CN113243479A - Application of metal organic framework material as remover to remove mycotoxin in food raw materials - Google Patents
Application of metal organic framework material as remover to remove mycotoxin in food raw materials Download PDFInfo
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- 239000002636 mycotoxin Substances 0.000 title claims abstract description 42
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- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-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)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 HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
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- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 description 1
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- RWQKHEORZBHNRI-BMIGLBTASA-N ochratoxin A Chemical compound C([C@H](NC(=O)C1=CC(Cl)=C2C[C@H](OC(=O)C2=C1O)C)C(O)=O)C1=CC=CC=C1 RWQKHEORZBHNRI-BMIGLBTASA-N 0.000 description 1
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- General Preparation And Processing Of Foods (AREA)
Abstract
The invention belongs to the technical field of removing agents, and discloses an application of a metal organic framework material as a removing agent for removing mycotoxin in food raw materials. The application of the invention provides a method for detoxifying mycotoxin, which is environment-friendly, energy-saving, high-efficiency in detoxification and has an outstanding effect on removing mycotoxin insoluble in water.
Description
Technical Field
The invention belongs to the technical field of removing agents, and relates to application of a metal organic framework material as a removing agent, in particular to application of the metal organic framework material as the removing agent for removing mycotoxin in food raw materials.
Background
Mycotoxins are natural toxins produced by various fungi under specific environmental conditions and are harmful to human health and are commonly found in food and feed. Among them, the most representative mycotoxins include: aflatoxin (AFT), Zearalenone (ZEN), fumonisin (FB1), Ochratoxin (OTA), Deoxynivalenol (DON), and the like. They mainly contaminate cereals, oilseeds, dried fruits and foodstuffs of animal origin, etc. Mycotoxins are food contaminants which easily cause pollution of food, soil and drinking water, and food-borne diseases caused by the food contaminants have increasingly influenced food safety, human health and economic development, and particularly, mycotoxins have overlapping toxicity to humans, animals and plants, carcinogenicity, nephrotoxicity, hepatotoxicity, cytotoxicity and the like.
At present, the detoxification method of mycotoxin mainly comprises physical, chemical and biological methods, including screening and stripping methods, heat treatment, water washing and grinding, radiation treatment, strong oxidants (strong acid, strong base, ozone and the like), adsorption, biodegradation and the like. These methods can convert mycotoxins into less or non-toxic substances but still present problems in large scale use, for example, the high temperature conditions of the heat treatment will affect the quality of the raw material; the mycotoxin and the by-product thereof are easy to remain after rinsing and stripping, and secondary pollution is formed; chemical substances such as strong acid and alkali can pollute food raw materials and the environment, and ozone detoxification requires special equipment and extra capital, so that detoxification cost is increased; the biological detoxification method is immature at present and has no obvious detoxification effect. In contrast, adsorption is the most direct and simple detoxification method. However, the adsorption method has difficult separation and poor detoxification effect aiming at aflatoxin, zearalenone, ochratoxin and other water-insoluble mycotoxins.
Metal Organic Frameworks (MOFs) are a new class of porous crystalline materials with coordination of central Metal and organic ligands, which have great application potential in various fields such as adsorption, separation and molecular recognition, but many MOFs (water-modified nano-silicate, cross-linked vitamin ketone, magnesium trisilicate, etc.) are made of non-renewable or toxic Metal materials, thereby limiting the application of MOFs in real life.
Disclosure of Invention
The invention aims to provide the application of a metal organic framework material used as a remover for removing mycotoxin in food raw materials, wherein the metal organic framework material prepared from natural biodegradable cyclic oligosaccharide and alkali metal hydroxide is used as the remover for removing mycotoxin in the food raw materials, so that the aims of environmental protection, energy conservation, high-efficiency detoxification and outstanding effect on removing mycotoxin insoluble in water are fulfilled.
In order to achieve the purpose, the invention adopts the technical scheme that:
use of a metal organic framework material as a remover for removing mycotoxins from a food material.
As a limitation, the metal-organic framework material is made of a naturally biodegradable cyclic oligosaccharide and an alkali metal hydroxide.
As a further limitation, the natural biodegradable cyclic oligosaccharide is a cyclodextrin.
Wherein the natural biodegradable cyclic oligosaccharide can also be maltooligosaccharide, coupling sugar or chitin oligosaccharide, and the cyclodextrin can be alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
As a second limitation, it is characterized in that the food material is a solid material or a water-insoluble liquid material.
As a further limitation, the solid feedstock is wheat, corn or peanut; the water-insoluble liquid raw material is corn germ oil, soybean oil, rapeseed oil, linseed oil or peanut oil.
As a third limitation, the mycotoxin is aflatoxin, zearalenone, fumonisin, ochratoxin, or deoxynivalenol.
As a fourth limitation, the method is to add the metal organic framework material into the solid raw material, mix, add water and mix evenly, stand, discard the supernatant and dry in the air, thus removing the mycotoxin in the solid raw material.
Wherein, water is added to ensure that the water is over the solid, and the weight ratio of the solid raw material to the water can be 1: 4-8.
As a further limitation, the weight ratio of the metal-organic framework material to the solid feedstock is 1-5: 100; the mixing is carried out for 5-15min at a constant speed of 200-250 rpm; the standing is to be carried out until solid-liquid separation is carried out.
Adding the metal organic framework material and water into the water-insoluble liquid raw material, shaking and uniformly mixing, centrifuging, standing, and removing a water layer to remove mycotoxin in the water-insoluble liquid raw material.
As a further limitation, the weight ratio of the metal organic framework material, the water-insoluble liquid raw material and the water is 5-8:100: 100;
the shaking and mixing is to shake for 30-40min and mix for 5-7 h;
the centrifugation is carried out at 12000-14000rpm for 8-12 min.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) the MOF is prepared from natural biodegradable cyclic oligosaccharide and alkali metal hydroxide, the natural biodegradable cyclic oligosaccharide in the raw materials can be generated in a large amount through the enzymatic action on starch, the raw materials are low in cost, energy-saving and environment-friendly, and the prepared MOF has the properties of no toxicity, edibility, low cost, reproducibility, biodegradability, easiness in modification, permanent porosity and high loading efficiency, and has a remarkable removing effect when used as a removing agent;
(2) the invention is suitable for removing the mycotoxins such as aflatoxin, zearalenone, fumonisin, ochratoxin or deoxynivalenol in solid food raw materials and water-insoluble liquid food raw materials, and particularly can wrap the water-insoluble mycotoxins into MOF materials to be converted into water-soluble compounds, thereby realizing the separation and removal of the mycotoxins;
the raw materials adopted by the invention have low cost, are renewable and biodegradable, and the using method is simple and efficient, can be applied to industrial production, and is suitable for removing mycotoxin in food raw materials.
The invention is described in further detail below with reference to the figures and the embodiments.
Drawings
FIG. 1 is a graph showing the results of HPLC analysis of ZEN concentration in examples 2 and 3 of the present invention;
FIG. 2 is a graph of the results of HPLC analysis of AFT concentrations for examples 2 and 3 of the present invention;
FIG. 3 is a graph of the results of HPLC analysis of ZEN and AFT concentrations in example 7 of the present invention;
FIG. 4 is an SEM image of CD-MOF of example 12 of the present invention;
FIG. 5 is an SEM image of soluble complex ZEN-CD-MOF formed by ZEN and CD-MOF in example 12 of the present invention;
FIG. 6 is a Fourier transform infrared spectrum of ZEN, CD-MOF and ZEN-CD-MOF in example 12 of the present invention;
FIG. 7 is an XRD diffractogram of ZEN, CD-MOF and ZEN-CD-MOF in example 12 of the present invention;
FIG. 8 is a graph showing the results of the adsorption capacity of ZEN on CD-MOF in example 12 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the described embodiments are only for illustrating the present invention and do not limit the present invention.
The experimental conditions in the following examples, if not indicated, are generally according to conventional conditions or according to the conditions recommended by the reagents company; reagents, consumables and the like used in the following examples can be obtained commercially without special instructions, analytically pure reagents meeting national standards are used during analysis, experimental water is pure water, and the used methods are conventional process methods in the field without special instructions.
Example 1 preparation of a Metal-organic framework Material
In the embodiment, two metal organic framework materials, namely a CD-MOF material and a gamma-CD-MOF material, are respectively prepared by two methods, specifically:
(I) CD-MOF material and preparation method thereof
I1) Accurately weighing CD (namely cyclodextrin 973g) and KOH (337g) according to the molar ratio of 1:8, adding 30L of pure water, stirring for 3-6h at room temperature under the condition of 100-; taking out the filtrate, transferring into a low temperature kettle containing 50L ethanol, culturing at constant temperature of 25-45 deg.C, and steam diffusing for 7-21 days.
I2) And after the transparent crystals grow out, carrying out vacuum filtration by adopting a 0.45-micrometer organic phase filter membrane, eluting the crystals for 3 times by using ethanol, and carrying out vacuum drying on the eluted crystals for 12-24 hours in a drying oven at 45 ℃ to obtain the CD-MOF.
The four CD-MOF materials prepared by the method are sequentially marked as CL1, CL2, CL3 and CL4, and specific parameters of the preparation method are shown in Table 1:
TABLE 1 detailed parameters of the four CD-MOF material preparation methods
(II) Gamma-CD-MOF material and preparation method thereof
II1) precisely weighing gamma-CD (gamma-cyclodextrin) and KOH according to the molar ratio of 1:8, dissolving in 200L of pure water, and magnetically stirring at 50 ℃ and 300rpm to prepare a mother solution.
II2) adding ethanol into the mother liquor, slowly adding 10L methanol and 250g PEG20000 to make the solution become turbid, shaking thoroughly, mixing well, heating the solution in water bath, and dissolving the precipitate again.
II3), standing at room temperature to fully separate out crystals and precipitate, centrifuging, removing supernatant, precipitating, washing with methanol and ethanol with 2 times of precipitation volume for 2 times respectively to remove unreacted impurities, and making into gamma-CD-MOF material, labeled as gamma CL.
The prepared metal organic framework materials CL1, CL2, CL3, CL4 and gamma CL can be used as a remover to remove Aflatoxin (AFT), Zearalenone (ZEN), fumonisin (FB1), Ochratoxin (OTA) or Deoxynivalenol (DON) and other mycotoxins in solid raw materials or water-insoluble liquid raw materials, and particularly, the removal effect on ZEN, AFT, OTA and other water-insoluble toxins is good.
Examples 2-6 use of MOF to remove mycotoxins from solid materials and removal Effect
Examples 2 to 6 are respectively the use and the removal effect of a metal organic framework material as a remover for removing mycotoxins from solid raw materials, and specifically the following are:
the method comprises the following steps: adding 1-5kg of the metal organic framework material prepared in the embodiment 1 into 100kg of solid raw material, uniformly stirring at the uniform speed of 250rpm of 200-.
The removing effect is as follows: taking 5g of solid raw materials before and after detoxification according to the method, adding 10mL of cold methanol for elution, standing, taking 1mL of suspension liquid in a centrifuge tube, carrying out vortex oscillation for 2min, centrifuging for 10min at 4 ℃ and 10000rpm, analyzing the mycotoxin concentration in the supernatant by using a High Performance Liquid Chromatography (HPLC), reducing the mycotoxin concentration by 85 percent or more, and marking as successful removal when the national standard requirement is met.
The specific parameters and the removal effect of the method are detailed in table 2:
TABLE 2 examples 2-6 method specific parameters and removal effectiveness
The removal effect shows that the methods of examples 2-6 can effectively remove the mycotoxin in the solid raw material, and figure 1 shows the result of HPLC analysis of ZEN concentration in examples 2 and 3; FIG. 2 is the result of HPLC analysis of AFT concentration in examples 2 and 3; the two figures show that the metal organic framework material has better effect on removing the toxin from the corn, and has more prominent effect on removing the toxin from the corn and the wheat polluted by the ZEN compared with the AFT.
Examples 7-11 use of MOF to remove mycotoxins from water-insoluble liquid feedstocks and Effect of removal
Examples 7 to 11 are respectively the use and the removal effect of a metal organic framework material as a remover for removing mycotoxins from a water-insoluble liquid raw material, and specifically the following are:
the method comprises the following steps: adding 5-8kg of the metal organic framework material prepared in the example 1 into 100kg of the water-insoluble liquid raw material, adding 100kg of pure water, shaking for 30-40min, stirring for 5-7h, uniformly mixing, centrifuging at 12000-14000rpm for 8-12min, standing, and removing a water layer to remove mycotoxin in the water-insoluble liquid raw material.
The removing effect is as follows: taking 5mL of water-insoluble liquid raw materials before and after detoxification according to the method, adding 5mL of acetonitrile, standing, taking 1mL of supernatant in a centrifuge tube, centrifuging at 13000rpm at 4 ℃ for 10min, analyzing the mycotoxin concentration in the supernatant by using a High Performance Liquid Chromatography (HPLC), reducing the mycotoxin concentration by 85% or more, and marking as successful removal when meeting the national standard requirement.
The specific parameters and removal effects of the method are detailed in table 3:
TABLE 3 concrete parameters and removal effects of the methods of examples 7 to 11
The removal effect shows that the method of the embodiment 2 to 6 can effectively remove the mycotoxin in the water-insoluble liquid raw material; figure 3 is the results of HPLC analysis of ZEN and AFT concentrations in example 7 showing that metal organic framework material provides better removal of ZEN toxins from corn germ oil.
Example 12 ZEN and ZEN-CD-MOF properties and ZEN adsorption removal curve (one) solubility of ZEN and ZEN-CD-MOF:
1) weighing 2mg of ZEN and CD-MOF materials (CL1) in a centrifuge tube respectively, fixing the volume to 10mL by pure water, placing the centrifuge tube in a shaker at 37 ℃, incubating for 2h under the condition of 150rpm, centrifuging and filtering, and taking 1mL of supernatant to dilute by 5 times;
2) and (3) passing the solution through a 0.22-micron microporous filter membrane to prepare a computer sample, and determining the content of ZEN according to an HPLC method.
The solubility (i.e. concentration) of ZEN and CD-MOF and soluble complex of ZEN-CD-MOF in water was calculated from a standard curve comparing the water solubility difference before and after ZEN was embedded and the solubility of ZEN and ZEN-CD-MOF in water is shown in table 4 below:
TABLE 4 solubility of ZEN and ZEN-CD-MOF in Water
The results show that the water solubility of ZEN is improved by about 89 times after being embedded by CD-MOF, so that water-insoluble mycotoxin can be removed from food raw materials.
(II) the chemical structures of ZEN, CD-MOF and ZEN-CD-MOF:
the structure detection of ZEN, CD-MOF and ZEN-CD-MOF resulted in the electron micrographs as shown in FIGS. 4-5, the spectrogram of FIG. 6 and the diffractogram of FIG. 7.
Wherein, FIG. 6 is a Fourier transform infrared spectrum of ZEN, CD-MOF and ZEN-CD-MOF. From the figure, the infrared spectrum peak shapes of ZEN-CD-MOF and CD-MOF are similar. The CD-MOF is shown to be embedded and adsorbed with ZEN toxin and maintain the original chemical structure, and a theoretical basis is provided for using the CD-MOF as a removing agent.
FIG. 7 is XRD diffractogram of ZEN, CD-MOF and ZEN-CD-MOF. From the figure, the original diffraction peak of ZEN is weakened after the ZEN is adsorbed by CD-MOF; in the process of containing ZEN, CD-MOF is found to have a change in crystal structure in combination with figures 4-5, and ZEN exists in CD-MOF in an amorphous state.
(III) ZEN adsorption and desorption curve:
the relationship between the adsorption amount of ZEN and CD-MOF is shown in FIG. 8. As can be seen from the figure, the adsorption equilibrium time of ZEN in CD-MOF is about 2 h. From FIG. 8, it can be seen that ZEN is adsorbed rapidly at 0-45min, the adsorption amount is increased almost linearly, then the adsorption speed gradually becomes slow and slowly approaches the equilibrium, and the adsorption is basically in the equilibrium state at 2-8 h. The CD-MOF is shown to have good adsorption and removal effects when used as a removal agent.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms, and any person skilled in the art may use the above-mentioned technical content as a teaching to make changes or modifications to the equivalent embodiments with equivalent changes, but all those simple changes, equivalent changes and modifications made to the above-mentioned embodiments without departing from the technical spirit of the present invention, and still all those embodiments are within the scope of the present invention as claimed in the claims.
Claims (10)
1. Use of a metal organic framework material as a remover for removing mycotoxins from a food material.
2. Use according to claim 1, wherein the metal-organic framework material is made of natural biodegradable cyclic oligosaccharides and alkali metal hydroxide.
3. Use according to claim 2, wherein the natural biodegradable cyclic oligosaccharide is a cyclodextrin.
4. Use according to claim 1, wherein the food material is a solid material or a water-insoluble liquid material.
5. Use according to claim 4, characterized in that the solid raw material is wheat, corn or peanut; the water-insoluble liquid raw material is corn germ oil, soybean oil, rapeseed oil, linseed oil or peanut oil.
6. Use according to claim 1, characterized in that the mycotoxin is aflatoxin, zearalenone, fumonisin, ochratoxin or deoxynivalenol.
7. The use according to any one of claims 1 to 6, wherein the mycotoxins in the solid material are removed by adding the metal organic framework material to the solid material, mixing, adding water to mix uniformly, standing, discarding the supernatant, and air-drying.
8. Use according to claim 7, wherein the weight ratio of the metal-organic framework material to the solid starting material is from 1 to 5: 100; the mixing is carried out for 5-15min at a constant speed of 200-250 rpm; the standing is to be carried out until solid-liquid separation is carried out.
9. The use according to any one of claims 1 to 6, wherein the mycotoxin in the water-insoluble liquid raw material is removed by adding the metal organic framework material and water into the water-insoluble liquid raw material, uniformly mixing by shaking, centrifuging, standing and discarding a water layer.
10. Use according to claim 9, wherein the weight ratio of metal organic framework material, water-insoluble liquid starting material and water is 5-8:100: 100;
the shaking and mixing is to shake for 30-40min and mix for 5-7 h;
the centrifugation is carried out at 12000-14000rpm for 8-12 min.
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