CN113308001B - Preparation method of nano particle-loaded antibacterial paper - Google Patents

Preparation method of nano particle-loaded antibacterial paper Download PDF

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CN113308001B
CN113308001B CN202110622118.8A CN202110622118A CN113308001B CN 113308001 B CN113308001 B CN 113308001B CN 202110622118 A CN202110622118 A CN 202110622118A CN 113308001 B CN113308001 B CN 113308001B
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crude extract
curcumin
hawthorn
solution
polysaccharide crude
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CN113308001A (en
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刘耀文
王玥
曾渊博
张海湉
沈思蔚
杨小
谢娟娟
朱慧彦
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Sichuan Agricultural University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/132Phenols containing keto groups, e.g. benzophenones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a preparation method of nano particle-loaded antibacterial paper, which comprises the following steps: s1, dissolving curcumin and hawthorn polysaccharide crude extract powder respectively, then dropwise adding a curcumin solution into a hawthorn polysaccharide crude extract solution, adding a sodium tripolyphosphate solution after dropwise adding is finished, starting stirring, and sequentially carrying out ultrasonic treatment, centrifugation and freeze drying after adding is stopped to obtain curcumin/hawthorn polysaccharide crude extract nanoparticles; s2, gelatinizing the corn starch, cooling, mixing with curcumin/hawthorn polysaccharide crude extract nanoparticles, adding glycerol into the mixture, uniformly mixing, carrying out tape casting to form a film, and drying to obtain the starch antibacterial paper. The nano particle-loaded antibacterial paper prepared by the method has excellent antibacterial and bacteriostatic effects, and has the advantages of simple preparation process, health, environmental protection, safety, easy degradation and the like.

Description

Preparation method of nano particle-loaded antibacterial paper
Technical Field
The invention relates to the technical field of antibacterial paper, in particular to a preparation method of antibacterial paper loaded with nano particles.
Background
Bacteria are ubiquitous, the health of human beings is threatened constantly, and along with the increasing demand for healthy living environment, people pay more and more attention to environmental microorganisms which are harmful to health. The antibacterial paper is a novel material with the function of killing or inhibiting microorganisms, is mainly used in the fields of food preservation and food safety, and has wide development space and market prospect.
At present, researchers prepare antibacterial paper with nanoparticles and use the antibacterial paper in the field of food preservation and freshness preservation, but the nanoparticles are mostly preserved in a single form of spraying or soaking and the like, and due to the small size of the nanoparticles, the nanoparticles can permeate into food and enter the body along with the food when being in direct contact with the food, and the safety is not determined. Therefore, there is a need for an environmentally friendly and stable antibacterial paper with good antibacterial and bacteriostatic effects and capable of avoiding direct contact of nanoparticles.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the preparation method of the antibacterial paper carrying the nano particles, which has the advantages of simple process, safety, environmental protection, no pollution, easy industrialization and good application prospect.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the antibacterial paper carrying the nano particles is characterized by comprising the following steps:
s1, dissolving curcumin and hawthorn polysaccharide crude extract powder respectively, then dropwise adding a curcumin solution into the hawthorn polysaccharide crude extract solution, adding a sodium tripolyphosphate solution after dropwise adding, starting stirring, and sequentially performing ultrasonic treatment, centrifugation and freeze drying after adding is stopped to obtain curcumin/hawthorn polysaccharide crude extract nanoparticles;
the CPP is a natural harmless compound, mostly exists in the hawthorn, has the functions of resisting oxidation and promoting digestion, can effectively protect a core material by being used as a wall material of the nano particles, prevents the core material from being oxidized and ineffective, and is harmless to a body even if the CPP is eaten by mistake; CUR has anti-inflammatory, antibacterial and antioxidant effects, has broad-spectrum antibacterial activity, but has poor water solubility, low bioavailability and poor chemical stability, and limits its wide application in food storage. The release rate of the CPP can be effectively controlled by wrapping the CPP in the oil, the use stability of the CPP is enhanced, and the CPP and the antioxidant property of the hawthorn polysaccharide are synergistically enhanced.
And S2, gelatinizing the corn starch, cooling, mixing with the CUR/CPP nano particles, adding glycerol into the mixture, uniformly mixing, carrying out tape casting to form a film, and drying to obtain the nano particle-loaded antibacterial paper.
The corn starch has the characteristics of low cost, wide source, high biodegradability, good film-forming property and the like, is used as a substrate of a nanoparticle loading system, has extremely high loading efficiency of nanoparticles, and simultaneously avoids the nanoparticles from directly contacting food, so that the nanoparticles are safer and more effective in preservation in the form of antibacterial paper.
Further, in the step S1, the curcumin solution is dropwise added at a speed of 4 drops per minute for 5-15 minutes.
Further, in the step S1, when the mass ratio of the sodium tripolyphosphate to the crude extract of the hawthorn polysaccharide reaches 1:5-1:30. at that time, the addition was stopped.
Further, in step S1, the preparation method of the crataegus polysaccharide crude extract powder comprises the following steps: dissolving hawthorn powder into distilled water according to a material-liquid ratio of 1-30-1 (70g/mL), then extracting by using a microwave extraction method, and sequentially centrifuging, precipitating and freeze-drying the obtained crude extract solution of the hawthorn polysaccharide to obtain the hawthorn polysaccharide crude extract; further, in the step S1, the material-liquid ratio of CPP used in the microwave extraction method to distilled water is 1-30-1.
Further, in the step S2, the CUR solution is dissolved in ethanol, and the concentration is 0.06-0.32w/v; the CPP powder is dissolved in distilled water at a concentration of 0.24% -0.48% w/v.
Further, in step S1, the pH of the solution should be adjusted to 2-6 after dissolving the crataegus polysaccharide crude extract powder.
Further, in step S2, the mass of the TPP and CPP is 1:5-1:30.
the invention also aims to provide the nano particle-loaded antibacterial paper prepared by the preparation method.
The antibacterial paper has the advantages of good antibacterial and bacteriostatic effects, diversified applications, natural and environment-friendly materials, low cost, and capability of preventing food from directly contacting with nanoparticles and protecting food safety.
The invention has the beneficial effects that:
1. the starch antibacterial paper prepared by the invention has the advantages of strong antibacterial and antioxidant properties, natural material, complete degradation, heating, no harmful components, low cost, capability of effectively prolonging the quality guarantee period of fresh meat by about 2 times, and wide application prospect.
2. Compared with the traditional preservative film material, the preservative film material is natural in material, has the advantages of corn starch, hawthorn polysaccharide and curcumin, has a more lasting and efficient preservative effect, and overcomes the problems of no antibacterial and antioxidant property, difficult degradation and the like of the traditional preservative film.
Drawings
FIG. 1 is a diagram: an electron microscope image of the nano particle-loaded antibacterial paper is shown;
FIG. 2 is a diagram of: the experimental results of example 2 are in line graph.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
A preparation method of antibacterial paper carrying nanoparticles comprises the following steps:
s1: according to the feed-liquid ratio of 1:50, dissolving 1.0g of hawthorn powder sample in a certain volume of distilled water, and putting the solution into a microwave extraction device. The parameters are set as microwave power 450W, time 5min and temperature 50 ℃. Then the CPP solution is added at 4000 r.min -1 Centrifuge for 15 minutes to obtain supernatant. Under magnetic stirring, 5 times volume of absolute ethyl alcohol is added dropwise, and precipitation is carried out for 1 hour. The mixed solution is at 4000 r.min -1 Centrifuging for 15min again under the condition to obtain precipitate, and freeze drying to obtain CPP powder.
S2: 12mg CUR was dissolved in 12mL ethanol to a final concentration of 1mg/mL. CPP powder was dissolved in 5mL of distilled water at a concentration of 0.24%. The pH was adjusted to pH =5 with NaoH and the CUR solution was added drop-wise to the CPP solution at a rate of 4 drops per minute. After 5-15min, TPP solution was added with constant magnetic stirring as the nanoparticles spontaneously formed. The volume of TPP solution used is chosen so that the weight ratio of TPP to CPP is 1. The samples were centrifuged at 4000RPM/min for 25 minutes after 10 minutes sonication. The precipitate was freeze-dried for 24 hours.
S3: placing corn starch in a water bath at 80 ℃ for 1h to finish gelatinization, cooling to room temperature, and mixing the corn starch and the nanoparticles in a mass ratio of 10:3 and then 1wt% of glycerol was added to the solution as a plasticizer. Finally, a certain amount of the mixed solution is weighed and evenly poured onto a glass plate, and the glass plate is placed in an oven at the temperature of 35 ℃ for 6-8h.
An electron microscope image of the nanoparticle-loaded antibacterial paper is shown in fig. 1.
Example 2
Experimental materials:
1. starch antibacterial paper: the procedure is as in example 1.
2. Conventional cling films are commercially available.
3. Pure corn starch paper: placing corn starch in water bath at 80 deg.C for 1h to complete gelatinization, cooling to room temperature, and adding 1-3wt% glycerol as plasticizer into the solution. Finally, a certain amount of mixed liquid is weighed and evenly poured onto a glass plate, and the glass plate is placed in an oven at the temperature of 35 ℃ for 6-8 hours.
Taking a fresh pork, slicing every three pork into one group, covering the starch antibacterial paper prepared in the example 1 on one group, covering the traditional preservative film and the pure corn starch paper on the other two groups respectively, taking the pork without any treatment as a control group, putting the 4 groups of pork slices into a covered sterile culture dish (the diameter is 15 cm) respectively, storing the pork slices in an incubator (25 ℃, the relative humidity is 65%) for 8 days, observing, and recording the changes of the pH, the volatile basic nitrogen, the T-thio-barbituric acid and the weight loss rate.
The results are shown in FIG. 2, and it can be seen from FIG. 2 that: 1. in eight days, the pH value of the pork of the antibacterial paper group is almost unchanged, and the pH values of the other three groups are obviously increased, which shows that the CS and the CUR in the antibacterial paper inhibit the growth of microorganisms, slow down the decomposition speed of amino acid and further inhibit the increase of the pH value. 2. In eight days, the content of volatile basic nitrogen and T-thiobarbituric acid in the pork of the four groups is obviously increased, but the increase of the antibacterial paper group is the least, the increase of the volatile basic nitrogen of the meat is due to the oxidation of protein and the proliferation of bacteria, and the T-thiobarbituric acid represents the oxidation degree of the sample fat. 3. The weight loss ratio antibacterial paper group is higher than the preservative film group and lower than the pure starch group and the blank group, but the preservative effect of the preservative film group is not the best because the air permeability of the preservative film is poor and water molecules generated in the meat spoilage process cannot pass through the preservative film.
It can be concluded that: the invention prepares the CUR/CPP functional nano particles with good embedding and releasing effects, realizes the protection and slow release of the CUR, ensures that the antibacterial and antioxidant effects of the CUR are lasting and efficient, and prolongs the fresh-keeping period. The longest time can prolong the shelf life of fresh pork to 5 days.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and is not to be construed as limited to the exclusion of other embodiments, and that various other combinations, modifications, and environments may be used and modifications may be made within the scope of the concepts described herein, either by the above teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A preparation method of nano particle-loaded antibacterial paper is characterized by comprising the following steps:
s1, dissolving curcumin and hawthorn polysaccharide crude extract powder respectively, then dropwise adding a curcumin solution into a hawthorn polysaccharide crude extract solution, adding a sodium tripolyphosphate solution after dropwise adding is finished, starting stirring, and sequentially carrying out ultrasonic treatment, centrifugation and freeze drying after adding is stopped to obtain curcumin/hawthorn polysaccharide crude extract nanoparticles;
s2, gelatinizing corn starch, cooling, uniformly mixing with curcumin/hawthorn polysaccharide nanoparticles, adding glycerol into the mixture, uniformly mixing, carrying out tape casting to form a film, and drying to obtain the nanoparticle-loaded antibacterial paper;
in the step S2, the mass ratio of the corn starch to the curcumin/hawthorn polysaccharide crude extract nanoparticles is 10.
2. The method of claim 1, wherein: in the step S1, the curcumin solution is dropwise added at a speed of 4 drops per minute for 5-15 minutes.
3. The production method according to claim 1, characterized in that: in the step S1, when the mass ratio of the sodium tripolyphosphate to the hawthorn polysaccharide crude extract reaches 1:5-1: at 30 hours, the addition was stopped.
4. The method of claim 1, wherein: in the step S1, the preparation method of the hawthorn polysaccharide crude extract powder comprises the following steps: dissolving hawthorn powder into distilled water according to a material-liquid ratio of 1-30-1 (70g/mL), then extracting by using a microwave extraction method, and sequentially centrifuging, precipitating, and freeze-drying the obtained hawthorn polysaccharide crude extract solution to obtain the hawthorn polysaccharide.
5. The method of claim 1, wherein: in step S1, the curcumin solution is dissolved in ethanol at a concentration of 0.06% -0.32% w/v; the crude extract powder of fructus crataegi polysaccharide is dissolved in distilled water, and has a concentration of 0.24-0.48% w/v.
6. The method of claim 1, wherein: in step S1, the pH of the solution should be adjusted to 2-6 after dissolving the hawthorn polysaccharide crude extract powder.
7. The antibacterial paper with the nano-particles prepared by the preparation method according to any one of claims 1 to 6.
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Publication number Priority date Publication date Assignee Title
EP2349237A4 (en) * 2008-07-31 2012-07-25 Santosh Kumar Kar Curcumin nanoparticles and methods of producing the same
CN104273522B (en) * 2013-07-03 2016-08-10 江南大学 A kind of curcumin nano complex and preparation method thereof
CN105286011B (en) * 2015-09-18 2018-05-15 华南理工大学 A kind of soluble soybean polysaccharide-soybean protein-curcumin complex and preparation and application
CN105297549B (en) * 2015-10-13 2017-04-26 封开县嘉诚纸业有限公司 Bacteriostatic paper containing radix curcuma and preparation method and application of bacteriostatic paper
US11612179B2 (en) * 2017-08-23 2023-03-28 Miguel Enrique Jesus Malnati Ramos Method for producing a nanoemulsion with encapsulated natural antioxidants for preserving fresh and minimally processed foods, and the nanoemulsion thus produced
CN108208834B (en) * 2018-01-05 2021-03-30 华南理工大学 Curcumin-loaded soybean protein-based nanoparticles and preparation method and application thereof
CN110089753A (en) * 2019-04-16 2019-08-06 东北农业大学 A kind of preparation method for the nanoparticle improving curcumin bioavailability
WO2021077380A1 (en) * 2019-10-25 2021-04-29 合肥工业大学 Bifunctional starch-based composite nanoparticle, preparation method therefor and use thereof

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