CN113481658A - Nano electrostatic spinning food preservative film mediated by butyl caffeate and endogenous NO type chitosan and preparation method and application thereof - Google Patents
Nano electrostatic spinning food preservative film mediated by butyl caffeate and endogenous NO type chitosan and preparation method and application thereof Download PDFInfo
- Publication number
- CN113481658A CN113481658A CN202110585024.8A CN202110585024A CN113481658A CN 113481658 A CN113481658 A CN 113481658A CN 202110585024 A CN202110585024 A CN 202110585024A CN 113481658 A CN113481658 A CN 113481658A
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- China
- Prior art keywords
- butyl
- cyclodextrin
- caffeate
- chitosan
- endogenous
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- Pending
Links
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- DBBCBZIFZYILRL-UHFFFAOYSA-N caffeic acid n-butyl ester Natural products CCCCOC(=O)C=CC1=CC=C(O)C(O)=C1 DBBCBZIFZYILRL-UHFFFAOYSA-N 0.000 title claims abstract description 68
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Images
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- A23B7/157—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract
本发明公开了一种由咖啡酸丁酯与内生NO型壳聚糖介导的纳米静电纺丝食品保鲜膜及其制备方法和应用。公开了这一种制备咖啡酸丁酯(CAC4)与内生NO型壳聚糖(NO‑CS)介导的超高效多功能纳米静电纺丝食品保鲜膜的方法。另外，还公开了该超高效纳米静电纺丝保鲜膜在在蓝莓鲜果保鲜中的应用，经过处理后的蓝莓鲜果不但能够长时间保持其功效，还有效降低了其贮藏成本。本发明作为新型高效保鲜材料，无味、无毒可食用，组分绿色安全环保，提升了咖啡酸丁酯的抑菌及抗氧化效果，有效地抑制了果蔬产品在贮藏、运输过程中致病菌的污染，能有效延长货架期，扩大了咖啡酸丁酯作为保鲜剂在食品领域的应用范围。
The invention discloses a nano-electrospinning food fresh-keeping film mediated by butyl caffeate and endogenous NO-type chitosan, and a preparation method and application thereof. Disclosed is a method for preparing an ultra-efficient and multifunctional nano-electrospinning food preservation film mediated by butyl caffeate (CAC4) and endogenous NO-type chitosan (NO-CS). In addition, the application of the ultra-efficient nano-electrospinning fresh-keeping film in the fresh-keeping of blueberry fresh fruit is disclosed. The processed blueberry fresh fruit can not only maintain its efficacy for a long time, but also effectively reduce its storage cost. As a novel and high-efficiency fresh-keeping material, the present invention is odorless, non-toxic and edible, the components are green, safe and environmentally friendly, the bacteriostatic and antioxidant effects of butyl caffeate are improved, and the pathogenic bacteria in the storage and transportation of fruit and vegetable products are effectively inhibited. It can effectively extend the shelf life and expand the application scope of butyl caffeate as a preservative in the food field.
Description
Technical Field
The invention relates to the field of food preservative films, in particular to an ultra-efficient multifunctional nano electrostatic spinning food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS), which is particularly suitable for fruit and vegetable preservation.
Background
In recent years, as antibiotics are abused, the resistance of bacteria has increased, and the task of developing new non-antibiotic killing or bacteriostatic agents has been urgent. Nitric Oxide (NO) is an important signal and functional molecule released from vascular endothelium and is widely involved in regulating various physiological processes. In addition, NO is an effective antibacterial and antiviral agent. NO-induced nitrosation and oxidative stress directly modify membrane proteins, which are believed to play a crucial role in antibacterial aspects. Such active substances may include NO radicals (NO.), nitrogen dioxide (NO)2-, dinitrogen trioxide (N)2O3) And peroxynitrite (ONOO). These oxidants induce DNA strand breaks by free radicals, promoting lipid peroxidation, a phenomenon that can kill cancer cells and bacteria. In antibacterial applications, NO can not only effectively kill a single strain, but also kill a mixed microbial strain. Thus, NO is considered a potential therapeutic agent against cancer and microorganisms. However, the currently studied NO donors have many disadvantages, such as poor biocompatibility, low NO loading, poor controlled-release and slow-release effects, and the like. In order to realize the controlled release of NO and fully exert the excellent long-acting bacteria control advantages, people begin to try to prepareThe various NO donors, an ideal NO-releasing macromolecular carrier, would be multifunctional and consist of multiple NO donors to achieve an ideal NO payload.
Chitosan is a natural carbohydrate copolymer obtained by deacetylating chitin. The basic constituent unit of chitosan is N-acetylglucosamine, and the basic structural unit is chitobiose. Chitosan is divided into three different forms: high molecular weight chitosan, medium molecular weight chitosan and low molecular weight chitosan. The chitosan has the characteristics of excellent degradability, solubility in weak acid, pH sensitivity, film forming property, biocompatibility, non-antigenicity, non-toxicity, low cost and the like. In addition, chitosan has a natural origin and many possible applications, such as the preparation of biodegradable films, blends, coatings, composites, nanocomposites, etc. After chemical modification, the chitosan derivatives thus produced can be endowed with new properties, and their potential use as multifunctional nanocarriers has been attracting attention. S-nitrosothiol-chitosan (SNO-CS) is a macromolecular scaffold with multiple biological effects, can combine the capability of NO release to generate super-strong antibacterial and anti-biofilm characteristics, and can be prepared into nano materials with various forms.
Cyclodextrins (CDs) are cyclic glucose oligomers produced by the transformation of starch with certain bacteria, such as Bacillus macerans, used commercially. The cyclodextrin structure generally presents a cone-shaped cylinder, which are donut-shaped molecules with a hydrophilic outer surface and a lipophilic central cavity, and the most common cyclodextrins are alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin, which are common food additives. The cavity is arranged by hydrogen atoms and a glucoside oxygen bridge, and the non-bonding electron pair of the glucoside oxygen bridge is oriented in the cavity to generate higher electron density and has certain Lewis alkali characteristics. In aqueous solutions, cyclodextrins can improve the aqueous solubility of some fat-soluble drugs by dissolving portions of them in the central lumen.
The phenolic acid compound has wide physiological activity and broad-spectrum antibacterial property, such as antibacterial, antiviral, antioxidant, antitumor, anti-free radical, platelet aggregation resistance and the like, can effectively prevent oxidative damage, is beneficial to preventing cardiovascular and cerebrovascular diseases, neurological diseases, cancers and other diseases, and has great application potential in the fields of food, medicine and the like. The subject group is dedicated to the modification and function development research of polyphenol for a long time, and the research shows that phenolic ester generated after the covalent grafting of phenolic acid and alkyl alcohol has stronger biological activity than the corresponding phenolic acid, such as stronger antioxidant and antibacterial effects, and can be used for improving the safety and quality of food and optimizing the food processing process. Wherein, the caffeic acid butyl ester (CAC4) is an alkyl derivative of caffeic acid of natural phenolic acid substances, and has good antioxidant and antibacterial effects.
Electrostatic spinning is a technology which is simple to operate and can continuously prepare polymer nano fibers, and the prepared nano fiber film has the advantages of high porosity, large specific surface area and easiness in recovery, so that the electrostatic spinning is widely applied to a plurality of research fields, and in recent years, the electrostatic spinning is also concerned in functional food packaging.
According to the existing research, the caffeic acid butyl ester mediated multifunctional food fresh-keeping nano packaging material prepared by utilizing the nano electrostatic spinning technology has good antibacterial and antioxidant properties, is edible, can be used as a carrier of nutrient substances and functional components, is safe, stable and efficient, and has a wide application range. For example, as a multifunctional food fresh-keeping material, on the basis of ensuring the excellent food fresh-keeping function, the invention not only can not generate toxic action on human bodies after being eaten and absorbed by people, but also can provide certain nutritive value for the human bodies; in the field of medical pharmacy, the packaging materials such as capsules and the like prepared by the invention can slowly release content medicaments in human bodies, thereby improving the safety and prolonging the action time of medicaments, and further playing a better treatment effect; in the aspect of environmental protection, the product belongs to a nano material, has natural raw materials, can be degraded after being treated by a nano electrostatic spinning technology, and is environment-friendly, biologically friendly and environment-friendly.
Blueberry, also known as blueberry, Vaccinium uliginosum, Duyingkaki, Duyingshi, Diguo and Vaccinium uliginosum is a small berry, small in particle, blue in fruit, coated by a layer of white fruit powder, fine in pulp, palatable in sweetness and sourness, and pleasant in fragrance. The blueberry is rich in nutrition, not only is rich in conventional nutrient components, but also contains extremely rich flavonoid and polysaccharide compounds, has good nutrition and health care effects, also has the functions of preventing cranial nerve aging, strengthening heart, resisting cancer, softening blood vessels, enhancing human body immunity and the like, and is popular with consumers. However, the blueberries are easy to decay and deteriorate due to mechanical damage and microbial contamination during transportation and storage, so the shelf life of the blueberries is short. Therefore, the development of the preservative film for blueberry packaging is particularly necessary for prolonging the shelf life of blueberries.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of an ultra-efficient multifunctional nano electrostatic spinning food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) and application of the preservative film in fruit and vegetable preservation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a nano electrostatic spinning food preservative film mediated by butyl caffeate and endogenous NO type chitosan comprises the following steps:
s1, mixing cyclodextrin and butyl caffeate to obtain a butyl caffeate/cyclodextrin supermolecular inclusion compound;
s2, preparing endogenous NO type chitosan by a method of covalently modifying natural chitosan;
and S3, mixing the caffeic acid butyl ester/cyclodextrin supermolecule inclusion compound with the endogenous NO type chitosan to obtain a homogeneous solution, processing the homogeneous solution into an ultra-efficient multifunctional nano electrostatic spinning film (namely a nano electrostatic spinning food preservative film) through an electrostatic spinning technology, and applying the ultra-efficient multifunctional nano electrostatic spinning film to storage and preservation of fresh blueberry fruits.
In step S1, cyclodextrin is mixed with butyl caffeate to obtain a butyl caffeate/cyclodextrin supramolecular inclusion compound, which specifically comprises:
dissolving cyclodextrin in water, and magnetically stirring until the cyclodextrin is completely dissolved to obtain cyclodextrin water solution; dropwise adding an absolute ethyl alcohol solution containing butyl caffeate into the cyclodextrin aqueous solution, and continuously stirring for 36-60 hours at the temperature of 55-65 ℃ after dropwise adding; standing in a refrigerator at the temperature of between-2 and-8 ℃ for 36 to 60 hours until white solid matters are separated out, filtering, collecting filtrate, refrigerating at the temperature of between-15 and-25 ℃ overnight, and freeze-drying at the temperature of between-40 and-50 ℃ for 18 to 30 hours to obtain the caffeic acid butyl ester-cyclodextrin supramolecular inclusion compound.
Preferably, cyclodextrin is dissolved in deionized water at room temperature, and the mixture is magnetically stirred until the cyclodextrin is completely dissolved; slowly dropwise adding an absolute ethyl alcohol solution containing butyl caffeate into the cyclodextrin aqueous solution, and continuously stirring for 48 hours at 60 ℃ after dropwise adding is finished; standing in a refrigerator at-4 ℃ for 48h until white solid matters are separated out, filtering, collecting filtrate, refrigerating in a refrigerator at-20 ℃ overnight, and freeze-drying at-45 ℃ for 24h to obtain the caffeic acid butyl ester-cyclodextrin supramolecular inclusion compound.
The molar ratio of the butyl caffeate to the cyclodextrin is 0.25-1.5: 1.
the complexation of Cyclodextrin (CD) provides a simple, convenient and safe way for improving the water solubility, dissolution rate, bioavailability and stability of the compound. Cyclodextrins are cyclic oligosaccharides having a truncated cone structure with a hydrophobic interior and a hydrophilic exterior. The hydrophobic cavity of the cyclodextrin may contain a non-polar guest molecule, while its hydrophilic exterior may allow the guest molecule to dissolve in water. The parent cyclodextrin comprises alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD) and gamma-cyclodextrin (gamma-CD), and consists of 6, 7 and 8 alpha- (1,4) glycosidic bonds connected with glucose subunits respectively.
Preferably, beta-CD or hydroxypropyl-beta-CD, as the most readily available and inexpensive CDs, is selected for its appropriate lumen diameter
And volume
Is widely applied in the fields of food, medicine, cosmetics and the like.
The cyclodextrin may be alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD), gamma-cyclodextrin (gamma-CD) and hydroxypropyl beta-cyclodextrin (HP-beta-CD).
In step S2, the preparation of endogenous NO type chitosan by covalent modification of natural chitosan specifically comprises:
s2.1, dissolving chitosan and lithium chloride in N, N-Dimethylaniline (DMA), adding triethylamine and p-toluenesulfonyl chloride into the system, stirring for reaction, precipitating with acetone, filtering and washing the precipitate, and removing the residual solvent in vacuum;
s2.2, adding the product obtained in the step S2.1 and lithium chloride into N, N-Dimethylaniline (DMA), continuously adding triethylamine and ethanedithiol (namely 1, 2-ethanedithiol), stirring overnight at 50-70 ℃ under the protection of nitrogen, precipitating with acetone, filtering and washing the precipitate, then suspending the precipitate in N, N-Dimethylaniline (DMA) containing dithiothreitol and triethylamine, stirring, filtering and washing the precipitate, and removing the solvent in vacuum;
s2.3, washing the product obtained in the step S2.2, re-suspending the product in N, N-Dimethylaniline (DMA)/methanol, adding tert-butyl nitrite, stirring for reaction, precipitating by using methanol after the reaction is finished, filtering, washing and precipitating, removing the solvent in vacuum to obtain the endogenous NO type chitosan (NO-CS), and storing the endogenous NO type chitosan (NO-CS) at the temperature of minus 20 ℃ for later use.
Further preferably, chitosan and lithium chloride are dissolved in DMA, triethylamine and p-toluenesulfonyl chloride are added to the system, stirred overnight, acetone precipitated, filtered and washed, and the residual solvent is removed in vacuo. Adding the product and lithium chloride into DMA, continuously adding triethylamine and ethanedithiol, stirring overnight at 60 ℃ under the protection of nitrogen, precipitating with acetone, filtering and washing the precipitate; then suspending it in DMA containing dithiothreitol, and stirring at room temperature; the precipitate was filtered and washed and the solvent removed in vacuo. Resuspending in DMA/methanol, adding tert-butyl nitrite, stirring at room temperature for 15 hr, precipitating with methanol after reaction, filtering and washing the precipitate, vacuum removing solvent to obtain endogenous NO type chitosan (NO-CS), and storing at-20 deg.C.
Chitosan (CS) has excellent biodegradability, biocompatibility, antimicrobial activity, non-toxicity and general chemical and physical properties, and can significantly improve the shelf life of fresh food as a new packaging material. The chitosan-based film and the coating effectively prolong the quality and the storability of food, and particularly have better effect with the composite film of some natural antioxidants and antibacterial agents.
The mass ratio of the chitosan to the lithium chloride is (0.25-1): 1; the mass ratio of the p-toluenesulfonyl chloride to the chitosan is (1-10): 1; the mass ratio of the 1, 2-ethanedithiol to the chitosan is (1-3): 1; the mass ratio of the tert-butyl nitrite to the chitosan is 0.3-6: 1. the dissolution used in washing the precipitate was: methanol, acetone or diethyl ether.
Reacting chitosan and p-toluenesulfonyl chloride at 0-5 ℃ for 20-24 h, namely in step S2.1, stirring and reacting conditions are as follows: reacting for 20-24 h at 0-5 ℃.
Reacting with tert-butyl nitrite at 20-25 ℃ for 10-20 h. Namely, in step S2.3, the conditions for the stirring reaction are: reacting for 10-20 h at 20-25 ℃.
In step S3, mixing caffeic acid butyl ester/cyclodextrin supramolecular inclusion compound and endogenous NO type chitosan to obtain homogeneous solution, specifically comprising:
adding endogenous NO type chitosan into hexafluoroisopropanol to obtain a chitosan solution, stirring for 1-5 hours, then adding caffeic acid butyl ester/cyclodextrin supramolecular inclusion compound, and stirring for 8-16 hours (preferably 12 hours) to obtain a homogeneous solution.
The dosage ratio of the butyl caffeate/cyclodextrin supermolecule inclusion compound to the chitosan solution is 3-10 g: 100mL, most preferably 6.8 g: 100 mL.
The ultra-efficient multifunctional nano electrostatic spinning film (namely the nano electrostatic spinning food preservative film) is processed by an electrostatic spinning technology and is applied to storage and preservation of fresh blueberry fruits.
The invention also provides a preparation method of the butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) mediated ultra-efficient multifunctional nano electrostatic spinning, which comprises the following specific steps:
the homogeneous solution was poured into a 20.0mL polypropylene syringe using a syringe needle with controlled flow rate. The fibers are gathered on the aluminum foil, and nano electrostatic spinning is sprayed out under the environment of external voltage of a high-voltage power supply and is accumulated into a film.
The conditions of the electrostatic spinning technology are as follows: the flow rate is adjusted to be 0.6-1.2 mL/h, the additional voltage is 12-18 kV, the vertical distance from the tip of the needle head to the conductive collecting device is 10-20 cm, and an aluminum foil is used as the conductive collecting device. The fibers are gathered on the aluminum foil, and nano electrostatic spinning is sprayed out under the environment of external voltage of a high-voltage power supply and is accumulated into a film.
Preferably, a 0.4mm inner diameter syringe needle is used and the flow rate is adjusted to 0.9mL h-1. The fibers were collected on an aluminum foil at a vertical distance of 15cm from the needle tip. The high voltage power supply is externally applied with 15kV voltage (22 ℃/45 +/-1% or 25 ℃/50%).
The invention also provides application of the nano electrostatic spinning food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) in storage and preservation of fresh blueberry fruits.
Preferably, the ultra-efficient antibacterial nano electrostatic spinning multifunctional food preservative film is used as a packaging material in the processing process of fresh blueberries and is used for preserving and storing the fresh blueberries. The nano electrostatic spinning multifunctional food preservative film is attached to the inner surface of the outer package of the blueberry fresh fruits, so that the difficulties that the blueberry fresh fruits are easily oxidized and easy to rot are effectively solved. The shelf life of the fresh blueberry fruit product is ensured, and the obtained product has excellent color and no bad flavor.
Further preferably, the processing process comprises:
(1) selecting materials: selecting proper blueberry fruit clusters to pick mature and stiff fresh blueberries, wherein the diameters of the fruits are not less than 0.7cm, and the fruits have no over-mature and peculiar smell.
(2) Cleaning: and repeatedly cleaning the blueberries with clean water until the water is clean after the blueberries are stirred.
(3) Selecting: draining water, and removing withered and shriveled parts.
(4) Preservative treatment: classifying fresh blueberries according to grades, and storing the fresh blueberries in a sterilized package with the ultra-high-efficiency multifunctional nano electrostatic spinning food preservative film attached to the inner surface, wherein the temperature for cold storage is 1-3 ℃. The method can effectively prevent the fresh blueberry fruits from being crushed or dehydrated and shrunk in the subsequent processing process to influence the value of finished products.
(5) The storage period of the product obtained by the method reaches 1-2 months.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts endogenous NO type chitosan (NO-CS) as a carrier of NO free radicals, which can provide long-acting slow-release NO free radicals and make the NO free radicals show excellent antibacterial and anti-biofilm characteristics. The substance is expected to be widely applied to the fields of food, hospitals, environments and the like.
(2) According to the invention, Cyclodextrin (CD) is adopted to encapsulate butyl caffeate to form an inclusion compound, the inclusion compound has better oxidation resistance, water solubility, super-strong antibacterial and anti-biofilm activity, and the nano electrostatic spinning multifunctional food preservative film is prepared by an electrostatic spinning technology. The nano spinning fiber membrane prepared by taking cyclodextrin as a non-polymer carrier has higher porosity and specific surface area, also has biocompatibility and has high application value in biomedicine, pharmacy, filtration and food packaging.
(3) The invention utilizes an ultra-efficient antibacterial nano electrostatic spinning multifunctional food preservative film mediated by a multifunctional food additive, namely butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS), as an inner surface active film of a blueberry fresh fruit package to prevent nutrient substances in the blueberry fresh fruit package from being oxidized and decayed. The processing and storage processes are simple, the raw materials are natural components, the production cost is low, and the difficulties that the fresh blueberry fruits are easily oxidized and easy to perish are effectively solved; the product shelf life is effectively prolonged, the flavor and the taste of the fresh blueberry are not influenced, and the fresh blueberry has a certain nutrition and health care function after being eaten, so that the production concept of modern healthy, environment-friendly and nutritional food is met.
(4) After the nano electrostatic spinning multifunctional food preservative film is applied to the inner surface of the outer package of the fresh blueberry fruits, the shelf life of the fresh blueberry fruits is effectively prolonged, the quality is good in the preservation period, the color and the flavor are well kept, the consumption concept of modern consumers is met, the commercial value of the fresh blueberry fruits is further improved, and the market demand is met; the method is easy to transport, the sale range of the fresh blueberry fruits is expanded, and particularly, gaps between market demands and actual supply quantities are made up well in inland major cities far away from the coast.
Drawings
Fig. 1 is an SEM image of an ultra-efficient multifunctional nano electrospun food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) obtained in embodiments 2 and 3 of the present invention.
FIG. 2 is a graph showing the change in the number of colonies of fresh blueberry fruits obtained in examples 2 to 3 and control groups 1 to 2 of the present invention.
FIG. 3 is a radar chart obtained by sensory evaluation of fresh blueberry fruits obtained in examples 2-3 and control groups 1-2 of the present invention.
FIG. 4 is a line graph showing the change of weight loss rate of fresh blueberries obtained in examples 4-5 and control group 3 of the invention during refrigeration.
Fig. 5 is a photograph of a sample of fresh blueberry fruits obtained in example 3 of the present invention and control 1 during the cold storage period (2 months).
Detailed Description
The invention is further described with reference to specific examples.
Example 1
1g of chitosan and 2g of lithium chloride were dissolved in 30mL of DMA and stirred overnight. To the system was added 7mL of triethylamine and 9.4g of p-toluenesulfonyl chloride in an ice-water bath, and stirring was continued overnight for 22 h. The product was precipitated with 200mL acetone, filtered, washed with 200mL methanol and acetone, and the residual solvent was removed in vacuo. Adding 0.4g of the reaction intermediate and 0.8g of lithium chloride into 20mL of DMA, continuously adding 0.8mL of triethylamine and 0.5mL of ethanedithiol, and stirring at 60 ℃ overnight under the protection of nitrogen; after the reaction is finished, precipitating by using 200mL of acetone, filtering, and cleaning by using 200mL of methanol and acetone; then it was resuspended in DMA containing 10mL dithiothreitol and 10mM triethylamine, and stirred at room temperature at 25 ℃ for 1 hour; after filtration, the mixture was washed with 200mL of methanol and 200mL of acetone, and the solvent was removed in vacuo. Resuspend in DMA/methanol, add 0.5mL tert-butyl nitrite (0.4g), stir at room temperature 25 ℃ for 15 hours; after the reaction is finished, 100mL of methanol is used for precipitation, after filtration, 100mL of acetone and ether are used for washing, the solvent is removed in vacuum, and the endogenetic NO type chitosan (NO-CS) is prepared and stored at the temperature of minus 20 ℃ for standby.
Example 2
A preparation method of an ultra-efficient multifunctional nano electrostatic spinning food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) comprises the following specific steps:
0.9g of endogenous NO type chitosan was added to 10mL of hexafluoroisopropanol, and the mixture was stirred at room temperature for 3 hours to obtain a chitosan solution. Dissolving beta-Cyclodextrin (CD) in a proper amount of water at room temperature of 25 ℃, and magnetically stirring butyl caffeate (CAC4) according to a proper proportion until the butyl caffeate is completely dissolved; slowly dropwise adding an absolute ethyl alcohol solution containing caffeic acid butyl ester into the cyclodextrin water solution (0.5:1, CAC4: CD, mol: mol), and continuously stirring at 60 ℃ for 48 hours after dropwise adding; standing in a refrigerator at-4 deg.C for 48 hr until white solid is precipitated, filtering, collecting filtrate, refrigerating at-20 deg.C overnight, and freeze drying at-45 deg.C for 24 hr to obtain caffeic acid butyl ester-cyclodextrin supramolecular clathrate (CAC 4/CD-IC). The inclusion compound is added into the chitosan solution according to a certain proportion (6.8 percent, w/v), and stirred for 12 hours at room temperature. Pouring the homogeneous solution into a 20.0mL polypropylene syringe, using an injection needle with an inner diameter of 0.4mm, and adjusting the flow rate to 0.9mL h-1. The fibers were collected on an aluminum foil at a vertical distance of 15cm from the needle tip. The high voltage power supply is externally applied with 15kV voltage (22 ℃/45 +/-1% or 25 ℃/50%).
The SEM image of the produced nano electrospun membrane is shown in fig. 1 (a).
A processing method for prolonging the storage period of fresh blueberries by acting a nano electrostatic spinning multifunctional food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) on the inner surface of a package of the fresh blueberries comprises the following steps:
(1) selecting materials: selecting proper blueberry fruit clusters to pick mature and stiff fresh blueberries, wherein the diameters of the fruits are not less than 0.7cm, and the fruits have no over-mature and peculiar smell.
(2) Cleaning: and repeatedly cleaning the blueberries with clean water until the water is clean after the blueberries are stirred.
(3) Selecting: draining water, and removing withered and shriveled parts.
(4) Preservative treatment: classifying fresh blueberries according to grades, and storing the fresh blueberries in a sterilized package with the ultra-high-efficiency multifunctional nano electrostatic spinning food preservative film attached to the inner surface, wherein the temperature for cold storage is 1-3 ℃. The method can effectively prevent the fresh blueberry fruits from being crushed or dehydrated and shrunk in the subsequent processing process to influence the value of finished products.
(5) The storage period of the product obtained by the method reaches 1-2 months.
The colony number variation curve of the obtained product is shown in figure 2; the quality change of the obtained product is shown in fig. 3.
Example 3
The difference between the embodiment and the embodiment 2 is that the proportion of the CAC4 in the system is increased, so as to improve the bacteriostatic and antioxidant effects of the nano electrostatic spinning film.
A preparation method of an ultra-efficient multifunctional nano electrostatic spinning food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) comprises the following specific steps:
0.9g of endogenous NO type chitosan was added to 10mL of hexafluoroisopropanol, and the mixture was stirred at room temperature for 3 hours. Dissolving beta-Cyclodextrin (CD) in a proper amount of water at room temperature of 25 ℃, and magnetically stirring butyl caffeate (CAC4) according to a proper proportion until the butyl caffeate is completely dissolved; slowly dropwise adding an absolute ethyl alcohol solution containing butyl caffeate into the cyclodextrin aqueous solution (1:1, CAC4: CD, mol: mol), and continuously stirring for 48 hours at 60 ℃ after dropwise adding; standing in a refrigerator at-4 deg.C for 48 hr until white solid is precipitated, filtering, collecting filtrate, refrigerating at-20 deg.C overnight, and freeze drying at-45 deg.C for 24 hr to obtain caffeic acid butyl ester-cyclodextrin supramolecular clathrate (CAC 4/CD-IC). The inclusion compound is added into the chitosan solution according to a certain proportion (6.8 percent, w/v), and stirred for 12 hours at room temperature. Pouring the homogeneous solution into a 20.0mL polypropylene syringe, using an injection needle with an inner diameter of 0.4mm, and adjusting the flow rate to 0.9mL h-1. The fibers were collected on an aluminum foil at a vertical distance of 15cm from the needle tip. The high voltage power supply is externally applied with 15kV voltage (22 ℃/45 +/-1% or 25 ℃/50%).
The SEM image of the produced nano electrospun membrane is shown in fig. 1 (b).
A processing method for prolonging the storage period of fresh blueberries by acting a nano electrostatic spinning multifunctional food preservative film mediated by butyl caffeate (CAC4) and endogenous NO type chitosan (NO-CS) on the inner surface of a package of the fresh blueberries comprises the following steps:
(1) selecting materials: selecting proper blueberry fruit clusters to pick mature and stiff fresh blueberries, wherein the diameters of the fruits are not less than 0.7cm, and the fruits have no over-mature and peculiar smell.
(2) Cleaning: and repeatedly cleaning the blueberries with clean water until the water is clean after the blueberries are stirred.
(3) Selecting: draining water, and removing withered and shriveled parts.
(4) Preservative treatment: classifying fresh blueberries according to grades, and storing the fresh blueberries in a sterilized package with the ultra-high-efficiency multifunctional nano electrostatic spinning food preservative film attached to the inner surface, wherein the temperature for cold storage is 1-3 ℃. The method can effectively prevent the fresh blueberry fruits from being crushed or dehydrated and shrunk in the subsequent processing process to influence the value of finished products.
(5) The storage period of the product obtained by the method reaches 1-2 months.
The colony number variation curve of the obtained product is shown in figure 2; the quality change of the obtained product is shown in fig. 3.
Comparative example 1
Referring to the preparation method of example 2, but without the processing step of the nano preservative film in the step (4), the ordinary packaging and storage are directly carried out, and the colony number change curve of the obtained product is shown in fig. 2; the quality change of the obtained product is shown in fig. 3.
Comparative example 2
Referring to the preparation method of example 2, but using natural chitosan, the colony number variation curve of the obtained product is shown in FIG. 2; the quality change of the obtained product is shown in fig. 3.
Example 4
The butyl caffeate (CAC4) prepared in the example 2 and the endogenetic NO type chitosan (NO-CS) mediated ultra-efficient multifunctional nano electrostatic spinning food preservative film are applied to fresh blueberry fruits (0.2mg/g), and the weight loss rate of the fresh blueberry fruits during refrigeration is tracked and determined for 2 months under the refrigeration condition of 0 ℃. The change result of the weight loss ratio of the obtained fresh blueberry fruits during refrigeration is shown in figure 4.
Example 5
The butyl caffeate (CAC4) prepared in the example 3 and the endogenetic NO type chitosan (NO-CS) mediated ultra-efficient multifunctional nano electrostatic spinning food preservative film are applied to fresh blueberry fruits (0.2mg/g), and the weight loss rate of the fresh blueberry fruits during refrigeration is tracked and determined for 2 months under the refrigeration condition of 0 ℃. The change result of the weight loss ratio of the obtained fresh blueberry fruits during refrigeration is shown in figure 4.
Comparative example 3
Referring to the method in example 4, but without any preservatives and preservative films, the weight loss rate change results of the obtained fresh blueberries during refrigeration at 0 ℃ are shown in fig. 4.
Comparative example 4
Referring to the method in example 4, the weight loss rate of the obtained fresh blueberry fruits during refrigeration at 0 ℃ is shown in fig. 4 by using only tea polyphenol as the preservative.
Claims (10)
1. A preparation method of a butyl caffeate and endogenous NO type chitosan mediated nano electrostatic spinning food preservative film is characterized by comprising the following steps:
s1, mixing cyclodextrin and butyl caffeate to obtain a butyl caffeate/cyclodextrin supermolecular inclusion compound;
s2, preparing endogenous NO type chitosan by a method of covalently modifying natural chitosan;
and S3, mixing the butyl caffeate/cyclodextrin supermolecule inclusion compound with the endogenous NO type chitosan to obtain a homogeneous solution, and processing the homogeneous solution into the nano electrostatic spinning food preservative film by an electrostatic spinning technology.
2. The method according to claim 1, wherein in step S1, the cyclodextrin is mixed with butyl caffeate to obtain the butyl caffeate/cyclodextrin supramolecular inclusion compound, which specifically comprises:
dissolving cyclodextrin in water, and magnetically stirring until the cyclodextrin is completely dissolved to obtain cyclodextrin water solution; dropwise adding an absolute ethyl alcohol solution containing butyl caffeate into the cyclodextrin aqueous solution, and continuously stirring for 36-60 hours at the temperature of 55-65 ℃ after dropwise adding; standing in a refrigerator at the temperature of between-2 and-8 ℃ for 36 to 60 hours until white solid matters are separated out, filtering, collecting filtrate, refrigerating at the temperature of between-15 and-25 ℃ overnight, and freeze-drying at the temperature of between-40 and-50 ℃ for 18 to 30 hours to obtain the caffeic acid butyl ester-cyclodextrin supramolecular inclusion compound.
3. The preparation method according to claim 2, wherein the molar ratio of the butyl caffeate to the cyclodextrin is 0.25-1.5: 1.
4. the method according to claim 1, wherein in step S1, the cyclodextrin is α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin or hydroxypropyl β -cyclodextrin.
5. The method of claim 1, wherein the step S2 of preparing endogenous NO type chitosan by covalent modification of natural chitosan comprises:
s2.1, dissolving chitosan and lithium chloride in N, N-dimethylaniline, adding triethylamine and p-toluenesulfonyl chloride into the system, stirring for reaction, precipitating with acetone, filtering and washing the precipitate, and removing the residual solvent in vacuum;
s2.2, adding the product obtained in the step S2.1 and lithium chloride into N, N-dimethylaniline, continuously adding triethylamine and ethanedithiol, stirring overnight at 50-70 ℃ under the protection of nitrogen, precipitating with acetone, filtering and washing the precipitate, then suspending the precipitate in N, N-dimethylaniline containing dithiothreitol and triethylamine, stirring, filtering and washing the precipitate, and removing the solvent in vacuum;
s2.3, washing the product obtained in the step S2.2, re-suspending the product in N, N-dimethylaniline/methanol, adding tert-butyl nitrite, stirring for reaction, after the reaction is finished, precipitating by using methanol, filtering, washing and precipitating, and removing the solvent in vacuum to obtain the endogenous NO type chitosan.
6. The preparation method according to claim 5, wherein the mass ratio of the chitosan to the lithium chloride is 0.25-1: 1;
the mass ratio of the p-toluenesulfonyl chloride to the chitosan is (1-10): 1;
the mass ratio of the ethanedithiol to the chitosan is (1-3): 1;
the mass ratio of the tert-butyl nitrite to the chitosan is (0.3-6): 1.
7. the process according to claim 5, wherein in step S2.1, the conditions for the stirring reaction are as follows: reacting for 20-24 h at 0-5 ℃;
in step S2.3, the conditions of the stirring reaction are: reacting for 10-20 h at 20-25 ℃.
8. The method of claim 1, wherein in step S3, the butyl caffeate/cyclodextrin supramolecular inclusion compound and endogenous NO-type chitosan are mixed to obtain a homogeneous solution, and the method specifically comprises:
adding endogenous NO type chitosan into hexafluoroisopropanol to obtain a chitosan solution, stirring for 1-5 hours, then adding caffeic acid butyl ester/cyclodextrin supermolecule inclusion compound, and stirring for 8-16 hours to obtain a homogeneous solution;
in step S3, the processing conditions of the electrospinning technique are as follows: the flow rate is adjusted to be 0.6-1.2 mL/h, the additional voltage is 12-18 kV, the vertical distance from the tip of the needle head to the conductive collecting device is 10-20 cm, and an aluminum foil is used as the conductive collecting device.
9. The nano electrostatic spinning food preservative film mediated by butyl caffeate and endogenous NO type chitosan prepared by the preparation method of any one of claims 1 to 8.
10. The use of the butyl caffeate-endogenous NO type chitosan mediated nano electrospun food preservative film as claimed in claim 9 in the storage and preservation of fresh blueberry fruits.
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