely the gamma-CD-MOFs nano-particles;
(2) dissolving gamma-CD-MOFs nano particles and anthocyanin in methanol, magnetically stirring uniformly in the dark, centrifuging the obtained mixed solution, collecting precipitate, adding methanol, ultrasonically dissolving to remove unencapsulated anthocyanin, centrifuging again, and vacuum-drying the precipitate in the dark overnight to obtain gamma-CD-MOF loaded with anthocyanin;
(3) preparing an electrostatic spinning solution;
preparing a hydrophobic antibacterial layer solution: firstly, mixing acetone and N, N-dimethylformamide solution, then adding polyvinylidene fluoride, adding a natural antibacterial material, blending, sealing, and stirring until the natural antibacterial material is completely dissolved to obtain a mixed solution which is an antibacterial hydrophobic layer solution;
preparing a freshness indicating layer solution: dissolving sodium alginate and polyvinyl alcohol in an aqueous solution, adding the gamma-CD-MOF nano particles loaded with anthocyanin into a sodium alginate/polyvinyl alcohol polymer solution under the action of ultrasound, sealing, and ultrasonically stirring until the gamma-CD-MOF nano particles are completely dissolved to obtain a mixed solution, namely a freshness indicating layer solution.
(4) Firstly, electrospinning a hydrophobic antibacterial outer layer solution containing a natural antibacterial agent onto a collecting roller by an electrostatic spinning technology, wherein a spray head is fixed in the spinning process, a receiving roller rotates to receive spinning until a spinning film is formed on the surface of the receiving roller, and the obtained spinning film is a hydrophobic antibacterial layer film; after electrostatic spinning of the hydrophobic antibacterial layer film is finished, spinning the freshness indicating layer solution in a specific area in the hydrophobic antibacterial layer film by an electrostatic spinning technology, stopping rotation of the collecting roller at the moment, enabling the spray head to move in a reciprocating manner, and enabling a film area obtained by reciprocating movement of the spray head to be the freshness indicating area film; after the electrostatic spinning of the freshness indicating area is finished, a double-layer film integrating the indicating area film and the antibacterial area film is obtained, namely the functional partitioned freshness indicating film.
2. The preparation method of the MOFs-supported anthocyanin functional partitioning type freshness indicating film according to claim 1, wherein the dosage ratio of the gamma-cyclodextrin, the potassium hydroxide and the ultrapure water in the step (1) is 1.3-3.48 g: 0.45-1.2 g: 20-50 mL; the volume ratio of the filtrate to the methanol A is 1: 1; the temperature of the constant-temperature water bath is 35 ℃, and the heating time is 2 h.
3. The preparation method of the MOFs anthocyanin-loaded functional partitioning type freshness indicating film according to claim 1, wherein the volume ratio of the clear solution in the step (1), the polyethylene glycol and the methanol B is 4:1: 1; the dosage ratio of the sediment A to the methanol C to the ethanol is 1 g: 1-2 mL: 12 mL; the dosage ratio of the precipitate B to the dichloromethane is 1 g: 2-3 mL; the rotating speed of the centrifugation is 1800r/min, and the centrifugation time is 10 min; the duration of the soaking period is 70-75 h.
4. The preparation method of the MOFs anthocyanin-loaded functional partitioned freshness indication film according to claim 1, wherein the dosage ratio of the anthocyanin, the gamma-CD-MOF and the methanol in the step (2) is 1.16-2.9 g: 1.75-4.4 g: 10 mL.
5. The method for preparing the MOFs anthocyanin-loaded functional partitioning type freshness indicating film according to claim 1, wherein the mass ratio of the precipitate in the step (2) to the methanol is 1: 1; the centrifugal speed is 1800r/min, and the centrifugal time is 10 min; the vacuum drying temperature was 50 ℃.
6. The method for preparing the MOFs anthocyanin-loaded functional partition type freshness indicating film according to claim 1, wherein the dosage ratio of the polyvinylidene fluoride, the acetone and the N, N-dimethylformamide solution in the step (3) is 2.5-3.25 g: 10mL of: 15 mL; the mass of the natural antibacterial material is 5-13% of that of polyvinylidene fluoride; the natural antibacterial material has broad-spectrum antibacterial activity; the natural antibacterial material is any one or combination of more of vanillin, carvacrol, eugenol, thymol and carvacrol.
7. The preparation method of the MOFs-supported anthocyanin functional partitioned freshness indication film according to claim 1, wherein the dosage ratio of the sodium alginate, the polyvinyl alcohol and the aqueous solution in the step (3) is 0.1-0.4 g: 2-2.4 g: 10 mL; the mass of the gamma-CD-MOF nano particles loaded with the anthocyanin in the solution is 1% -5% of the total mass of the sodium alginate and the polyvinyl alcohol.
8. The preparation method of the MOFs anthocyanin-loaded functional partition type freshness indicating film according to claim 1, wherein the technical condition parameters of the electrostatic spinning of the hydrophobic antibacterial layer thin film in the step (4) are as follows: the voltage applied by a high-voltage power supply is 12-17 kV, the receiving distance is 10-20 cm, the solution advancing speed is 0.5-0.8 mL/h, the spinning temperature is 15-30 ℃, and the rotating speed of a collecting roller is 70 r/min.
9. The preparation method of the MOFs anthocyanin-loaded functional partition type freshness indicating film according to claim 1, wherein the technical condition parameters of the electrostatic spinning of the freshness indicating layer film in the step (4) are as follows: the voltage applied by a high-voltage power supply is 25-35 kV, the receiving distance is 10-20 cm, the solution advancing speed is 0.1-0.3 mL/h, the spinning temperature is 25-40 ℃, and the relative humidity is 20-30%.
10. The MOFs anthocyanin-loaded functional partitioned freshness-indicating film prepared by the method of any one of claims 1 to 9, wherein the freshness-indicating film is used for bacteriostasis and indicating freshness of meat.
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| CN114591542A (en) * | 2022-04-25 | 2022-06-07 | 江南大学 | Sodium alginate-based antioxidant antibacterial bioactive composite membrane added with IRMOF-3/carvacrol and preparation method thereof |
| CN116808006A (en) * | 2023-08-29 | 2023-09-29 | 吉林农业科技学院 | Fibrous membrane with hemostatic, anti-inflammatory and wound healing promoting functions, and preparation method and application thereof |
| CN117782412A (en) * | 2024-02-23 | 2024-03-29 | 中国农业大学 | Pressure indicator and application thereof |
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| CN114591542A (en) * | 2022-04-25 | 2022-06-07 | 江南大学 | Sodium alginate-based antioxidant antibacterial bioactive composite membrane added with IRMOF-3/carvacrol and preparation method thereof |
| CN114591542B (en) * | 2022-04-25 | 2022-11-18 | 江南大学 | Sodium alginate-based antioxidant antibacterial bioactive composite membrane added with IRMOF-3/carvacrol and preparation method thereof |
| CN116808006A (en) * | 2023-08-29 | 2023-09-29 | 吉林农业科技学院 | Fibrous membrane with hemostatic, anti-inflammatory and wound healing promoting functions, and preparation method and application thereof |
| CN116808006B (en) * | 2023-08-29 | 2023-11-10 | 吉林农业科技学院 | Fibrous membrane with hemostatic, anti-inflammatory and wound healing promoting functions, and preparation method and application thereof |
| CN117782412A (en) * | 2024-02-23 | 2024-03-29 | 中国农业大学 | Pressure indicator and application thereof |
| CN117782412B (en) * | 2024-02-23 | 2024-05-24 | 中国农业大学 | Pressure indicator and application thereof |
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