CN115053909B - Bio-based green composite antibacterial agent and preparation method and application thereof - Google Patents
Bio-based green composite antibacterial agent and preparation method and application thereof Download PDFInfo
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- CN115053909B CN115053909B CN202210713465.6A CN202210713465A CN115053909B CN 115053909 B CN115053909 B CN 115053909B CN 202210713465 A CN202210713465 A CN 202210713465A CN 115053909 B CN115053909 B CN 115053909B
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- antibacterial agent
- packaging material
- green composite
- antibacterial
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 86
- 239000011174 green composite Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 53
- 239000005022 packaging material Substances 0.000 claims abstract description 33
- 239000002262 Schiff base Substances 0.000 claims abstract description 26
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 25
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000012141 vanillin Nutrition 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 150000001413 amino acids Chemical class 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 14
- 235000001014 amino acid Nutrition 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 239000004473 Threonine Substances 0.000 claims description 5
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
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Abstract
The invention discloses a bio-based green composite antibacterial agent, a preparation method and application thereof. And the hydroxyl group on the benzene ring of vanillin may have a certain antibacterial effect, so that cytoplasm is condensed to reduce the running power of protons, and the hydroxyl group and the imino group of Schiff base play a role in synergistic antibacterial effect, thereby improving the antibacterial effect. The invention further uses the antibacterial agent in the packaging material, not only endows the packaging material with antibacterial performance, but also improves the mechanical property, safety and environmental protection of the packaging material, and solves the problems of poor thermal stability and weaker antibacterial performance of the existing antibacterial agent.
Description
Technical Field
The invention relates to the technical field of preparation of antibacterial materials, in particular to a bio-based green composite antibacterial agent, and a preparation method and application thereof.
Background
Plastic packaging brings many convenience to the life of people, but also has the problems of harmful ingredients, difficult degradation and the like. With the continuous enhancement of environmental awareness, the adoption of environment-friendly degradable plastics to replace the traditional plastic packaging materials has become a trend. PVA film is a green environment-friendly packaging material, which is highly focused by people because of its excellent water solubility and degradability. Meanwhile, the nontoxic and odorless PVA film has very good mechanical property, antistatic property, organic solvent resistance and moisture-permeable and gas-blocking properties, so that the PVA film is widely applied to various industries and is one of the most widely applied films on the market at present.
However, PVA, which is a food package, does not have antibacterial properties, and needs to be modified by adding an antibacterial agent to satisfy antibacterial requirements. The existing antibacterial agents are mainly divided into inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. The inorganic antibacterial agent mainly comprises metal ion antibacterial agent such as silver zeolite, silver silica gel, silver activated carbon, silver hydroxyapatite based antibacterial agent, etc., and photocatalytic metal oxide antibacterial agent such as nanometer titanium dioxide and nanometer zinc oxide, etc. Is the most widely applied antibacterial agent variety with the market prospect at present. Initially scientists added silver directly to the resin, but this method tends to result in a significant decrease in other properties of the antimicrobial plastic and silver ions are easily precipitated in contact water, so that the antimicrobial lifetime of this method is short. At present, a porous structure carrier is mainly adopted, silver ions are loaded in the structure to form stable chelation, and therefore the antibacterial effect is achieved. The antibacterial agent has high temperature resistance, low toxicity and broad antibacterial spectrum, but the silver antibacterial agent is easy to change color, the processing and manufacturing process is complicated and high in cost, and the production cost of the antibacterial agent is improved to a certain extent, so that the application prospect of the antibacterial agent is limited. The organic antibacterial agent mainly comprises organic compounds taking petroleum groups as raw materials, such as quaternary ammonium salts, quaternary phosphonium salts, phenols, isothiazoles, thiazoles, organic metals and the like. Compared with inorganic antibacterial agents, the antibacterial agents have the advantages of high sterilization speed and good mildew-proof effect, the process operability of the antibacterial agents added into plastics is superior to that of the inorganic antibacterial agents, and the antibacterial agents are more stable in color in storage, circulation, transportation and use. However, the use of these antibacterial agents in antibacterial packaging materials such as plastics has been greatly limited even if they have been developed earlier in industrial applications than inorganic antibacterial agents because of their poor heat resistance, easy precipitation, toxic decomposition products, and easy occurrence of drug resistance. The natural antibacterial agent mainly comes from extracts of natural substances, and has the advantages of environmental protection, natural raw materials, wide sources, broad antibacterial spectrum, high safety, environmental protection, no toxicity or harm, good biocompatibility and the like compared with other two antibacterial agents. However, the natural antibacterial agent has poor thermal stability, and compared with other two antibacterial agents, part of the antibacterial agent has weaker antibacterial performance, so that larger addition amount is needed, and the antibacterial agent has higher cost and poorer application value and is not suitable for being used in a large amount in plastics.
In CN202110525566.6, a preparation method of aldehyde amine condensation Schiff base modified protein composite membrane is disclosed, aldehyde reagent and alcohol amine reagent are adopted to synthesize aldehyde amine condensation Schiff base, which plays a role of an antibacterial modifier on one hand, imparts antibacterial property to the composite membrane, plays a role of a plasticizer on the other hand, and improves mechanical property of the composite membrane. However, the alcohol amine reagent and the aldehyde reagent are adopted for condensation reaction, and as the alcohol amine reagent belongs to substances containing hydroxyl and amino, the antibacterial property of the synthesized substances is weak, and the antibacterial property of the protein composite membrane can be effectively endowed only when the addition amount of the synthesized aldehyde amine condensation Schiff base is more than 10%, so that the antibacterial requirement is difficult to meet. In addition, the alcohol amine reagent is a non-biological base material, and once the residual alcohol amine reagent after synthesis migrates and seeps out from the packaging material, the alcohol amine reagent can cause strong irritation to human skin, eyes, mucous membranes and the like. And the substance is harmful to the environment, especially the water body causes environmental damage, so the application of the antibacterial film in food packaging has a certain problem.
Disclosure of Invention
The invention aims to solve the technical problems of poor thermal stability and weak antibacterial performance of the existing antibacterial agent and provides a bio-based green composite antibacterial agent.
The invention further provides a preparation method and application of the bio-based green composite antibacterial agent.
The aim of the invention is realized by the following technical scheme:
A bio-based green composite antimicrobial agent comprising the steps of:
The biological base green composite antibacterial agent is prepared from raw materials including vanillin and amino acid through Schiff base reaction. The specific reactions are as follows:
Vanillin is a natural organic substance extracted from the kidney bean, a plant of the family Rutaceae, and is usually prepared by lignin degradation. Amino acids are widely found in proteins of higher plants and animals, and can be synthesized by proteolytic purification. The multifunctional Schiff base antibacterial agent is prepared by reacting vanillin and amino acid through the Schiff base, so that the antibacterial efficiency of the natural antibacterial agent is ensured, and meanwhile, the efficient imine antibacterial functional group is introduced, so that the antibacterial performance of the film is improved.
Further, the molar ratio of vanillin to amino acid is 1:0.1-10.
Further, the amino acids include one or more of tryptophan, cysteine, tyrosine, threonine, phenylalanine, aspartic acid, glycine, and alanine.
The preparation method of the bio-based green composite antibacterial agent comprises the following steps:
S1, dissolving amino acid in an alkaline organic solvent, heating, reacting until the mixed liquid is colorless and transparent, and cooling;
S2, dripping the colorless and transparent mixed liquid in the S1 into an organic solvent containing vanillin, carrying out recrystallization after the reaction, and drying to obtain the bio-based green composite antibacterial agent.
Further, in the step S1, the alkaline substance is one or more of inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and the like, or organic bases such as tertiary amine and the like, and can replace H of carboxyl on an amino acid structure, so that the carboxyl is converted into an ester group, the amino is protected to smoothly perform schiff base reaction, but not amide reaction, and the amino of the amino acid can be activated to perform esterification protection, and then the amino is in the form of ammonium salt, and can be dissociated by adding the base. Preferably, the molar ratio of amino acid to base material in step S1 is 1:1.
Further, the organic solvent is a neutral solvent of methanol or ethanol.
Further, the reaction temperature in the step S1 is 50-80 ℃ and the reaction time is 0.5-1 h.
Further, in step S2, an ethanol solution containing vanillin is used.
Further, the reaction time in the step S2 is 1-3 h.
Further, the bio-based green composite antibacterial agent is applied to a high polymer packaging film or a paper packaging material.
Further, the bio-based green composite antibacterial agent is prepared into a film by blending with a packaging material matrix solution, melt blending or coating, so as to obtain the bio-based green composite antibacterial packaging material.
Further, the step of solution blending includes: and adding a certain proportion of bio-based green composite antibacterial agent into the solution containing the packaging material matrix, stirring, and preparing the uniform mixed solution into a film to obtain the bio-based green composite antibacterial packaging material.
Further, the step of melt blending includes: the polymer and the antibacterial agent are evenly blended in a molten state to prepare the film forming to obtain the bio-based green composite antibacterial packaging material.
Further, the step of coating includes: and adding a certain proportion of bio-based green composite antibacterial agent into the solution containing the packaging material matrix, uniformly blending, and coating on the surface of the packaging material to form a coating with an antibacterial function.
Further, the mass of the packaging material matrix is 3-10% of the mass of the solution.
Further, the addition amount of the bio-based green composite antibacterial agent is 0.01-10% of the mass of the packaging material matrix. Preferably, the addition amount of the bio-based green composite antibacterial agent is 0.1-5% of the mass of the packaging material matrix.
Further, a plasticizer, which is glycerol, can be added into the packaging material to improve the mechanical properties of the film.
Further, the addition amount of the plasticizer is 5-35% of the mass of the packaging material matrix. Preferably, the plasticizer is added in an amount of 15-25% of the mass of the packaging material matrix.
Further, the preparation film forming mode comprises casting, solution film forming, coating, coextrusion, melt blown film or melt tabletting film forming.
Compared with the prior art, the beneficial effects are that:
The invention adopts natural green vanillin and amino acid to prepare a bio-based green composite antibacterial agent through Schiff base reaction, the cell membrane of microorganism is composed of double-layer phospholipid groups and is mainly provided with negative charges, the hybridization orbit of Schiff base imino in the bio-based green composite antibacterial agent is provided with lone pair electrons, and the Schiff base reacts with anions or sulfhydryl groups in a combined way to influence the synthesis of a biological membrane, so that the growth and the propagation of the microorganism are inhibited. The vanillin belongs to natural bio-based phenols, and the hydroxyl group on the benzene ring may have a certain antibacterial effect, so that cytoplasm is condensed to reduce the running power of protons, and simultaneously, the amino acid structure contains the anji and the carboxyl, the carboxyl can have a destructive effect on bacteria, and the two have a synergistic antibacterial effect with the imino group of Schiff base, so that the antibacterial effect is improved.
The bio-based green composite antibacterial agent is applied to the packaging material, so that the antibacterial property of the packaging material is endowed, and the mechanical property of the packaging material is improved. And the antibacterial agent has low migration in the film material, so that the safety of the film in use is ensured. And the moisture permeability of the packaging material can be improved, and the natural temperature bed for the growth and propagation of microorganisms is avoided, so that the antibacterial performance is further improved.
The raw materials used in the invention are all purely natural and degradable, the preparation method is simple, and the preparation method makes positive contribution for promoting the green chemical new material and sustainable development, and has very broad application prospect.
Drawings
FIG. 1 is a schematic diagram of the antibacterial mechanism of a bio-based green composite antibacterial agent;
FIG. 2 is an infrared spectrum of the bio-based Schiff base prepared in examples 1-5;
FIG. 3 is a graph of the antimicrobial properties of bio-based Schiff base prepared in examples 1-5;
wherein a is an escherichia coli detection chart, and b is a staphylococcus aureus detection chart;
FIG. 4 is a schematic diagram of the curves of the bio-based Schiff base antimicrobial TG prepared in examples 1-5;
FIG. 5 is a graph of the antimicrobial properties of a bio-based Schiff base containing antimicrobial film against Staphylococcus aureus;
FIG. 6 is a schematic diagram of a DSC curve of an antimicrobial film containing bio-based Schiff base;
FIG. 7 is the mechanical properties of the antimicrobial film;
wherein a is a tensile strength schematic diagram, and b is an elongation at break schematic diagram.
Detailed Description
The present invention is further illustrated and described below with reference to examples, which are not intended to be limiting in any way. Unless otherwise indicated, the methods and apparatus used in the examples were conventional in the art and the starting materials used were all conventional commercially available.
The specific structures of tryptophan, cysteine, tyrosine, threonine and phenylalanine are used in this example as follows:
example 1
The embodiment provides a method for preparing a bio-based green composite antibacterial agent by taking vanillin and tryptophan as raw materials, which comprises the following steps:
S1.5 mmol of tryptophan and 5mmol of potassium hydroxide are dissolved in 40mL of ethanol, condensed and refluxed for 30 minutes at 60 ℃, and the mixed liquid is colorless and transparent and cooled to room temperature;
S2, slowly dripping the mixed liquid into 25mL of ethanol solution containing 5mmol of vanillin, performing reaction for two hours, steaming the redundant solvent in a rotary way, recrystallizing, and drying at 80 ℃ for 3 hours to obtain orange powder, namely the bio-based green composite antibacterial agent, which is named as Trp.SB.
Example 2
The embodiment provides a method for preparing a bio-based green composite antibacterial agent by taking vanillin and cysteine as raw materials, which comprises the following steps:
s1.5 mmol of cysteine and 5mmol of potassium hydroxide are dissolved in 40mL of ethanol, condensed and refluxed for 30 minutes at 60 ℃, and the mixed liquid is colorless and transparent and then cooled to room temperature;
S2, slowly dripping the mixed liquid into 25mL of ethanol solution containing 5mmol of vanillin, performing reaction for two hours, steaming the redundant solvent in a rotary way, recrystallizing, and drying at 80 ℃ for 3 hours to obtain light orange powder, namely the bio-based green composite antibacterial agent, and naming the Cys.SB.
Example 3
The embodiment provides a method for preparing a bio-based green composite antibacterial agent by taking vanillin and tyrosine as raw materials, which comprises the following steps:
S1.5 mmol of tyrosine and 5mmol of potassium hydroxide are dissolved in 55mL of ethanol, condensed and refluxed for 30 minutes at 60 ℃, and the mixed liquid is cooled to room temperature after being milky white;
S2, slowly dripping the mixed liquid into 25mL of ethanol solution containing 5mmol of vanillin, performing reaction for two hours, steaming the redundant solvent in a rotary way, recrystallizing, and drying at 80 ℃ for 3 hours to obtain brown powder, namely the bio-based green composite antibacterial agent, and naming the green composite antibacterial agent as Tyr.
Example 4
The embodiment provides a method for preparing a bio-based green composite antibacterial agent by taking vanillin and threonine as raw materials, which comprises the following steps:
S1.5 mmol of threonine and 5mmol of potassium hydroxide are dissolved in 40mL of ethanol, condensed and refluxed for 30 minutes at 60 ℃, and the mixed liquid is colorless and transparent and cooled to room temperature;
S2, slowly dripping the mixed liquid into 25mL of ethanol solution containing 5mmol of vanillin, performing reaction for two hours, steaming the redundant solvent in a rotary way, recrystallizing, and drying at 50 ℃ for 3 hours to obtain golden powder, namely the bio-based green composite antibacterial agent, which is named as Thr.SB.
Example 5
The embodiment provides a method for preparing a bio-based green composite antibacterial agent by taking vanillin and phenylalanine as raw materials, which comprises the following steps:
S1.5 mmol of phenylalanine and 5mmol of potassium hydroxide are dissolved in 40mL of ethanol, condensed and refluxed for 30 minutes at 60 ℃, and the mixed liquid is colorless and transparent and then cooled to room temperature;
s2, slowly dripping the mixed liquid into 25mL of ethanol solution containing 5mmol of vanillin, performing reaction for two hours, steaming the redundant solvent in a rotary way, recrystallizing, and drying at 80 ℃ for 3 hours to obtain yellow powder, namely the bio-based green composite antibacterial agent, which is named as Phe.SB.
Example 6
The embodiment provides a preparation method of an antibacterial film containing bio-based Schiff base, which comprises the following steps:
4.5g of PVA is fully dissolved in 90g of deionized water, 0.045g of bio-based green composite antibacterial agent and 0.9g of glycerol are added into the film liquid according to 1% and 20% of PVA mass, the film liquid is heated and dissolved for 1 hour at 90 ℃ to obtain uniform solution, the film is cast and formed, and the film is dried for 5 hours at 80 ℃ to obtain the antibacterial film.
PVA/Trp.SB, PVA/Cys.SB, PVA/Tyr.SB, PVA/Thr.SB and PVA/Phe.SB antimicrobial films were obtained as described above using Trp.SB, cys.SB, tyr.SB, thr.SB and Phe.SB prepared in examples 1-5, respectively.
Experimental example
1. Infrared spectrum detection of bio-based green composite antibacterial agent
As can be seen from FIG. 2, trp.SB, cys.SB, tyr.SB, thr.SB and Phe.SB were all synthesized successfully by the method of the present invention. And, the yields of the bio-based green composite antibacterial agents prepared in examples 1 to 5 are shown in the following table 1:
TABLE 1
| Trp.SB | Cys.SB | Tyr.SB | Thr.SB | Phe.SB | |
| Weight of product (g) | 1.8756 | 1.5027 | 1.7963 | 1.5265 | 1.6930 |
| Yield (%) | 91 | 91 | 92 | 93 | 91 |
2. Antibacterial performance detection of bio-based green composite antibacterial agent
The bio-based green composite antibacterial agents prepared in examples 1 to 5 were subjected to antibacterial activity tests on escherichia coli and staphylococcus aureus representing gram-negative bacteria and gram-positive bacteria, respectively, and the results are shown in table 2:
TABLE 2
As can be seen from table 2 and fig. 3, in the zone of inhibition test, the diameter of the zone of inhibition is related to the sensitivity of the microorganism to the antimicrobial agent, and generally the larger the zone of inhibition, the better the antimicrobial performance. The bio-based green composite antibacterial agent prepared by the invention has obvious antibacterial effect on colibacillus and staphylococcus aureus representing gram-negative bacteria and gram-positive bacteria, and has better antibacterial performance of Trp.SB, tyr.SB and Phe.SB, and the diameter of a bacteriostasis ring is slightly larger than that of Cys.SB and Thr.SB.
3. Thermal performance detection of bio-based green composite antimicrobial
The bio-based green composite antibacterial agents prepared in examples 1 to 5 were subjected to thermal stability detection, and the detection results are shown in table 3:
TABLE 3 Table 3
| Trp.SB | Cys.SB | Tyr.SB | Thr.SB | Phe.SB | |
| T5％(℃) | 183 | 203 | 151 | 169 | 182 |
| T10％(℃) | 227 | 225 | 167 | 183 | 223 |
| T50％(℃) | 560 | 579 | 490 | 695 | 616 |
As can be seen from Table 3 and FIG. 4, among the five Schiff bases synthesized by the present invention, the initial decomposition temperature was higher and more stable.
4. Antibacterial property detection of antibacterial film
As can be seen from FIG. 5, bacteria still grow on the film without the antimicrobial agent, and no test bacteria grow in the coverage area of the film with the antimicrobial agent added, and only no bacteria grow in the coverage area. The film added with the antibacterial agent can well play the antibacterial effect, and the migration amount of the antibacterial agent in the film in the solid culture medium is insufficient to inhibit the growth of the tested strain, even the migration is probably not generated, so that the film has better biocompatibility.
5. Thermal performance detection of antimicrobial films
As can be seen from fig. 6, the melting point was slightly lowered after the antibacterial agent was added to the PVA film, which indicates that the crystallization regularity of the film to which the antibacterial agent was added was lowered, and the melting peak was increased, which indicates that the crystallinity of the film was increased, as compared with the pure PVA film.
6. Moisture permeability detection of antibacterial film
The five antibacterial films were subjected to perspective performance test, and the test results are shown in table 4 below:
TABLE 4 Table 4
The water vapor transmission capacity (WVT) is an important parameter of the fresh-keeping capability of the packaging film, and as shown in table 4, trp.sb, cys.sb, tyr.sb, thr.sb and phe.sb have larger moisture absorption due to the carboxyl and potassium ions in the packaging film, the polarity of the materials is improved to different degrees, the moisture permeability of PVA is improved, and the condensation is effectively prevented, so that the condensation in the packaging film is prevented from providing a natural temperature bed for the growth and propagation of microorganisms, and the improvement of the moisture permeability enhances the antibacterial performance of the packaging to a certain extent.
7. Mechanical property detection of antibacterial film
By taking the pure PVA film as a control group, the tensile strength and the mechanical property of the elongation at break of the antibacterial film are detected, and as can be seen from fig. 7, the tensile strength of the film added with the antibacterial agent is improved to a certain extent compared with the PVA film without the antibacterial agent, and the use requirements are met.
Application example
Five antibacterial films were used to seal and package commercially available cherry tomatoes, and the cherry tomatoes were stored under the same conditions, and the appearance changes and weight loss changes of the cherry tomatoes during storage were recorded, and the results are shown in the following table 5 appearance changes and table 6 weight loss rates:
TABLE 5
Wherein, the color and hardness are expressed by grades, 5 is the best, and the color and hardness are reduced in sequence. Representing that spoilage has occurred, and is not evaluated.
TABLE 6
| Film-free | PVA | PVA/Trp.SB | PVA/Cys.SB | PVA/Tyr.SB | PVA/Thr.SB | PVA/Phe.SB | |
| Day 1 (%) | — | — | — | — | — | — | — |
| Day 2 (%) | 3.75 | — | — | — | — | — | — |
| Day 3 (%) | 8.72 | — | — | — | — | — | — |
| Day 5 (%) | 10.33 | 2.12 | — | — | — | — | — |
| Day 7 (%) | — | 6.97 | 4.32 | 4.12 | 3.68 | — | — |
| Day 9 (%) | — | 9.36 | 6.78 | 6.45 | 6.12 | — | — |
| Day 11 (%) | — | — | 7.98 | 7.54 | 7.33 | 4.87 | 4.53 |
| Day 13 (%) | — | — | 8.87 | 8.64 | 8.34 | 6.37 | 5.92 |
| Day 15 (%) | — | — | 8.98 | 8.88 | 8.55 | 7.56 | 7.12 |
Wherein-the changes and their faint or spoiled changes are not evaluated.
In the process of storing cherry tomatoes, the skin of the cherry tomatoes is fragile and the cherry tomatoes breathes, so that the moisture loss is caused after the skin is broken, and the cherry tomatoes provide needed nutrients for the growth of bacteria and fungi. As can be seen from tables 5 and 6, the antibacterial film of the present invention reduces the contact of cherry tomatoes with external air to some extent, and the film added with the bio-based Schiff base antibacterial agent can effectively prevent the growth of bacterial colonies, and can directly inhibit the growth of bacteria even in the case that cherry tomatoes are ruptured and juice flows out, compared with the film without the bio-based Schiff base antibacterial agent, the antibacterial film package used in the present invention prolongs the shelf life of cherry tomatoes by 2 to 4 days.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (4)
1. An antibacterial packaging material containing bio-based Schiff base is characterized in that the raw materials comprise a packaging material matrix and a bio-based green composite antibacterial agent, wherein the bio-based green composite antibacterial agent comprises vanillin and amino acid, the amino acid comprises one or more of tryptophan, cysteine, tyrosine, threonine and phenylalanine, the vanillin and the amino acid are prepared into the bio-based green composite antibacterial agent through Schiff base reaction,
The preparation method comprises the following steps:
S1, dissolving amino acid in an alkaline organic solvent, heating to 50-80 ℃, reacting for 0.5-1 h until the mixed liquid is colorless and transparent, and cooling;
S2, dripping the colorless and transparent mixed liquid in the S1 into an organic solvent containing vanillin, reacting for 1-3 hours, recrystallizing, and drying to obtain the bio-based green composite antibacterial agent;
s3, carrying out solution blending, melt blending or coating on the packaging material matrix and the bio-based green composite antibacterial agent to prepare a film so as to obtain the bio-based green composite antibacterial packaging material;
The addition amount of the bio-based green composite antibacterial agent is 1% of the mass of the packaging material matrix.
2. The antimicrobial packaging material comprising a biobased schiff base according to claim 1, wherein the molar ratio of vanillin to amino acid is 1:0.1-10.
3. The antibacterial packaging material containing bio-based schiff base according to claim 1, wherein the organic solvent in step S1 is methanol or ethanol.
4. The antimicrobial packaging material containing bio-based schiff base according to claim 1, wherein the film forming mode comprises casting, solution film forming, coating, co-extrusion, melt blown film or melt tabletting film forming.
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