CN115651232B - Preparation method and application of fruit biological preservative film loaded with curcumin and gamma-CD-MOFs - Google Patents
Preparation method and application of fruit biological preservative film loaded with curcumin and gamma-CD-MOFs Download PDFInfo
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 title claims abstract description 106
- 239000013119 CD-MOF Substances 0.000 title claims abstract description 62
- 229940109262 curcumin Drugs 0.000 title claims abstract description 54
- 239000004148 curcumin Substances 0.000 title claims abstract description 54
- 235000012754 curcumin Nutrition 0.000 title claims abstract description 53
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000002335 preservative effect Effects 0.000 title claims abstract description 16
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920001218 Pullulan Polymers 0.000 claims abstract description 48
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- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims abstract description 48
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims abstract description 48
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- 239000000243 solution Substances 0.000 claims description 25
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 22
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 2
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Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a preparation method and application of a fruit biological preservative film of gamma-CD-MOFs loaded with curcumin, and relates to the technical field of preparation of food active packaging materials. The cyclodextrin metal organic frameworks (Cur-CD-MOFs) are synthesized and loaded with curcumin, and on the basis, the in-vitro cytotoxicity and antibacterial performance of the Cur-CD-MOFs are measured, and the hydrophilicity of the cyclodextrin metal organic frameworks can enable the cyclodextrin metal organic frameworks to be well dispersed in a pullulan/trehalose (Pul/Tre) composite film to be used as an antibacterial agent for food packaging. The influence of the biological preservative film on the fruit preservation effect is studied by taking coreless white heart grapes as a research object. The effectiveness of Cur-CD-MOFs-Pul/Tre in maintaining fruit freshness was demonstrated. The Cur-CD-MOFs-Pul/Tre composite film is a green edible food packaging material and has potential application prospect in the aspect of food packaging.
Description
Technical Field
The invention relates to the technical field of preparation of food active packaging materials, in particular to a packaging material of a biological preservative film which is edible and takes pullulan/trehalose (Pul/Tre) as a matrix, adds a cyclodextrin metal organic framework (Cur-CD-MOFs) loaded with a bioactive substance-curcumin, and adopts a tape casting method to prepare Cur-CD-MOFs-Pul/Tre.
Background
Food spoilage and waste from microbial infection is an increasingly prominent problem. In order to prolong the preservation time of foods and reduce the environmental pollution at the same time, there is considerable interest in developing environmentally friendly antibacterial preservation materials. Curcumin is a low molecular weight polyphenol found in turmeric rootstock. Curcumin is nontoxic, is considered safe even at higher doses, and is known for its antioxidant, antibacterial and anti-inflammatory activity. However, free curcumin has low water solubility and is easily and rapidly degraded under high temperature and ultraviolet irradiation conditions, which limits the application of free curcumin in food preservation. In fact, these problems can be overcome by encapsulation in nanocarriers. In recent years, encapsulation techniques such as nanoparticles, nanoemulsions, and microcapsules have been explored to improve stability, water solubility, and bioavailability of curcumin. In view of the diversity of food systems, researchers are more interested in designing new carriers to meet the various requirements of environmentally friendly packaging materials.
The metal organic frameworks (Metal organic frameworks, MOFs) are inorganic crystalline porous polymer materials formed by self-assembling organic ligands and metal ions through metal coordination bonds, and have been widely studied in the aspects of drug packaging and delivery in recent years due to the characteristics of easy synthesis, high drug carrying capacity, slow release and the like. For food preservation applications, new considerations are focused on the preparation of systems by using materials that are safe and biocompatible. Unfortunately, most MOFs are not recyclable in their preparation, and the high toxicity of the synthetic components or the high toxicity of the selected chemicals greatly limits the use of MOFs in the food industry. Thus, biocompatible metal ions (Ca 2+ 、K + ) And organic ligands (amino acids, polypeptides, carbohydrates) can promote the synthesis of green MOFs and their use in the food industry.
Cyclodextrin-metal organic frameworks (CD-MOFs) based on Cyclodextrin (CD) are of interest to food researchers because of their typically edible, biodegradable and good biocompatibility. CD-MOFs have been shown to encapsulate hydrophobic components into their porous structure, but their application as slow release carriers for antimicrobial drugs in edible bioactive films has not been reported.
The invention takes gamma-CD-MOFs as a carrier to synthesize Cur-CD-MOFs and load curcumin, and on the basis, the cytotoxicity and antibacterial performance of Cur-CD-MOFs in vitro are measured, and the hydrophilicity of the Cur-CD-MOFs can be well dispersed in a pullulan/trehalose (Pul/Tre) composite film to be used as an antibacterial agent for food packaging. The influence of Cur-CD-MOFs on the fresh-keeping effect of fruits is studied by taking coreless white heart grapes as a study object. It is therefore a primary object of the present invention to provide an effective synthetic strategy for antimicrobial preservation materials to avoid wastage of food.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for preparing the Cur-CD-MOFs-Pul/Tre edible composite preservative film, and research on the in-vitro toxicity and antibacterial activity of the Cur-CD-MOFs and the influence of the doping of the Cur-CD-MOFs on the mechanical property, barrier property, structural property and preservative effect of the Pul/Tre composite film.
The preparation method of the Cur-CD-MOFs-Pul/Tre edible composite preservative film comprises the following steps:
(1) Preparation of Cur-CD-MOFs:
step (a) Synthesis of gamma-CD-MOFs
gamma-CD and potassium hydroxide were combined according to 1:8 in a 50mL beaker of aqueous solution, 5mL of methanol was added to the above solution, and the beaker was placed in a large beaker containing 40mL of methanol. After standing in a constant-temperature water bath at 50 ℃ for 5 hours, the molar ratio of the added gamma-CD to the gamma-CD is 4: cetyl trimethylammonium bromide (CTAB) of 5, incubated overnight at 15 ℃. The pellet was then washed twice with ethanol and methanol by centrifugation at 5000rpm for 5 minutes. Finally, the precipitate was dried in vacuo at 50℃for 5h to give a free-flowing white cube powder, i.e., gamma-CD-MOFs.
Step (b) Synthesis of Cur-CD-MOFs
Curcumin and gamma-CD-MOFs were combined according to 2:3 was simultaneously dissolved in methanol and stirred in the dark for 3 hours. The mixture was centrifuged at 5000rpm for 20 minutes. The precipitate was collected and washed twice with methanol. Finally, curcumin-loaded γ -CD-MOFs (Cur-CD-MOFs) were obtained by vacuum drying overnight.
(2) Pullulan and trehalose were mixed according to 1:1, stirring at room temperature for 1h to dissolve completely to obtain polysaccharide solution
(3) And (3) adding a certain amount of plasticizer and Cur-CD-MOFs into the solution in the step (2), placing the blend into a water bath constant temperature magnetic stirrer, and stirring for 30min at 50 ℃ to obtain a film forming solution.
(4) Taking a film forming liquid, forming a film by adopting a tape casting method, and drying for 8 hours by blowing at 60 ℃; and taking out the film after the film is formed, and cooling to room temperature to obtain the preservative film.
The concentration of the polysaccharide solution in the step (2) is 2g/50mL.
The plasticizer in the step (3) is glycerol, and the addition amount of the plasticizer is 15 percent based on the total mass ratio of pullulan to trehalose.
The addition amount of Cur-CD-MOFs in the step (3) is 10% based on the total mass ratio of pullulan to trehalose.
The invention has the beneficial effects that:
(1) The Cur-CD-MOFs prepared by the method is a nontoxic microporous material with an antibacterial effect, and can promote the synthesis of green MOFs and the application of the green MOFs in the food industry.
(2) The incorporation of Cur-CD-MOFs improves the mechanical, barrier and structural properties of the Pul/Tre composite membrane.
(3) The effectiveness of Cur-CD-MOFs-Pul/Tre in maintaining freshness of fruits was demonstrated by coreless white heart grapes. The Cur-CD-MOFs-Pul/Tre composite film is a green edible food packaging material and has potential application prospect in the aspect of food packaging.
Drawings
FIG. 1 is a scanning electron microscope image of gamma-CD (left), gamma-CD-MOFs (middle) and Cur-CD-MOFs (right).
FIG. 2 is a graph of nitrogen adsorption-desorption experimental data for gamma-CD-MOFs and Cur-CD-MOFs.
FIG. 3 is an XRD diffraction pattern of Curcumin (Curcumin), gamma-CD-MOFs and Cur-CD-MOFs.
FIG. 4 is a Fourier infrared spectrum of Curcumin (Curcumin), gamma-CD-MOFs and Cur-CD-MOFs.
FIG. 5 is a thermogravimetric plot of Curcumin (Curcumin), gamma-CD-MOFs and Cur-CD-MOFs.
FIG. 6 is a histogram of in vitro toxicity of gamma-CD-MOFs and Cur-CD-MOFs.
FIG. 7 is a graph showing the antibacterial effect of Cur-CD-MOFs. In the figure, A is the bacteriostasis effect (change with time) of escherichia coli (E.coli) and staphylococcus aureus (S.aureus), B is a bacteriostasis rate histogram (change with time), C is an E.coli scanning electron microscope image before and after bacteriostasis, D is an S.aureus scanning electron microscope image before and after bacteriostasis, E is a colony image of penicillium expansum (Penicillium expansum) before and after bacteriostasis, and F is a colony image of Botrytis cinerea before and after bacteriostasis.
Fig. 8 is a scanning electron microscope image of the plane (up) and cross section (down) of different composite films. The figure sequentially shows a pullulan/trehalose composite film (Pul/Tre), a curcumin-pullulan/trehalose composite film (Cur-Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (Cur-CD-MOFs-Pul/Tre) from left to right.
Figure 9 is an XRD diffractogram of the different composite films. The figure sequentially shows a pullulan/trehalose composite film (Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (Cur-CD-MOFs-Pul/Tre) from top to bottom.
Fig. 10 is a fourier transform attenuated total reflection infrared spectrum of different composite films. The figure sequentially shows a pullulan/trehalose composite film (Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (Cur-CD-MOFs-Pul/Tre) from top to bottom.
Figure 11 is a bar graph of the mechanical properties of different composite films. The figure sequentially shows a pullulan/trehalose composite film (Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (Cur-CD-MOFs-Pul/Tre) from left to right.
FIG. 12 is a bar graph of moisture content and water vapor transmission rate for various composite films. The figure sequentially shows a pullulan/trehalose composite film (Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film (Cur-CD-MOFs-Pul/Tre) from left to right.
FIG. 13 shows the characteristic peak intensity ratio (I) of the Raman spectrum of soybean oil treated with different composite films (970) /I (1438) And I (1656) /I (1746) ). In the figure, a film-free covering group (Control), a pullulan/trehalose composite film covering group (Pul/Tre), a gamma cyclodextrin metal organic framework-pullulan/trehalose composite film covering group (gamma-CD-MOFs-Pul/Tre) and a curcumin-loaded gamma cyclodextrin metal organic framework-pullulan/trehalose composite film covering group (Cur-CD-MOFs-Pul/Tre) are sequentially arranged from left to right.
Fig. 14 is a schematic diagram of preservation effect of coreless white heart grapes under different conditions, wherein a is a visual diagram of preservation effect of coreless white heart grapes, B is a schematic diagram of oxidation dryness of coreless white heart grape stems, CON represents a non-film-coating treatment group, pul/Tre represents a pullulan/trehalose film-coating treatment group, and Cur-CD-MOFs-Pul/Tre represents a curcumin-carrying gamma cyclodextrin metal organic frame-pullulan/trehalose film-coating treatment group.
FIG. 15 is a graph of the weight loss rate of coreless white heart grapes treated under different conditions. In the figure, CON represents a non-coating treatment group, pul/Tre represents a pullulan/trehalose coating treatment group, and Cur-CD-MOFs-Pul/Tre represents a curcumin-carrying gamma cyclodextrin metallo-organic framework-pullulan/trehalose coating treatment group.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. The invention will be described in further detail below in connection with specific examples and with reference to the data. It should be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
In the following examples, the Chinese names, english names or abbreviations of the following nouns may be used, but whether the Chinese names, english names or abbreviations are used, they represent a compound or a pharmaceutical or an agent. Specifically as shown in table 1:
table 1 Chinese and English control abbreviation table
The reagents and sources used in the present invention are shown in Table 2:
table 2 experimental materials
Comparative example 1: pul/Tre composite membrane
And (3) blending 1g of pullulan and 1g of trehalose in an aqueous solution, stirring at room temperature for 1h to completely dissolve, preparing a polysaccharide solution with the concentration of 2g/50mL, adding glycerol accounting for 15% of the total mass ratio of the pullulan and the trehalose, and blending with the polysaccharide solution at 50 ℃ for 30min to obtain a uniform pullulan/trehalose film-forming solution (Pul/Tre). 15mL of the film forming liquid is taken out in a culture dish with the diameter of 9cm, and is dried for 6 hours at 50 ℃ to obtain the Pul/Tre composite film.
Comparative example 2: cur-Pul/Tre composite membrane
And (3) blending 1g of pullulan and 1g of trehalose in an aqueous solution, stirring at room temperature for 1h to completely dissolve, preparing a polysaccharide solution with the concentration of 2g/50mL, adding glycerol accounting for 15% of the total mass ratio of the pullulan and the trehalose, and blending with the polysaccharide solution at 50 ℃ for 30min to obtain a uniform pullulan/trehalose film-forming solution (Pul/Tre). Curcumin (5% accounting for the total mass ratio of pullulan and trehalose) is mixed into 50mL of Pul/Tre film forming liquid, stirred for 30min at 50 ℃, and the Cur-Pul/Tre composite film is obtained by referring to the method for preparing the Pul/Tre composite film in comparative example 1.
Comparative example 3: gamma-CD-MOFs-Pul/Tre composite membrane
And (3) blending 1g of pullulan and 1g of trehalose in an aqueous solution, stirring at room temperature for 1h to completely dissolve, preparing a polysaccharide solution with the concentration of 2g/50mL, adding glycerol accounting for 15% of the total mass ratio of the pullulan and the trehalose, and blending with the polysaccharide solution at 50 ℃ for 30min to obtain a uniform pullulan/trehalose film-forming solution (Pul/Tre). Dissolving gamma-CD-MOFs (10% of total mass ratio of pullulan and trehalose) in 50mL of Pul/Tre film forming solution, stirring for 30min at 50 ℃, and obtaining the gamma-CD-MOFs-Pul/Tre composite film by referring to the method for preparing the Pul/Tre composite film in comparative example 1.
Example 1: synthesis of gamma-CD-MOFs and Cur-CD-MOFs
(a) Synthesis of gamma-CD-MOFs
1.62g of gamma-CD (25 mmol/L) was dissolved in 50mL of aqueous potassium hydroxide (200 mmol/L), 5mL of methanol was added to the above solution, and the beaker was placed in a large beaker containing 40mL of methanol. After standing in a constant temperature water bath at 50℃for 5 hours, 365mg of cetyltrimethylammonium bromide was added and incubated overnight at 15 ℃. The pellet was then washed twice with ethanol and methanol by centrifugation at 5000rpm for 5 minutes. Finally, the precipitate was dried in vacuo at 50℃for 5h to give a free-flowing white cube powder, i.e., gamma-CD-MOFs.
(b) Synthesis of Cur-CD-MOFs
Curcumin 2mg/mL and gamma-CD-MOFs 3mg/mL were simultaneously dissolved in methanol and stirred in the dark for 3 hours. The mixture was centrifuged at 5000rpm for 20 minutes. The precipitate was collected and washed twice with methanol. Finally, curcumin-loaded γ -CD-MOFs (Cur-CD-MOFs) were obtained by vacuum drying overnight.
Example 2: preparation of composite membranes
And (3) blending 1g of pullulan and 1g of trehalose in an aqueous solution, stirring at room temperature for 1h to completely dissolve, preparing a polysaccharide solution with the concentration of 2g/50mL, adding glycerol accounting for 15% of the total mass ratio of the pullulan and the trehalose, and blending with the polysaccharide solution at 50 ℃ for 30min to obtain a uniform pullulan/trehalose film-forming solution (Pul/Tre). 15mL of the film forming liquid is taken out in a culture dish with the diameter of 9cm, and is dried for 6 hours at 50 ℃ to obtain the Pul/Tre composite film. Respectively dissolving gamma-CD-MOFs (10% of total mass ratio of pullulan and trehalose) and Cur-CD-MOFs (10% of total mass ratio of pullulan and trehalose) in 50mL of Pul/Tre film forming liquid, stirring for 30min at 50 ℃, and obtaining the gamma-CD-MOFs-Pul/Tre composite film and Cur-CD-MOFs-Pul/Tre composite film by referring to a method for preparing the Pul/Tre composite film.
Experimental example 1: structure determination of gamma-CD-MOFs and Cur-CD-MOFs
The experimental method comprises the following steps: the morphology of the samples was observed using a scanning electron microscope (S-3400N) at an accelerating voltage of 5 kV. Using a fully automatic specific surface area porosity analyzer (BET) (NOVA 3000 e) at 77k with N 2 The specific surface area and pore volume of the samples were determined by adsorption-desorption, each sample being degassed at 80 ℃ for 4 hours before measurement. XRD spectra of the samples were obtained with an x-ray diffractometer at 5/min in the range 5 DEG to 40 deg. Using FTIR spectrometer at 4000-600cm -1 Within the range of (2), 16 scans were performed and FTIR spectra of the samples were recorded. Thermal stability of the samples was performed on a comprehensive thermal analyzer (STA 449 F3 Jupiter), at N 2 Heated from 30℃to 500℃at a rate of 10℃per minute under an atmosphere.
By SEM and N 2 And observing the morphology and the porosity of the material by an adsorption-desorption method, and determining the micropore structure and the curcumin doping amount of the material. The results indicate that the morphology of gamma-CD-MOFs and Cur-CD-MOFs exhibit a typical cubic structure (FIG. 1). Notably, the fidgetiness of the surface of Cur-CD-MOFs may be due to local exposure of curcumin. As shown in FIG. 2, gamma-CD-MOFs and Cur-CD-MOFs vs. N at low relative pressure 2 Their similar microporous structure may cause a typical type I adsorption isotherm. The specific surface area was reduced from 322.344m2/g (γ -CD-MOFs) to 45.884m2/g (Cur-CD-MOFs), which was related to the occupation of the interior space of γ -CD-MOFs by curcumin. Furthermore, as can be seen from fig. 2 (right), the decrease in pore volume of γ -CD-MOFs occurs mainly at a pore width of 1-2nm, which again demonstrates that curcumin occupies the micropore space of γ -CD-MOFs. The crystal structure of the material was analyzed by XRD (fig. 3). After encapsulation by gamma-CD-MOFs, the representative diffraction peak of curcumin in Cur-CD-MOFs disappeared, indicating that curcumin was incorporated at the molecular level. The interactions of gamma-CD-MOFs with curcumin were studied using FTIR and TGA.As shown in FIG. 4, the characteristic peaks of curcumin in Cur-CD-MOFs were each measured from 856.1cm -1 、1283.1cm -1 Move to 861.7cm -1 、1302.1cm -1 。1628.1cm -1 ，1500cm -1 The characteristic peak disappears. In addition, changes in v-OH indicate hydrogen bonding between them. The above results demonstrate successful binding of curcumin to gamma-CD-MOFs, which is further demonstrated in both thermogravimetric losses (fig. 5). The first weight loss stage is below 120 ℃, and the second weight loss stage is about 240 ℃, and the volatilization of curcumin molecules corresponds to adsorbed water and ethanol. The weight loss ratio of Cur-CD-MOFs was 55.63% compared to gamma-CD-MOFs, indicating that the mass percent of incorporated curcumin reached 9.36%. These evidence indicate that curcumin was successfully encapsulated into gamma-CD-MOFs.
Experimental example 2: cytotoxicity assessment of gamma-CD-MOFs and Cur-CD-MOFs
Toxicity of gamma-CD-MOFs and Cur-CD-MOFs components to HepG2 cells was determined by CCK 8. mu.L of HepG2 cells (5X 10) 4 cell/mL) was inoculated in 96-well plates at 37℃C (5% CO 2 95% rh) for 24h. The medium was discarded, and after addition of different concentrations (0-32. Mu.g/mL) of gamma-CD-MOFs and Cur-CD-MOFs complete medium for 12h, the supernatant was removed and 110. Mu.L of medium (containing 10. Mu.L of CCK 8) was added. After shaking for 1 hour, absorbance was measured at 450nm with a microplate reader.
Considering the key cytotoxicity of candidate fresh-keeping materials, the invention takes a human liver cancer cell line (HepG 2) as a material, and adopts a CCK-8Kit method to evaluate the in vitro cytotoxicity and biocompatibility of gamma-CD-MOFs and Cur-CD-MOFs. The results showed that HepG2 cell viability was >100% (fig. 6) without cytotoxicity after 12h incubation with gamma-CD-MOFs and Cur-CD-MOFs materials. The gamma-CD-MOFs have good cell compatibility and can be used as a potential curcumin carrier.
Experimental example 3: antibacterial Activity study of Cur-CD-MOFs
The experimental method comprises the following steps: the antibacterial activity of Cur-CD-MOFs was evaluated on two representative strains, E.coli and Staphylococcus aureus (S.aureus). Incubating at 37 ℃ to obtain fresh bacterial liquid, and adjusting bacterial suspension to 10 ℃ with 0.9% sodium chloride solution 7 CFU/mL. Will not be asThe same sample (4 mg/mL) was added to a Erlenmeyer flask containing 50mL of the bacterial suspension. The incubation time of the material with E.coli and S.aureus is 0-4h and 0-8h, respectively. After the bacterial liquid was diluted to a proper concentration with physiological saline, 100. Mu.L of the bacterial liquid was applied to the surface of LB solid medium, and cultured at 37℃for 24 hours, and untreated bacterial suspension was used as a control group. The antibacterial properties of the different samples were studied using standard colony counting methods. The diluted bacteria (40 mL,10 7 CFU/mL) was fixed with 2.5% glutaraldehyde at 4 ℃ for 6 hours, and then washed twice with sterile physiological saline. Subsequently, the samples were dehydrated in gradient alcohol (30, 50, 70, 90 and 100%) for 15 minutes. Taking 0.1ml of bacterial liquid, drying at 37 ℃ and observing by a scanning electron microscope. A filter paper method is adopted to carry out bacteriostasis test on penicillium expansum (P. Expansum) and botrytis cinerea (B. Cinerea). The filter paper with the diameter of 0.5mm is soaked in the eluted spore suspension for 2min, taken out and placed on a PDA culture medium, and cultured in a culture box at 25 ℃ for 5 days. Wherein, the PDA culture medium contains 4mg/mL of Cur-CD-MOFs, and the control group is not added with Cur-CD-MOFs.
As shown in FIG. 7A, cur-CD-MOFs are time dependent on the antibacterial effect of E.coli and S.aureus. When Cur-CD-MOFs were incubated with E.coli and S.aureus for 4h and 8h, the mortality rate of the bacteria reached 100% (FIGS. 7A, 7B). As shown in fig. 7c,7d, in SEM images, the untreated bacterial surface was full and smooth, complete in shape, and free of deformation and defects. After Cur-CD-MOFs treatment, deformation occurred in E.coli and S.aureus. Wherein, the cell surface morphology of e.coli showed wrinkles, lesions and holes (fig. 7C), and the cell surface morphology of s.aureus was severely distorted (fig. 7D). In contrast, e.coli is more severely damaged, its cytoplasm leaks and collapses completely. As shown in fig. 7E and 7F, the colony morphology of the control group was convex and dense in texture. After being treated by Cur-CD-MOFs, the bacterial colony is flat in shape, loose in texture and transparent in edge, which proves that Cur-CD-MOFs can effectively inhibit the growth of mould, and especially has the most obvious effect on the growth inhibition of aerial mycelium.
Experimental example 4: structure and performance measurement of composite film
The experimental method comprises the following steps: the microstructure of the surface and cross section of the film was observed with a scanning electron microscope (JSM-7001F) at an accelerating voltage of 15 kV. Using x-ray diffractometer at 10 deg. in 2 theta rangeXRD patterns of the films were obtained at-80℃and 5℃per minute. Recording films at 4000-600cm using ATR-FTIR spectrometer -1 FTIR spectra in between. The Tensile Strength (TS), elongation At Break (EAB) and Young's modulus (E) of the film samples were measured by a physical property instrument. The water vapor transmission rate (WVP) was measured using ASTM standard method E96. The oxygen transmission (OP) was measured by raman spectroscopy, 50ml soybean oil samples were placed in 250ml conical flasks, sealed with film samples, and placed in a 60 ℃ incubator for 7 days to accelerate oxidation of the oil, and the oil samples were collected by DXRTM3 raman spectroscopy. The Moisture Content (MC) of the film was determined by drying to constant weight at 105 ℃.
The surface and cross-sectional microstructure of the different films were observed by SEM images (fig. 8). Curcumin has hydrophobicity and is easy to separate. Cur-CD-MOFs have good compatibility in the Pul/Tre matrix, and the composite membrane has a uniform structure and no phase separation. Therefore, the gamma-CD-MOFs are used as carriers for conveying the curcumin, and the solubility of the curcumin is obviously improved on the premise of not influencing the film structure. XRD (fig. 9) results show that the diffraction peak at 2θ=19° is mainly due to the presence of a significant covalent bond between Pul and Tre. Cur-CD-MOFs are encapsulated in the polysaccharide network as an active filler, without significant impact on the crystallization properties of the film. The ATR-FTIR spectra of the different samples are shown in FIG. 10. Addition of Cur-CD-MOFs resulted in shift of the characteristic hydroxyl peak (from 3347cm -1 To 3342cm -1 To 3339cm -1 ) Indicating that new hydrogen bonds are formed between Cur-CD-MOFs and the matrix molecules. This is due to the interaction between C-O in Cur-CD-MOFs and-OH in polysaccharides. An increase in the number of hydrogen bonds will result in more intermolecular forces and a denser polymer matrix, as evidenced by an improvement in mechanical properties (fig. 11) and barrier properties (fig. 12, 13). Wherein the EBA of the composite film is reduced from 152% to 130%, and TS and Young's modulus are respectively 7.76N/mm 2 9.35MPa rise to 10.49N/mm 2 15.39MPa (FIG. 11). WVP is from 7.15X10 -12 g m -1 s - 1 Pa -1 Down to 5.03X10 -12 g m -1 s -1 Pa -1 (FIG. 12). Characteristic peak ratio in Raman spectra of soybean oil under different treatments for OPValue representation (fig. 13). I (970) /I (1438) And I (1656) /I (1746) Indicating changes in the trans and cis double bonds, respectively. Wherein I is (970) /I (1438) In a downward trend (indicating a decrease in trans structure), I (1656) /I (1746) The rising trend (showing the reduction of cis double bond loss) shows that the Cur-CD-MOFs-Pul/Tre membrane can effectively block O 2 And delay the oxidation of the oil. In addition, the addition of Cur-CD-MOFs reduced the moisture content of the Pul/Tre films (FIG. 12). This further demonstrates that the interaction of C-O on Cur-CD-MOFs with-OH on Pul/Tre reduces the effectiveness of the interaction of-OH with water.
Application example: test of preservation effect of composite film coating on coreless white chicken heart grape
In the application examples, pul/Tre, gamma-CD-MOFs-Pul/Tre and Cur-CD-MOFs-Pul/Tre film forming liquid are the same as the film forming liquid before drying in the preparation of Pul/Tre, gamma-CD-MOFs-Pul/Tre and Cur-CD-MOFs-Pul/Tre composite films in the experimental examples. Fresh coreless white heart grapes are selected, immersed in Pul/Tre, gamma-CD-MOFs-Pul/Tre and Cur-CD-MOFs-Pul/Tre film forming liquid for 1min respectively, taken out, placed in a fume hood, quickly dried and placed at room temperature, coreless white heart grapes coated with no film are selected as a control, and the change is detected within 14 days.
The appearance of the coreless white heart grape after the spraying treatment is not greatly changed, and the coreless white heart grape is acceptable. As shown in fig. 14A, the Control (CON) group decayed on day 4. The Pul/Tre group showed decay on day 8, the surface of the sample had atrophic and dehydration was severe. In contrast, the Cur-CD-MOFs-Pul/Tre group samples remained relatively intact on day 10. Also, as can be seen from fig. 14B, the stems of the CON group samples dried up on day 4, the Pul/Tre group dried up on day 8, and the Cur-CD-MOFs-Pul/Tre group remained green on day 10. Furthermore, the samples of the Cur-CD-MOFs-Pul/Tre group showed more weight retention than the CON and Pul/Tre groups (FIG. 15). Specifically by day 10, the weight loss rates of the three groups were 28.22%, 20.75% and 9.31%, respectively. Due to the high barrier property of Cur-CD-MOFs-Pul/Tre and the antibacterial property of Cur-CD-MOFs, putrefaction and water loss of coreless white heart grape and oxidation and drying of stems are delayed.
Claims (6)
1. The preparation method of the fruit biological preservative film loaded with curcumin and gamma-CD-MOFs is characterized by comprising the following steps of:
(1) Dissolving gamma-CD and potassium hydroxide in an aqueous solution, adding methanol to the solution, and placing the solution in a large beaker containing methanol; after standing for 5 hours in a constant-temperature water bath at 50 ℃, adding cetyltrimethylammonium bromide and incubating overnight at 15 ℃; then centrifuging at 5000rpm for 5 minutes, and washing the precipitate twice with ethanol and methanol; finally, the precipitate was dried in vacuo at 50 ℃ for 5h to give a free-flowing white cube powder, γ -CD-MOFs; then, curcumin and gamma-CD-MOFs are simultaneously dissolved in methanol and stirred in the dark for 3 hours; the mixture was centrifuged at 5000rpm for 20 minutes; collecting precipitate, washing twice with methanol; finally, the curcumin-loaded gamma-CD-MOFs are obtained by vacuum drying overnight;
(2) Pullulan and trehalose were mixed according to 1:1, stirring at room temperature for 1 hr to dissolve completely, and preparing into polysaccharide solution with concentration of 2g/50mL
(3) Adding plasticizer with certain mass concentration and Cur-CD-MOFs into the polysaccharide solution in the step (2), placing the blend into a water bath constant temperature magnetic stirrer, and stirring for 30min at 50 ℃ to obtain a film-forming solution;
(4) Taking a film forming liquid, forming a film by adopting a tape casting method, and drying for 8 hours by blowing at 60 ℃; and taking out the film after the film is formed, and cooling to room temperature to obtain the preservative film.
2. The method for preparing the fruit biological preservative film loaded with the gamma-CD-MOFs of curcumin according to claim 1, wherein the plasticizer in the step (3) is glycerol, and the addition amount of the plasticizer is 15% of the total mass ratio of pullulan to trehalose.
3. The method for preparing the fruit biological preservative film loaded with the gamma-CD-MOFs of curcumin according to claim 1, wherein the addition amount of the Cur-CD-MOFs in the step (3) is 10% based on the total mass ratio of pullulan to trehalose.
4. The method for preparing the fruit biological preservative film loaded with the curcumin and the gamma-CD-MOFs is characterized in that gamma-CD and potassium hydroxide are mixed according to the following ratio of 1:8 in molar ratio.
5. The method for preparing the fruit biological preservative film loaded with the gamma-CD-MOFs of curcumin according to claim 1, which is characterized in that the molar ratio of the added curcumin to the gamma-CD is 4: cetyl trimethylammonium bromide of 5.
6. The method for preparing the fruit biological preservative film loaded with the gamma-CD-MOFs of the curcumin according to claim 1, which is characterized in that the mass ratio of the curcumin to the gamma-CD-MOFs is 2:3.
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| CN1723803A (en) * | 2005-07-18 | 2006-01-25 | 南京雨润食品有限公司 | Natural membrane forming preservation agent used for crystal-like delicious meat |
| CN112870371A (en) * | 2021-01-27 | 2021-06-01 | 广州新济药业科技有限公司 | Application of cyclodextrin-metal organic framework in preparation of inhalant and inhalant |
| CN114573884A (en) * | 2022-03-09 | 2022-06-03 | 浙江工业大学 | Preparation method and application of natural edible fruit and vegetable fresh-keeping packaging film |
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| CA3021005A1 (en) * | 2017-10-16 | 2019-04-16 | Mcmaster University | Method of long-term preservation of chemical and biological species using sugar glasses |
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| CN1723803A (en) * | 2005-07-18 | 2006-01-25 | 南京雨润食品有限公司 | Natural membrane forming preservation agent used for crystal-like delicious meat |
| CN112870371A (en) * | 2021-01-27 | 2021-06-01 | 广州新济药业科技有限公司 | Application of cyclodextrin-metal organic framework in preparation of inhalant and inhalant |
| CN114573884A (en) * | 2022-03-09 | 2022-06-03 | 浙江工业大学 | Preparation method and application of natural edible fruit and vegetable fresh-keeping packaging film |
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