CN116039199B - ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material and preparation method thereof - Google Patents
ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material and preparation method thereof Download PDFInfo
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- CN116039199B CN116039199B CN202310060336.6A CN202310060336A CN116039199B CN 116039199 B CN116039199 B CN 116039199B CN 202310060336 A CN202310060336 A CN 202310060336A CN 116039199 B CN116039199 B CN 116039199B
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- film
- solution
- caprolactone
- sio
- polyvinyl alcohol
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Classifications
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Abstract
The invention provides a ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material and a preparation method thereof, and belongs to the technical field of antibacterial materials. The composite material is a film with a two-layer structure; the structure of the layer is a poly epsilon-caprolactone film containing SiO 2 nano particles; the other layer of structure is a polyvinyl alcohol/quaternized chitosan film containing zeolite imidazole ester framework material; the zeolite imidazole ester framework material contains a photosensitizer. The composite material has high tensile strength and good hydrophobicity, can reduce the transmission of ultraviolet light, and can well inhibit the growth and adhesion of bacteria. The anti-microbial food preservative can be used as an anti-microbial food packaging material or a preservative film, and can prevent food from being polluted by microorganisms and isolate damage of ultraviolet rays to the food. In addition, the composite material provided by the invention is biodegradable, green and environment-friendly, accords with the current thought of green development, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material and a preparation method thereof.
Background
Food-borne diseases are a serious public health problem that is recognized worldwide. Pathogenic bacterial contamination and uncontrolled growth of planktonic microorganisms are one of the main causes of food spoilage. Food preservative films are effective barriers for isolating microbial contamination, and therefore, there is a great deal of attention to packaging materials with efficient sterilization. In daily life, polyethylene materials, petroleum-based materials or inherent antibacterial polymers are mostly used for preserving foods. However, in the preservation of foods, direct contact of a single active agent with the foods only exhibits short-term antimicrobial effects, which is detrimental to long-term preserved foods; in the process of heating food and preservative film together, the preservative film which is not heat-resistant, poor in ultraviolet resistance or low in safety can decompose harmful substances into the food to damage the nutrient substances of the food, so that the preservative film has a certain influence on the health of people; in addition, the degradation speed of petroleum-based materials is low, the irreversible damage to the environment caused by plastic garbage incineration is not edible, the biocompatibility is poor, and the like, which is a problem to be solved urgently at present.
Poly epsilon-caprolactone (PCL) is a low melting point polymer obtained by ring opening polymerization of epsilon-caprolactone. Due to its low toxicity, low cost, good hydrophobicity and excellent elongation, it is widely used in food preservative films. In addition, it is also a biodegradable material approved by the Food and Drug Administration (FDA) and can be completely decomposed by microorganisms in both anaerobic and aerobic environments, however, because it is thermolabile, melting occurs only at 60 ℃, and food is not suitable to be heated together with a preservative film, which shortens the application range of the material. Polyvinyl alcohol (PVA) has excellent chemical resistance and good mechanical properties and is widely used in pharmaceuticals, industrial fields, and food packaging. In addition, the biodegradable PVA film is a novel plastic product in internationally brand-new corner, can be completely degraded into CO 2 and H 2 O by utilizing two degradation characteristics of viscosity, film forming property, water and biology of PVA, and is a real environment-friendly high-new environment-friendly packaging material. However, PVA and PCL do not have antibacterial performance, and can not effectively block microorganisms from polluting foods.
The patent application with publication number CN102101928A discloses an antibacterial preservative film, which is added with silver ion antibacterial agent, so that the preservative film has antibacterial function. Patent application publication No. CN101824177A discloses a special-effect antibacterial PE (polyethylene) preservative film, wherein a glass carrier silver ion antibacterial agent is added into PE to obtain the antibacterial preservative film with good and durable antibacterial performance. However, these antibacterial preservative films use antibacterial agents to perform antibacterial action, which may cause drug resistance to bacteria and cannot effectively remove the bacteria. Meanwhile, the antibacterial preservative films have ultraviolet resistance, and can not prevent ultraviolet rays from damaging food and damaging food proteins to influence the edibility of the food when the food and packaging materials are heated together by microwave ultraviolet rays.
Therefore, developing a film which has high efficiency, is antibacterial, ultraviolet resistant and biodegradable has great potential in the application of food packaging materials.
Disclosure of Invention
The invention aims to provide a ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material and a preparation method thereof.
The invention provides a multifunctional composite material which is a film with a two-layer structure; the structure of the layer is a poly epsilon-caprolactone film containing SiO 2 nano particles; the other layer of structure is a polyvinyl alcohol/quaternized chitosan film containing zeolite imidazole ester framework material;
the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight: 50-60 parts of polyvinyl alcohol, 1-10 parts of zeolite imidazole ester framework material, 20-30 parts of quaternized chitosan and 10-15 parts of glycerol;
The zeolite imidazole ester framework material contains a photosensitizer.
Further, the mass fraction of SiO 2 nano particles in the poly epsilon-caprolactone film containing SiO 2 nano particles is 0.5-5%; preferably 1%.
Further, the preparation method of the poly epsilon-caprolactone film containing the SiO 2 nano particles comprises the following steps:
And (3) dissolving the poly epsilon-caprolactone in an organic solvent, adding SiO 2 nano particles, stirring, casting the suspension on a hot glass plate, evaporating the organic solvent, and drying to obtain the product.
Further, the number average molecular weight of the poly epsilon-caprolactone is 80000MW to 100000MW; preferably 80000MW;
And/or the particle size of the SiO 2 nano-particles is 10-20 nm; preferably 20nm;
and/or the organic solvent is dichloromethane or N, N-dimethylformamide;
And/or, dissolving the poly epsilon-caprolactone in an organic solvent, performing ultrasonic treatment for 30-60 min, and then adding SiO 2 nano particles;
And/or, stirring when adding SiO 2 nano-particles;
and/or the temperature of the hot glass plate is 40-60 ℃; preferably 40 ℃;
and/or drying at 30-40 deg.c in vacuum.
Further, the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight: 50 parts of polyvinyl alcohol, 1-8 parts of zeolite imidazole ester framework material, 20 parts of quaternized chitosan and 12 parts of glycerol;
And/or the mass of the zeolite imidazole ester framework material is 5-40% of that of poly epsilon-caprolactone;
Preferably, the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight: 50 parts of polyvinyl alcohol, 8 parts of zeolite imidazole ester framework material, 20 parts of quaternized chitosan and 12 parts of glycerol;
and/or the mass of the zeolite imidazole ester framework material is 40% of that of poly epsilon-caprolactone.
Further, the preparation method of the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material comprises the following steps:
(1) Dissolving polyvinyl alcohol in a solvent to obtain a polyvinyl alcohol solution;
(2) Dispersing a zeolite imidazole ester framework material in a medium to obtain a suspension;
(3) Mixing the polyvinyl alcohol solution of step (1) and the suspension of step (2) to form a dispersion A;
(4) Dissolving quaternized chitosan and glycerol in a solvent to form a solution B;
(5) Adding the dispersion A in the step (3) into the solution B in the step (4) to obtain a film-forming solution;
(6) And (5) forming a film by the film forming solution in the step (5), and drying to obtain the film.
Further, the method comprises the steps of,
In the step (1), the solvent is water;
and/or, in the step (1), the concentration of the polyvinyl alcohol solution is 1-5%;
And/or, in the step (2), the medium is an ethanol aqueous solution;
and/or, in the step (2), the concentration of the zeolite imidazole ester framework material in the suspension is 0.1-0.8%;
and/or, in the step (4), the solvent is water;
And/or in the step (4), the concentration of the quaternized chitosan in the solution B is 1-5%;
and/or, in step (6), the drying is vacuum drying;
Preferably, the method comprises the steps of,
In the step (1), the concentration of the polyvinyl alcohol solution is 5%;
And/or, in the step (2), the concentration of the ethanol water solution is 40% -50%;
and/or, in step (2), the concentration of zeolitic imidazolate framework material in the suspension is 0.8%;
And/or, in the step (4), the concentration of quaternized chitosan in the solution B is 2%;
And/or in the step (6), the temperature of the vacuum drying is 60-80 ℃ and the drying time is 1-5 h.
Further, the preparation method of the zeolite imidazole ester framework material containing the photosensitizer comprises the following steps:
1) Dissolving zinc nitrate hexahydrate in a solvent;
2) Dissolving dimethylimidazole and a photosensitizer in a solvent;
3) Adding the solution obtained in the step 1) into the solution obtained in the step 2), stirring, aging, centrifuging, washing and drying to obtain the product;
Preferably, the method comprises the steps of,
The mass ratio of the zinc nitrate hexahydrate in the step 1) to the dimethylimidazole and the photosensitizer in the step 2) is 15-20: 30-40: 1, a step of; preferably 15:30:1, a step of;
and/or, in step 1), the solvent is methanol;
And/or, in the step 2), the solvent is methanol;
more preferably, in step 2), the photosensitizer is manassam red.
Preferably, in the multifunctional composite material, the thickness of the poly epsilon-caprolactone film containing SiO 2 nano particles is 4-5 mu m, and the thickness of the polyvinyl alcohol/quaternized chitosan film containing zeolite imidazole ester framework material is 15-16 mu m; the total thickness of the multifunctional composite material is about 20 mu m.
The invention also provides a method for preparing the multifunctional composite material, which comprises the following steps:
A. Preparing a poly epsilon-caprolactone film containing SiO 2 nano particles according to the preparation method;
B. Preparing a film forming solution according to the preparation method;
C. Casting the film forming solution in the step B onto the poly epsilon-caprolactone film containing the SiO 2 nano particles in the step A to form a film, and drying to obtain the film;
Preferably, in step C, 10mL of film-forming solution is cast onto each 200 to 250 square centimeters of the poly epsilon-caprolactone film containing SiO 2 nanoparticles.
The invention also provides application of the multifunctional composite material in preparing food packaging materials and/or preservative films.
The invention designs and synthesizes a photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material based on ZIF-8 through a simple and environment-friendly casting method, PCL and PVA-QCS are used as a composite film matrix, and 1% (w/w) SiO 2 nano particles are added into a PCL layer to enhance the hydrophobicity and ultraviolet resistance; an antibacterial photosensitizer RB@ZIF-8 nano particle is embedded in the PVA-QCS layer, and active oxygen is generated to kill bacteria under the irradiation of green light (525 nm) so as to exert the photodynamic antibacterial effect. Finally synthesizing the PCL-SiO 2/PVA-QCS-RB@ZIF-8 composite film, namely PQZ.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention provides a ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material as a preservative film, wherein all raw materials are easy to obtain in the natural world, and the preservative film is good in biocompatibility, safe, reliable, biodegradable and environment-friendly. Therefore, the composite material obtained by the invention has the same biodegradability and is environment-friendly.
2. The PCL single film is not suitable for high-temperature materials, melts at 60 ℃, combines with PVA, can improve the defect of thermolabile property, and furthermore, siO 2 NPs are introduced into the PCL to provide a solid foundation for the ultraviolet resistance of the composite film.
3. The photosensitizer of the invention has poor stability and low bioavailability of the manassantin, and the manassantin is encapsulated in ZIF-8 by adopting a one-pot method, so that the encapsulation efficiency is high, and the stability and the bioavailability of the manassantin are improved.
4. Traditional antibacterial preservative films can generate drug resistance to bacteria and cannot effectively eliminate the bacteria. The invention combines photodynamic therapy to kill bacteria, can effectively sterilize, prevent drug-resistant bacteria from appearing and prevent bacterial biofilm from forming.
5. The invention adopts a simple casting method to prepare the composite film, and the method is simple, efficient and quick, and saves resources and cost.
6. The composite film has good antibacterial property, excellent film forming property and mechanical property and good waterproof property, can prevent microbial pollution and keeps food fresh.
In conclusion, the invention provides the ZIF-8-based photodynamic antibacterial ultraviolet-resistant biodegradable multifunctional composite material which has high tensile strength and good hydrophobicity, can reduce ultraviolet light transmission, and can well inhibit bacterial growth and adhesion. The anti-microbial food preservative can be used as an anti-microbial food packaging material or a preservative film, and can prevent food from being polluted by microorganisms and isolate damage of ultraviolet rays to the food. In addition, the composite material provided by the invention is biodegradable, green and environment-friendly, accords with the current thought of green development, and has a good application prospect.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a schematic view showing the appearance of the composite materials prepared in examples 1 to 4 and comparative example 1 according to the present invention; wherein a is PQZ 0; b is PQZ 1; c is PQZ 2; d is PQZ 3; e is PQZ 4.
Fig. 2 is a stress-strain curve of the P layer and PQZ 4 film.
Fig. 3 shows the contact angle test results for each film: wherein a is a pure PCL layer; b is a P layer; c is QZ; d is PQZ 0; e is PQZ 1; f is PQZ 2; g is PQZ 3; h is PQZ 4.
FIG. 4 is an ultraviolet-visible spectrum of each film.
Figure 5 shows the survival of bacteria on each composite membrane: wherein A is E.coli; b is Staphylococcus aureus S.aureus.
FIG. 6 shows antibacterial adhesion results for each composite film: wherein A is E.coli; b is Staphylococcus aureus S.aureus.
FIG. 7 shows the plasticity results of PQZ 4 films.
FIG. 8 shows the results of heat resistance studies of the respective films.
Detailed Description
The materials and equipment used in the embodiments of the present invention are all known products and are obtained by purchasing commercially available products.
The specific implementation method comprises the following steps: the photosensitizer is Bengalhong; the number average molecular weight of the polyvinyl alcohol is 57000-66000MW, and the viscosity is 20.0-30.0mPa; the degree of substitution of Quaternized Chitosan (QCS) was 95%, purchased from shanghai maclin biochemical technologies limited; the plasticizer is glycerol. The particle size of the nano silicon dioxide is 20nm; the number average molecular weight of the poly epsilon-caprolactone was 80000MW.
Example 1 preparation of multifunctional composite Material according to the invention
1. Preparation of RB@ZIF-8 nanoparticles
0.15G of zinc nitrate hexahydrate (zinc nitrate hexahydrate) was dissolved in 5mL of methanol solution, 0.3g of dimethylimidazole (2-methylimidazole) and 10mg of Bengalia (RB) were dissolved in 10 milliliters (mL) of methanol, then a zinc nitrate solution was added to the above solution, and after stirring for 3 minutes, the solution was clarified to become a rose bengal suspension. At this point RB@ZIF-8 nanoparticles were formed. After stirring for 30min, the product was aged overnight, centrifuged at 6000rpm for 5min, then washed with methanol solution for 3 times, and the washed sample was dried overnight under vacuum at 37℃to finally obtain the product RB@ZIF-8 nanoparticles.
2. Preparation of PCL-SiO 2 outer film
The invention adopts an environment-friendly and simple casting method to prepare the composite film. Briefly, 200mg of particles of poly epsilon-caprolactone (PCL) were dissolved in 16mL of methylene chloride, stirred after 30 minutes of sonication, 2mg of SiO 2 nanoparticles were added to the stirring, and after stirring for 1 hour, the suspension was cast on a hot plate glass (15X 15cm 2 round glass plate) at 40℃and the solvent was allowed to evaporate for more than 30 minutes. Finally, the film was dried in vacuo at 30 ℃ and used for subsequent experiments, this film being designated P-layer.
3. Preparation of PVA-QCS-RB@ZIF-8 inner membrane solution and preparation of PQZ 1 composite membrane
0.5G of polyvinyl alcohol (PVA) was added to 10mL of distilled water, and the mixture was stirred at 95℃for 2 hours to dissolve, thereby preparing a PVA solution having a concentration of 5%, and then the solution was cooled to room temperature for use.
10Mg of RB@ZIF-8 nanoparticles were weighed according to W RB@ZIF-8：WPCL =5%, and the RB@ZIF-8 nanoparticles were dispersed in 10mL of a 40vol% ethanol-water mixed solution to form a RB@ZIF-8 suspension, and the suspension was mixed with a PVA solution to form a dispersion A.
0.20G of Quaternized Chitosan (QCS) and 0.12g of glycerol were dissolved in 10mL of deionized water to form solution B. Finally, dispersion a was added to solution B and stirred at room temperature overnight to make a film solution.
10ML of the film-forming solution was cast onto the above P layer to form a composite film. Finally, the composite film is dried in vacuum at 60 ℃ for 3 hours, the dried composite film (PQZ 1) is peeled off from the glass plate, and the composite film is stored in a vacuum drying oven at 30 ℃ for subsequent property study.
EXAMPLE 2 preparation of multifunctional composite Material according to the invention
1. Preparation of RB@ZIF-8 nanoparticles
As in example 1.
2. Preparation of PCL-SiO 2 outer film
As in example 1.
3. Preparation of PVA-QCS-RB@ZIF-8 inner membrane solution and preparation of PQZ 2 composite membrane
Prepared as in example 1, except that the mass ratio of rb@zif-8 nanoparticles to PCL was changed, W RB@ZIF-8：WPCL =10%, i.e. 20mg of rb@zif-8 nanoparticles were weighed. The composite film prepared was PQZ 2.
EXAMPLE 3 preparation of multifunctional composite Material according to the invention
1. Preparation of RB@ZIF-8 nanoparticles
As in example 1.
2. Preparation of PCL-SiO 2 outer film
As in example 1.
3. Preparation of PVA-QCS-RB@ZIF-8 inner membrane solution and preparation of PQZ 3 composite membrane
Prepared as in example 1, except that the mass ratio of rb@zif-8 nanoparticles to PCL was changed, W RB@ZIF-8：WPCL =20%, 40mg of rb@zif-8 nanoparticles were weighed. The composite film prepared was PQZ 3.
EXAMPLE 4 preparation of multifunctional composite Material according to the invention
1. Preparation of RB@ZIF-8 nanoparticles
As in example 1.
2. Preparation of PCL-SiO 2 outer film
As in example 1.
3. Preparation of PVA-QCS-RB@ZIF-8 inner membrane solution and preparation of PQZ 4 composite membrane
Prepared as in example 1, except that the mass ratio of rb@zif-8 nanoparticles to PCL was changed, W RB@ZIF-8：WPCL =40%, 80mg of rb@zif-8 nanoparticles were weighed. The composite film prepared was PQZ 4.
Preparation of a composite film cross section: taking a film with the thickness of 2 multiplied by 2cm 2, obtaining a cross section through brittle fracture under liquid nitrogen, and detecting the cross section under a scanning electron microscope to obtain the thickness of the film. The cross-section of the P layer and PQZ 4 film was measured by Scanning Electron Microscopy (SEM), and found to be about 4.4 μm for the P layer, about 15.2 μm for the film layer, and about 20 μm for the total film thickness.
Comparative example 1 preparation of composite Material
1. Preparation of RB@ZIF-8 nanoparticles
As in example 1.
2. Preparation of PCL-SiO 2 outer film
As in example 1.
3. Preparation of PVA-QCS-RB@ZIF-8 inner membrane solution and preparation of PQZ 0 composite membrane
Prepared according to the method of example 1, only changing the mass ratio of rb@zif-8 nanoparticles to PCL, W RB@ZIF-8：WPCL =0%, i.e. weighing 0mg of rb@zif-8 nanoparticles. The composite film prepared was PQZ 0.
The beneficial effects of the present invention are demonstrated by specific test examples below.
Test example 1 appearance of multifunctional composite Material according to the invention
The composite films prepared in examples 1-4 and comparative example 1 were overlaid on the text, and the results were observed and photographed, as shown in fig. 1. As can be seen from fig. 1: the composite film prepared by the invention has good light transmittance, and along with the increase of the addition amount of the RB@ZIF-8 nano particles, the rose color of the composite film is gradually deepened, and the light transmittance is still good.
Test example 2 mechanical properties of multifunctional composite materials of the invention and test of contact angle with Water
The mechanical properties of the films (P layer prepared in example 1 and PQZ 4 prepared in example 4) were measured according to ISO 527-3 using a universal tester. The film was cut into 5cm by 2cm strips and run in a stretching mode with a crosshead speed of 30mm/min. At least 10 samples were tested per group.
In addition, the hydrophobicity of the films (pure PCL layer, P layer prepared in example 1, QZ, examples 1 to 4 and PQZ 0～PQZ4 prepared in comparative example 1) was analyzed using a contact angle meter (Shanghai Chen digital technology instruments Co., ltd., china). Each sample was tested 5 times in duplicate.
The preparation method of the pure PCL layer comprises the following steps: 200mg of particles of poly epsilon-caprolactone (PCL) were dissolved in 16mL of methylene chloride, stirred after 30 minutes of sonication, and after stirring for 1 hour, the solution was cast on a hot plate glass at 40℃and the solvent was allowed to evaporate for more than 30 minutes. Finally, the film was dried in vacuo at 30 ℃ and used for subsequent experiments, the film being a pure PCL film.
The preparation method of QZ comprises the following steps: 0.5g of polyvinyl alcohol (PVA) was added to 10mL of distilled water, and the mixture was stirred at 95℃for 2 hours to dissolve, thereby preparing a PVA solution having a concentration of 5%, and then the solution was cooled to room temperature for use. 80mg of RB@ZIF-8 nanoparticles (prepared as in example 1) were dispersed in 10mL of a 40vol% ethanol-water mixed solution to form a RB@ZIF-8 suspension, which was then mixed with the PVA solution to form dispersion A.
0.20G QCS and 0.12g glycerol were dissolved in 10mL deionized water to form solution B. Finally, dispersion a was added to solution B and stirred at room temperature overnight to make a film solution. The film-forming solution was cast onto a glass plate at room temperature. Finally, the composite film was vacuum dried at 60 ℃ for 3 hours, the dried film (QZ) was peeled off from the glass plate, and stored in a vacuum oven at 30 ℃ for subsequent property studies.
Fig. 2 is a stress-strain curve of the P layer and PQZ 4 film. As can be seen from fig. 2: the composite film has good elongation at break of a single-layer film, improves the tensile strength of the film, and has good mechanical property for food preservation, wherein the tensile strength of the composite film can reach 43.4 MPa.
Fig. 3 shows the contact angle test results of each film. As can be seen from fig. 3: the P layer film with SiO 2 NPs added has a larger water contact angle than the pure PCL film by about 105 degrees, which shows that the P layer film has stronger water pollution isolation capability. However, for the photodynamic antibacterial layer, the water contact angle of the QZ layer is only about 70 °, and after modification into a composite film, the water contact angle increases. And the water contact angle is slightly improved along with the increase of the content of RB@ZIF-8 NPs. This is probably due to the increased roughness of the QZ layer by the RB@ZIF-8NPs, which increases its hydrophobic properties. Therefore, the composite film has good waterproof capability.
Test example 3 test of the ultraviolet resistance effect of the multifunctional composite Material of the present invention
Ultraviolet radiation (200-400 nm) is one of the important factors responsible for food deterioration, so that it is necessary to study ultraviolet resistance. The films (pure PCL layer, P layer prepared in example 1, QZ, examples 1 to 4 and PQZ 0～PQZ4 prepared in comparative example 1, pure PCL layer and QZ preparation method were cut into films of 3X 5cm 2 as in test example 2) and were obtained by testing at 200 to 800nm using an ultraviolet-visible spectrophotometer.
As shown in FIG. 4, the transmittance of pure PCL, QZ, P and PQZ 0 in visible light (400-800 nm) is more than 95%, and the pure PCL and QZ have almost no blocking ability in the ultraviolet region. However, P and PQZ 0 have a tendency to decrease in UV light transmission, which suggests that SiO 2 NPs have some UV blocking capability. As the content of the RB@ZIF-8NPs is gradually increased, the ultraviolet transmittance is continuously reduced, which indicates that the RB@ZIF-8NPs also have certain ultraviolet blocking capability. Therefore, the composite film has certain ultraviolet radiation resistance and has potential application in preparing ultraviolet radiation resistant packaging materials.
Test example 4 test of the antibacterial Effect of the multifunctional composite Material of the present invention
The antibacterial ability of the composite films (examples 1 to 4 and PQZ 0～PQZ4 prepared in comparative example 1) was measured by a plate count method by selecting two representative bacteria of E.coli and S.aureus. A film cut into 2X2cm 2 was first irradiated with ultraviolet radiation for 30min to remove bacteria from the surface, and then 100. Mu.L of a bacterial suspension (1X 10 6 CFU/mL) was dropped onto the film surface. After 60min of irradiation with green light 525nm,2.2mW/cm 2, 10. Mu.L of the bacterial suspension was taken in a solid LB medium and cultured overnight in a constant temperature incubator at 37℃to examine the antibacterial property. Green light irradiation was not used as a control.
To further examine the antibacterial adhesion properties of the composite films (examples 1 to 4 and PQZ 0～PQZ4 prepared in comparative example 1), each film was contaminated with bacteria and irradiated with green light (525 nm,2.2mW/cm 2) for 30min by the above method, and then the film was taken out and washed three times with sterile buffered saline to remove unattached bacteria. Next, after the film was sonicated in sterile water, 10. Mu.L of the solution was incubated overnight in a constant temperature incubator at 37℃and the anti-adhesion ability of the film was measured by plate counting. Green light irradiation was not used as a control.
As shown in fig. 5: after 60min of green light radiation, the sterilizing rate of the composite film on two bacteria is correspondingly increased gradually along with the gradual increase of the RB@ZIF-8NPs content, which shows that the composite film can generate active oxygen for sterilizing bacteria under the green light radiation, and the PDT effect is exerted. Furthermore, for PQZ 4 composite membranes, the survival rate for E.coli is only about 5%, whereas Staphylococcus aureus can be nearly completely killed (100%). In the non-green irradiated group, the trend of the composite membrane for antibiosis was similar to that of the illuminated group, probably due to the fact that ZIF-8 can release metal ions (Zn 2+) to damage cell membranes to kill bacteria. In addition, ZIF-8 pH responsive released 2-MIM is also a good antimicrobial factor. Under the same operation, PQZ composite membranes have slight differences in the killing effect on two bacteria. Since gram-negative bacteria have cell walls, the penetration of antimicrobial factors is slightly lower, which is different from gram-positive staphylococcus aureus monolayer cell membranes. So that the staphylococcus aureus has lower tolerance to active oxygen than the escherichia coli.
As shown in fig. 6: as the RB@ZIF-8NPs content in the composite film increases, the adhesion of bacteria on the composite film gradually decreases regardless of the presence or absence of green light. Has good antibacterial adhesion capability. This is probably due to the antibacterial factor released by ZIF-8 being resistant to bacterial adhesion. In addition, the chitosan quaternary ammonium salt with positive points in the composite film has a certain disinfection effect on bacteria, and is a good low-toxicity antibacterial agent. In addition, the adhesion ability of bacteria on the composite film was reduced under green light irradiation, indicating that the anti-adhesion ability of the composite film was enhanced under green light irradiation. In addition, adhesion of the composite membrane to bacteria is also affected by factors such as surface roughness, hydrophilicity and hydrophobicity, protein adsorption tendency, and the like. As for the roughness, it can be understood that as the content of RB@ZIF-8NPs gradually increases, the roughness increases correspondingly, and the bacterial adhesion gradually decreases; the hydrophobicity gradually increases and the bacterial adhesiveness decreases; meanwhile, as the content of RB@ZIF-8NPs is gradually increased, the metal ion zinc (Zn 2+) is also gradually increased, the metal ion has a certain destructive effect on the protein of bacteria, trace amount has no influence on human body, and the sterilization effect can be realized. Thus the adhesion of bacteria to the film is poor.
Therefore, the multifunctional composite material has excellent antibacterial effect.
Test example 5 plasticity and Heat resistance of multifunctional composite Material according to the invention
1. Plasticity of
PQZ 4 films prepared in example 4 were selected, cut into 2X 2cm 2 squares, and subjected to a film bending folding test to see if the films were plastic. The results are shown in FIG. 7: the film can be folded at will, can be tiled, bent and rolled, and has good plasticity.
2. Heat resistance
The thermal stability of the composite membrane was studied by thermogravimetric analysis, the specific method is as follows:
Thermogravimetric analysis was performed using a mertrer-tolidol thermogravimetric analyzer (TGDSC +). 10mg of the samples (P layer prepared in example 1, PQZ 0～PQZ4 prepared in examples 1 to 4 and comparative example 1) were subjected to a heating test at a rate of 10℃min -1 in argon at 30℃to 800 ℃.
The results are shown in FIG. 8: the P-layer film has a very low weight, almost near 0, and poor thermal stability at near 400 ℃. In contrast, there are mainly two weight losses for composite membranes, the first stage being about 250 ℃ and possibly due to the decomposition of the manglared. The loss at around 400 ℃ may be due to degradation of the composite membrane matrix, but still some weight is present. This demonstrates that there is some improvement in the thermal stability of the film by modification, showing potential in food packaging materials.
In conclusion, the RB is efficiently packaged into the ZIF-8 through a simple one-pot method, the RB@ZIF-8 Nano Particles (NPs) are synthesized, and the stability of the RB is improved. In addition, RB@ZIF-8NPs are doped into the PCL/PVA-QCS film to form PQZ composite film, so that excellent photodynamic sterilization efficiency is provided. In the presence of light radiation, the killing rate of bacteria is close to 99%, and the antibacterial adhesiveness of the composite film is also very good. Because PQZ composite film has good plasticity and heat resistance, the inadequacy of PCL is overcome, and the tensile strength of the composite film is improved. By adding SiO 2 NPs into PCL, the waterproof performance of the film is improved, and the film has certain blocking capability on sewage. Meanwhile, due to the addition of SiO 2 NPs and RB@ZIF-8NPs, the blocking capability of the film to ultraviolet rays is improved, and the adverse effect of the ultraviolet rays on food is reduced. In a word, PQZ multifunctional composite film can be used as a novel antibacterial material for food packaging and fresh-keeping.
Claims (13)
1. A multifunctional composite material, characterized in that: it is a film with a two-layer structure; the structure of the layer is a poly epsilon-caprolactone film containing SiO 2 nano particles; the other layer of structure is a polyvinyl alcohol/quaternized chitosan film containing zeolite imidazole ester framework material;
the mass fraction of SiO 2 nano particles in the poly epsilon-caprolactone film containing the SiO 2 nano particles is 1%;
The polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight: 50 parts of polyvinyl alcohol, 1-8 parts of zeolite imidazole ester framework material, 20 parts of quaternized chitosan and 12 parts of glycerol;
the mass of the zeolite imidazole ester framework material is 5-40% of that of poly epsilon-caprolactone;
the zeolite imidazole ester framework material contains a photosensitizer; the photosensitizer is Bengalhong;
the preparation method of the zeolite imidazole ester framework material containing the photosensitizer comprises the following steps:
1) Dissolving zinc nitrate hexahydrate in a solvent;
2) Dissolving dimethylimidazole and a photosensitizer in a solvent;
3) Adding the solution obtained in the step 1) into the solution obtained in the step 2), stirring, aging, centrifuging, washing and drying to obtain the product.
2. The multifunctional composite according to claim 1, wherein: the preparation method of the poly epsilon-caprolactone film containing the SiO 2 nano particles comprises the following steps:
And (3) dissolving the poly epsilon-caprolactone in an organic solvent, adding SiO 2 nano particles, stirring, casting the suspension on a hot glass plate, evaporating the organic solvent, and drying to obtain the product.
3. The multifunctional composite according to claim 2, characterized in that: the number average molecular weight of the poly epsilon-caprolactone is 80000 MW to 100000MW;
And/or the particle size of the SiO 2 nano-particles is 10-20 nm;
and/or the organic solvent is dichloromethane or N, N-dimethylformamide;
And/or, dissolving the poly epsilon-caprolactone in an organic solvent, performing ultrasonic treatment for 30-60 min, and then adding SiO 2 nano particles;
And/or, stirring when adding SiO 2 nano-particles;
and/or the temperature of the hot glass plate is 40-60 ℃;
and/or drying at 30-40 deg.c in vacuum.
4. A multifunctional composite according to claim 3, characterized in that: the number average molecular weight of the poly epsilon-caprolactone is 80000MW;
and/or the particle size of the SiO 2 nano-particles is 20nm;
and/or the temperature of the hot glass plate is 40 ℃.
5. The multifunctional composite according to claim 1, wherein: the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight:
The polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material is prepared from the following raw materials in parts by weight: 50 parts of polyvinyl alcohol, 8 parts of zeolite imidazole ester framework material, 20 parts of quaternized chitosan and 12 parts of glycerol;
and/or the mass of the zeolite imidazole ester framework material is 40% of that of poly epsilon-caprolactone.
6. The multifunctional composite according to claim 1, wherein: the preparation method of the polyvinyl alcohol/quaternized chitosan film containing the zeolite imidazole ester framework material comprises the following steps:
(1) Dissolving polyvinyl alcohol in a solvent to obtain a polyvinyl alcohol solution;
(2) Dispersing a zeolite imidazole ester framework material in a medium to obtain a suspension;
(3) Mixing the polyvinyl alcohol solution of step (1) and the suspension of step (2) to form a dispersion A;
(4) Dissolving quaternized chitosan and glycerol in a solvent to form a solution B;
(5) Adding the dispersion A in the step (3) into the solution B in the step (4) to obtain a film-forming solution;
(6) And (5) forming a film by the film forming solution in the step (5), and drying to obtain the film.
7. The multi-functional composite of claim 6, wherein:
in the step (1), the solvent is water;
and/or, in the step (1), the concentration of the polyvinyl alcohol solution is 1-5%;
And/or, in the step (2), the medium is an ethanol aqueous solution;
and/or, in the step (2), the concentration of the zeolite imidazole ester framework material in the suspension is 0.1-0.8%;
and/or, in the step (4), the solvent is water;
And/or in the step (4), the concentration of the quaternized chitosan in the solution B is 1-5%;
and/or, in the step (6), the drying is vacuum drying.
8. The multi-functional composite of claim 7, wherein:
in the step (1), the concentration of the polyvinyl alcohol solution is 5%;
And/or, in the step (2), the concentration of the ethanol water solution is 40% -50%;
and/or, in step (2), the concentration of zeolitic imidazolate framework material in the suspension is 0.8%;
And/or, in the step (4), the concentration of quaternized chitosan in the solution B is 2%;
And/or in the step (6), the temperature of the vacuum drying is 60-80 ℃ and the drying time is 1-5 h.
9. The multifunctional composite according to claim 1, wherein:
The mass ratio of the zinc nitrate hexahydrate in the step 1) to the dimethylimidazole and the photosensitizer in the step 2) is 15-20: 30-40: 1, a step of;
and/or, in step 1), the solvent is methanol;
and/or, in the step 2), the solvent is methanol.
10. The multifunctional composite of claim 9, wherein: the mass ratio of the zinc nitrate hexahydrate in the step 1) to the dimethylimidazole and the photosensitizer in the step 2) is 15:30:1.
11. A method of preparing the multifunctional composite of any one of claims 1-10, characterized by: it comprises the following steps:
A. Preparing a poly epsilon-caprolactone film containing SiO 2 nano particles according to the method for preparing a film as set forth in any one of claims 2 to 4;
B. Preparing a film forming solution according to the method of preparing a film as claimed in claim 6;
C. And (3) casting the film forming solution in the step (B) onto the poly epsilon-caprolactone film containing the SiO 2 nano particles in the step (A) to form a film, and drying to obtain the film.
12. The method according to claim 11, wherein: in the step C, 10mL of film forming solution is cast on the poly epsilon-caprolactone film containing SiO 2 nano particles every 200-250 square centimeters.
13. Use of the multifunctional composite material according to any one of claims 1-10 for the preparation of food packaging material and/or cling film.
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