CN111298775B - Chitin magnetic microsphere adsorbent and preparation method and application thereof - Google Patents

Chitin magnetic microsphere adsorbent and preparation method and application thereof Download PDF

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CN111298775B
CN111298775B CN202010142432.1A CN202010142432A CN111298775B CN 111298775 B CN111298775 B CN 111298775B CN 202010142432 A CN202010142432 A CN 202010142432A CN 111298775 B CN111298775 B CN 111298775B
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microspheres
chitin
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chitin magnetic
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CN111298775A (en
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王国珍
刘小涢
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Wuhan Polytechnic University
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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    • 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
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

Abstract

The invention discloses a chitin magnetic microsphere adsorbent and a preparation method and application thereof. The chitin magnetic microsphere adsorbent is prepared by taking chitin magnetic microspheres as a carrier and loading polyhydroxy compounds, and combines the advantages of the chitin magnetic microspheres and the polyhydroxy compounds, so that the obtained adsorbent has high-efficiency toxin adsorption capacity on vomitoxin in food and/or feed.

Description

Chitin magnetic microsphere adsorbent and preparation method and application thereof
Technical Field
The invention relates to the technical field of adsorbents, and particularly relates to a chitin magnetic microsphere adsorbent as well as a preparation method and application thereof.
Background
Vomitoxin (vomitoxin) is an important pollution toxin commonly existing in food crops and finished products thereof, is also called Deoxynivalenol (DON), is a trichothecene compound, can cause toxic symptoms such as animal vomiting and the like, and is called vomitoxin. Vomitoxin has strong toxicity and is mainly reflected in two aspects: has cytotoxicity; ② has strong immunosuppressive property. In the aspect of cytotoxicity, vomitoxin can seriously damage prokaryotic cells, eukaryotic cells, plant cells, tumor cells and the like. In addition, emetic toxins have severe toxic effects on hematopoietic cells, T cells, B cells, and the like, and have potent immunosuppressive properties. Research indicates that vomitoxin has toxic effects in different degrees due to the concentration, usually causes cell death by inhibiting cell protein synthesis, and also has embryotoxicity and induces tumor, etc. Thus, vomitoxin has been shown in many studies to be a serious "triprodogenic" toxin, i.e., carcinogenic, teratogenic, mutagenic. Animals with excessive involvement of emetic toxins or prolonged use of food containing emetic toxins may exhibit various significant toxic symptoms such as vomiting, diarrhea, skin irritation, food refusal, neurological disorders, miscarriage and stillbirth. DON is widely existed in the global scope, particularly in grains and products thereof in warm and humid areas, such as the United states, Canada, south China and the like, the DON detection rates of grains in the north and middle parts of Europe respectively reach 70 percent and 66 percent, and the domestic situation is not optimistic. In recent years, with the deterioration of climatic conditions, DON gradually spreads to the north, and the detectable rate in Zhejiang, Jiangsu, Shandong, Henan and the like is increasing. Therefore, how to remove vomitoxin in food and feed has become an urgent problem to be solved.
The vomitoxin has high stability, and has high acid resistance, pressure resistance and heat resistance. Are difficult to remove during grain processing. Currently known detoxification methods for removing vomitoxin mainly include physical detoxification methods, chemical detoxification methods, nutritional detoxification methods, toxin adsorption methods and biological enzymolysis methods. The physical detoxification methods mainly comprise a water washing method, an elimination method, an embryo removal detoxification method, a solvent extraction method, a heating detoxification method and the like, and the methods are often not ideal in effect due to the high stability of vomitoxin. The chemical detoxification method mainly adopts alkali or oxidant to carry out treatment detoxification. However, this treatment method is not suitable for the feed industry and the breeding industry in practical application. The operation is complicated, the treatment of large batch of feed raw materials cannot be carried out, and the nutrition and the palatability of the feed are often reduced after the chemical treatment. The nutritional detoxification method is characterized in that yeast selenium, antioxidant and the like are added into the mildewed feed to relieve the toxic effect of vomitoxin on cells. Although the method has a certain detoxification effect, the method can also cause the waste of nutrient substances and the lack of certain nutrient substances. The enzyme degradation treatment method has little loss and influence on the nutrient components of the feed, but the wide application of the method is limited due to high cost and unstable effect. Therefore, the toxin adsorption method is an economical and convenient method. For decades, the addition of montmorillonite has been commonly used to address the problem of mycotoxin contamination. However, researches show that the aluminosilicate adsorbent has a hydrophilic negative charge surface and is only suitable for adsorbing mycotoxins with polar groups, such as aflatoxin. And for those vomitoxin with weak polarity, the vomitoxin is not easy to be absorbed. Moreover, the adsorbent adsorbs trace elements and vitamins, which affects the production performance and health of animals. Therefore, a new adsorbent which can adsorb vomitoxin in a targeted manner is urgently needed.
Disclosure of Invention
The invention mainly aims to provide a chitin magnetic microsphere adsorbent as well as a preparation method and application thereof, and aims to provide an adsorbent capable of pertinently adsorbing vomitoxin.
In order to achieve the above purpose, the present invention provides a chitin magnetic microsphere adsorbent, which comprises chitin magnetic microspheres and polyhydroxy compounds loaded on the surfaces of the chitin magnetic microspheres.
Optionally, the polyol comprises any one of tannin and tea polyphenol.
In order to achieve the above object, the present invention further provides a method for preparing the chitin magnetic microsphere adsorbent, comprising the following steps:
step S10, stirring isooctane and Span-85 under the condition of ice-water bath for 25-35 min for reaction, adding a chitin solution, continuously stirring for reaction for 0.5-2 h, adding Tween-85, continuously stirring for reaction for 0.5-1 h, and obtaining a reaction product with solid microspheres;
step S20, heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, then adjusting the pH value to be neutral, and then cleaning and drying the solid microspheres to obtain chitin microspheres;
step S30, FeCl2·4H2Dissolving O in water, adding the chitin microspheres to form a suspension, adding a hydrogen peroxide solution into the suspension in an oxygen-isolated environment, and stirring for reaction until Fe2+Is completely oxidized into Fe3 +To prepare chitin magnetic microspheres;
step S40, adding the chitin magnetic microspheres into a polyhydroxy compound solution, and reacting until polyhydroxy compounds are loaded on the surfaces of the chitin magnetic microspheres to obtain the chitin magnetic microsphere adsorbent.
Alternatively, in step S40:
the mass concentration of the polyhydroxy compound in the polyhydroxy compound solution is 0.01-0.1 g/mL, and 3-7 g of chitin magnetic microspheres are added into every 50mL of the polyhydroxy compound solution.
Optionally, the polyhydroxy compound in step S40 is a tannin, correspondingly, step S40 comprises:
dissolving tannin in distilled water, and adjusting pH to neutral to obtain tannin solution as clear solution;
and adding the chitin magnetic microspheres into the tannin solution, reacting for 2-4 hours at 20-30 ℃, separating the microspheres after the reaction is finished, and washing the microspheres until the microspheres are neutral to prepare the chitin magnetic microsphere adsorbent.
Alternatively, the polyhydroxy compound in step S40 is tea polyphenol, and correspondingly, step S40 includes:
dissolving tea polyphenols in distilled water to obtain tea polyphenols solution;
adding the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 1-3 min at the temperature of 88-92 ℃ and the rotating speed of 300-600 rpm, and separating the microspheres after the reaction is finished to prepare the chitin magnetic microsphere adsorbent.
Optionally, before step S10, the method further includes:
dispersing purified chitin powder in a mixed system of sodium hydroxide, urea and water to form suspension;
freezing the suspension for 4-8 h at-25 to-35 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution;
and centrifuging the transparent solution at the rotating speed of 6000-10000 rpm for 15-20 min at the temperature of 0-2 ℃ to obtain the chitin solution.
Optionally, step S20 includes:
heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, adding dilute hydrochloric acid to adjust the pH value to be neutral, and separating out the solid microspheres;
firstly, washing the solid microspheres by using water and ethanol, then carrying out solvent replacement by using tert-butyl alcohol, and then carrying out freeze drying to obtain the chitin microspheres.
Optionally, step S30 includes:
FeCl is added2·4H2Dissolving O in water to obtain FeCl2Concentration of 15 ^ c45mmol/L FeCl2After the solution, the following ratio (0.2-0.4): 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension;
under the nitrogen atmosphere, according to the following formula (5-20): 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until Fe2+Is completely oxidized into Fe3+And obtaining the chitin magnetic microspheres.
Furthermore, the invention also provides application of the chitin magnetic microsphere adsorbent in adsorbing vomitoxin in food and/or feed, wherein the chitin magnetic microsphere adsorbent is prepared by the preparation method of the chitin magnetic microsphere adsorbent.
In the technical scheme provided by the invention, the chitin magnetic microsphere adsorbent is prepared by taking chitin magnetic microspheres as a carrier and loading polyhydroxy compounds, the advantages of the chitin magnetic microspheres and the polyhydroxy compounds are combined, and the obtained adsorbent has high-efficiency toxin adsorption capacity on vomitoxin in food and/or feed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing a chitin magnetic microsphere adsorbent provided by the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Aiming at the problem of poor detoxification effect of a detoxification method for removing vomitoxin in the prior art, the invention provides a chitin magnetic microsphere adsorbent, which comprises chitin magnetic microspheres and polyhydroxy compounds loaded on the surfaces of the chitin magnetic microspheres.
In the technical scheme provided by the invention, the chitin magnetic microsphere adsorbent is prepared by taking chitin magnetic microspheres as a carrier and loading polyhydroxy compounds, the advantages of the chitin magnetic microspheres and the polyhydroxy compounds are combined, and the obtained adsorbent has high-efficiency toxin adsorption capacity on vomitoxin in food and/or feed. The chitin is a second most renewable biological resource next to cellulose, widely exists in shrimp shells, crab shells and certain plants, has wide sources, and the prepared chitin-based magnetic microspheres have porous structures, large specific surface areas and many active sites, have strong adsorption effect and can efficiently adsorb vomitoxin; in addition, the chitin serving as polycation electrolyte can be used as a flocculating agent to induce the precipitation of anionic compounds, and contains a large amount of acetamido groups, so that the chitin has certain antibacterial property, bactericidal property, immunity enhancement and other properties, and the chitin magnetic microsphere adsorbent further has the additional effects of antibiosis, sterilization and immunity enhancement.
Further, the polyol includes any one of tannin and tea polyphenol. The tea polyphenol can eliminate harmful free radicals, block lipid peroxidation process and improve the activity of enzyme in human body, thereby having the effects of resisting mutation and cancer, and the tea polyphenol can improve the total immune globulin amount of human body and maintain the immune globulin amount at a high level, stimulate the change of antibody activity, thereby improving the overall immunity of human body and promoting the self-conditioning function of human body. The effect of tea polyphenol for indirectly inhibiting or killing various pathogens, germs and viruses by regulating the amount and the activity of immunoglobulin is proved by medical experiments. The tea polyphenol has strong adsorption effect on heavy metals, can form a complex with the heavy metals to generate precipitates, and is favorable for reducing the toxic action of the heavy metals on organisms. Therefore, when the chitin magnetic microsphere adsorbent loaded with tea polyphenol is applied to feed, the chitin magnetic microsphere adsorbent not only has high-efficiency vomitoxin adsorption capacity, but also is beneficial to improving the immunity of animals eating the feed, and plays a role in inhibiting or killing various pathogens.
Tannin is a cheap and widely-existing natural polymer, is a polyphenol secondary metabolite of higher plants, is a natural water-soluble organic compound, and has a molecular weight of 500-3000 daltons. Tannin is rich in source, and the plants for extracting tannin are developed as follows: valonia, red root, gallnut, larch, waxberry, pomelo, casuarina equisetifolia, sophora japonica and the like. Tannin molecules have negative charges in aqueous solution and can be used as a flocculating agent. Meanwhile, tannin has various physiological activities such as hemostasis, microorganism inhibition, antianaphylaxis, antimutation, anticancer, antitumor, anti-aging and the like. However, the natural plant tannin is used as a natural polymer and has the defects that the tannin molecule has smaller charge density and more active property, and is easy to generate oxidation reaction or degradation reaction, thereby losing activity; meanwhile, tannin is dissolved in water and directly serves as an adsorption material to easily cause secondary pollution, and the chitin magnetic microsphere loaded tannin serves as the adsorption material, so that the problems existing when the tannin is used as the adsorption material alone can be effectively solved, and the adsorption capacity and the adsorption effect on vomitoxin can be improved by combining the porous adsorption performance of the chitin magnetic microsphere.
Based on the chitin magnetic microsphere adsorbent, the invention also provides a preparation method of the chitin magnetic microsphere adsorbent, and fig. 1 shows an embodiment of the preparation method of the chitin magnetic microsphere adsorbent provided by the invention. Referring to fig. 1, in the present embodiment, a method for preparing a magnetic chitin microsphere adsorbent includes the following steps:
step S10, stirring isooctane and Span-85 under the condition of ice-water bath for 25-35 min for reaction, adding a chitin solution, continuously stirring for reaction for 0.5-2 h, adding Tween-85, continuously stirring for reaction for 0.5-1 h, and obtaining a reaction product with solid microspheres;
the chitin solution is prepared by dissolving chitin powder in an alkaline solution, and the specific steps comprise: dispersing purified chitin powder in a mixed system of sodium hydroxide, urea and water to form suspension; freezing the suspension for 4-8 h at-25 to-35 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution; centrifuging the transparent solution at the rotating speed of 6000-10000 rpm for 15-20 min at the temperature of 0-2 ℃, and removing bubbles and impurities to prepare a chitin solution; wherein the mass fraction of the chitin in the chitin solution is 6-8%.
After the chitin solution is prepared, the adding proportion and the stirring speed of reactants during the preparation of the chitin microspheres through reaction are not particularly limited, and can be limited according to the yield requirement of the chitin microspheres. In the embodiment, 50g of isooctane can be taken firstly, 1-3 g of Span-85 (Span-85) is correspondingly added, then stirring is carried out for 25-35 min under the ice-water bath condition at the rotating speed of 600-1300 rpm, then 5-25 g of chitin solution is added into the mixture of the isooctane and the Span-85 within 5min, stirring and reacting are carried out for 0.5-2 h under the same rotating speed, 4-6 g of Tween-85 (Tween-85) is added, stirring and reacting are carried out for 0.5-1 h under the same rotating speed, so as to obtain a reaction product with solid microspheres, and the whole reaction process is carried out under the ice-water bath condition of 0 ℃.
Step S20, heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, then adjusting the pH value to be neutral, and then cleaning and drying the solid microspheres to obtain chitin microspheres;
after the solid microspheres are heated to be solidified, impurities and solvents on the surfaces of the solid microspheres are removed by cleaning, and then the residual solvents and water are further removed by drying, so that the chitin microspheres are prepared, wherein the cleaning and drying modes are not particularly limited, and the impurities and the solvents on the surfaces of the microspheres can be sufficiently removed. In the present embodiment, step S20 includes: heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, adding 10% by mass of dilute hydrochloric acid to adjust the pH value to 7.0, and separating out the solid microspheres; and (2) repeatedly cleaning the solid microspheres by using water and ethanol, performing solvent replacement by using tert-butyl alcohol, and performing freeze drying to obtain the chitin microspheres.
Step S30, FeCl2·4H2Dissolving O in water, adding the chitin microspheres to form a suspension, adding a hydrogen peroxide solution into the suspension in an oxygen-isolated environment, and stirring for reaction until Fe2+Is completely oxidized into Fe3 +To prepare chitin magnetic microspheres;
the oxygen-free environment may be achieved by introducing a protective gas, such as an inert gas, e.g., nitrogen or argon, into the reaction vessel containing the reactants. In the present embodiment, the implementation method of step S30 is as follows: FeCl is added2·4H2Dissolving O in water to obtain FeCl2FeCl with the concentration of 15-45 mmol/L2After the solution, the following ratio (0.2-0.4): 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension; and then, under a nitrogen atmosphere, according to the following formula (5-20): 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until the mixture is completely dissolvedFe2+Is completely oxidized into Fe3+In this case, magnetic Fe is produced in the reaction system3O4Particles of and the Fe3O4Once the particles are generated, the chitin microspheres are loaded to prepare the chitin magnetic microspheres, so that the chitin microspheres have magnetism, and are convenient to separate and recycle in the actual application process.
Step S40, adding the chitin magnetic microspheres into a polyhydroxy compound solution, and reacting until polyhydroxy compounds are loaded on the surfaces of the chitin magnetic microspheres to obtain the chitin magnetic microsphere adsorbent.
In the embodiment, the mass concentration of the polyhydroxy compound in the polyhydroxy compound solution is 0.01-0.1 g/mL, and 3-7 g of the chitin magnetic microspheres are added into 50mL of the polyhydroxy compound solution. The polyhydroxy compound can be selected from polyhydroxy compounds such as tannin, tea polyphenol and the like, and when the selected substances are different, the mode of preparing the polyhydroxy compound solution is also different.
Wherein, when the polyhydroxy compound is tannin, correspondingly, step S40 comprises: dissolving tannin in distilled water, and adjusting pH to neutral to obtain tannin solution as clear solution; and then adding the chitin magnetic microspheres into the tannin solution, reacting for 2-4 hours at 20-30 ℃, separating the microspheres after the reaction is finished, and washing the microspheres until the microspheres are neutral to prepare the tannin-loaded chitin magnetic microsphere adsorbent.
When the polyol is tea polyphenol, step S40 includes, correspondingly: dissolving tea polyphenols in distilled water to obtain tea polyphenols solution; and then adding the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 1-3 min at the temperature of 88-92 ℃ and the rotating speed of 300-600 rpm, and separating the microspheres after the reaction is finished to prepare the tea polyphenol chitin-loaded magnetic microsphere adsorbent.
The chitin magnetic microsphere adsorbent prepared by the preparation method provided by the embodiment of the invention has an excellent adsorption effect on vomitoxin, and can be used for adsorbing the vomitoxin in food and feed, so that the invention further provides an application of the chitin magnetic microsphere adsorbent in adsorbing the vomitoxin in food and/or feed, and the chitin magnetic microsphere adsorbent is prepared by the preparation method of the chitin magnetic microsphere adsorbent. The chitin magnetic microsphere adsorbent can be used for efficiently adsorbing vomitoxin in food and/or feed, and is beneficial to correspondingly improving the performance of the food and the feed due to the corresponding physiological activity of tannin or tea polyphenol.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Dispersing 7g of purified chitin powder in 93g of a mixed system of sodium hydroxide, urea and water (the mass ratio of the sodium hydroxide to the urea to the water is 11:4:85) to form a suspension; freezing the suspension for 4h at-30 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution; centrifuging the transparent solution at 7200rpm for 15min at 0 deg.C to remove bubbles and impurities to obtain chitin solution;
(2) adding 50g of isooctane into a three-mouth flask, adding 1.1g of Span-85, stirring for 30min under the condition of ice-water bath at the rotating speed of 1000rpm, then adding 5g of prepared chitin solution into the three-mouth flask within 5min, continuously stirring and reacting for 1h at the same rotating speed, adding 5g of Tween-85 into the three-mouth flask, and continuously stirring and reacting for 1h at the same rotating speed to obtain a reaction product with solid microspheres;
(3) heating the obtained reaction product to 60 ℃, preserving heat for 5min until solid microspheres in the reaction product are solidified, then adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH value to 7.0, and separating out the solid microspheres in the reaction product; repeatedly cleaning the solid microspheres with water and ethanol, performing solvent replacement with tert-butyl alcohol, and freeze-drying to obtain chitin microspheres;
(4) FeCl is added2·4H2Dissolving O in water to obtainFeCl2FeCl with concentration of 30mmol/L2After the solution, the ratio was then adjusted to 0.3: 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension; then, under a nitrogen atmosphere, the ratio of 15: 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until Fe2+Is completely oxidized into Fe3+To prepare chitin magnetic microspheres;
(5) dissolving 2.5g of tannin in 50mL of distilled water, and adjusting the pH value to 7.0 to prepare a tannin solution which is a clear solution; and then adding 5g of the chitin magnetic microspheres into the tannin solution, reacting for 2h at 25 ℃, separating the microspheres from the tannin solution after the reaction is finished, and washing the microspheres to be neutral to prepare the tannin-loaded chitin magnetic microsphere adsorbent.
Example 2
(1) Dispersing 7g of purified chitin powder in 93g of a mixed system of sodium hydroxide, urea and water (the mass ratio of the sodium hydroxide to the urea to the water is 11:4:85) to form a suspension; freezing the suspension for 8h at-25 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution; centrifuging the transparent solution at 2 deg.C at 6000rpm for 20min to remove bubbles and impurities to obtain chitin solution;
(2) adding 50g of isooctane into a three-neck flask, adding 2.2g of Span-85, stirring for 25min under the condition of ice-water bath at the rotating speed of 1300rpm, then adding 15g of prepared chitin solution into the three-neck flask within 5min, continuously stirring and reacting for 0.5h at the same rotating speed, adding 4g of Tween-85 into the three-neck flask, and continuously stirring and reacting for 0.5h at the same rotating speed to obtain a reaction product with solid microspheres;
(3) heating the obtained reaction product to 80 ℃, preserving heat for 7min until solid microspheres in the reaction product are solidified, then adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH value to 7.0, and separating out the solid microspheres in the reaction product; repeatedly cleaning the solid microspheres with water and ethanol, performing solvent replacement with tert-butyl alcohol, and freeze-drying to obtain chitin microspheres;
(4) FeCl is added2·4H2Dissolving O in water to obtain FeCl2FeCl with concentration of 15mmol/L2After the solution, the ratio of 0.2: 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension; then, under a nitrogen atmosphere, the ratio of 5: 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until Fe2+Is completely oxidized into Fe3+To prepare chitin magnetic microspheres;
(5) dissolving 0.5g of tannin in 50mL of distilled water, and adjusting the pH value to 7.0 to prepare a tannin solution which is a clear solution; and then adding 3g of the chitin magnetic microspheres into the tannin solution, reacting for 3h at 25 ℃, separating the microspheres from the tannin solution after the reaction is finished, and washing the microspheres to be neutral to prepare the tannin-loaded chitin magnetic microsphere adsorbent.
Example 3
(1) Dispersing 7g of purified chitin powder in 93g of a mixed system of sodium hydroxide, urea and water (the mass ratio of the sodium hydroxide to the urea to the water is 11:4:85) to form a suspension; freezing the suspension for 4-8 h at-25 to-35 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution; centrifuging the transparent solution at 1 deg.C at 10000rpm for 18min to remove bubbles and impurities to obtain chitin solution;
(2) adding 50g of isooctane into a three-neck flask, adding 3g of Span-85, stirring for 35min under the ice-water bath condition at the rotating speed of 800rpm, then adding 25g of prepared chitin solution into the three-neck flask within 5min, continuously stirring and reacting for 2h at the same rotating speed, adding 4-6 g of Tween-85 into the three-neck flask, and continuously stirring and reacting for 0.8h at the same rotating speed to obtain a reaction product with solid microspheres;
(3) heating the obtained reaction product to 95 ℃, preserving the heat for 10min until solid microspheres in the reaction product are solidified, then adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH value to 7.0, and separating out the solid microspheres in the reaction product; repeatedly cleaning the solid microspheres with water and ethanol, performing solvent replacement with tert-butyl alcohol, and freeze-drying to obtain chitin microspheres;
(4) FeCl is added2·4H2Dissolving O in water to obtain FeCl2FeCl with concentration of 45mmol/L2After the solution, the ratio was then adjusted to 0.4: 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension; then, under a nitrogen atmosphere, the ratio of 20: 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until Fe2+Is completely oxidized into Fe3+To prepare chitin magnetic microspheres;
(5) dissolving 5g of tannin in 50mL of distilled water, and adjusting the pH value to 7.0 to prepare a tannin solution which is a clear solution; and then adding 7g of the chitin magnetic microspheres into the tannin solution, reacting for 4h at 25 ℃, separating the microspheres from the tannin solution after the reaction is finished, and washing the microspheres to be neutral to prepare the tannin-loaded chitin magnetic microsphere adsorbent.
Example 4
(1) The steps of (1) to (4) are the same as in example 1;
(5) dissolving 2.5g of tea polyphenol in 50mL of distilled water to prepare a tea polyphenol solution; and then adding 5g of the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 1min at the temperature of 88 ℃ and the rotating speed of 300rpm, and separating the microspheres after the reaction is finished to prepare the tea polyphenol-loaded chitin magnetic microsphere adsorbent.
Example 5
(1) The steps of (1) to (4) are the same as in example 2;
(5) dissolving 2.5g of tea polyphenol in 50mL of distilled water to prepare a tea polyphenol solution; and then adding 7g of the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 2min at the temperature of 90 ℃ and the rotation speed of 500rpm, and separating the microspheres after the reaction is finished to prepare the tea polyphenol-loaded chitin magnetic microsphere adsorbent.
Example 6
(1) The steps of (1) to (4) are the same as in example 3;
(5) dissolving 2.5g of tea polyphenol in 50mL of distilled water to prepare a tea polyphenol solution; and then adding 7g of the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 3min at the temperature of 92 ℃ and the rotation speed of 600rpm, and separating the microspheres after the reaction is finished to prepare the tea polyphenol-loaded chitin magnetic microsphere adsorbent.
The chitin magnetic microspheres prepared in step (5) of example 1 are used as a comparative example, and the chitin magnetic microspheres adsorbent prepared in examples 1 to 6 are used as an adsorbent for adsorbing vomitoxin, and the adsorption performance of the chitin magnetic microspheres adsorbent is tested, and the method and the result are as follows:
preparing a vomitoxin solution with the concentration of 10 mug/mL, correspondingly adding 5mg of chitin magnetic microsphere adsorbent into every 2mL of the vomitoxin solution, magnetically stirring for 24 hours at normal temperature at the rotating speed of 500rpm, separating microspheres in the solution after stirring, and detecting the content of the vomitoxin in filtrate by using high performance liquid chromatography, wherein the results are shown in the following table 1.
TABLE 1 concentration of emetic toxin solution before and after treatment with chitin magnetic microsphere adsorbent
Figure BDA0002398788950000121
As can be seen from the results in table 1, compared with the chitin magnetic microspheres in the comparative example, the chitin magnetic microspheres loaded with tannin or tea polyphenol have more remarkable adsorption capacity to vomitoxin, and the highest adsorption rate can reach 95%; in addition, the loading capacity of tannin or tea polyphenol on the magnetic chitin carbonized microspheres has a large influence on the adsorption effect of the finally prepared adsorbent on the vomitoxin, and the effect of the chitin magnetic microspheres loaded with tea polyphenol on adsorbing the vomitoxin is slightly good under the same condition.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (9)

1. The chitin magnetic microsphere adsorbent is characterized by comprising chitin magnetic microspheres and polyhydroxy compounds loaded on the surfaces of the chitin magnetic microspheres;
wherein the polyhydroxy compound comprises any one of tannin and tea polyphenol.
2. The preparation method of the chitin magnetic microsphere adsorbent is characterized by comprising the following steps of:
step S10, stirring isooctane and Span-85 under the condition of ice-water bath for 25-35 min for reaction, adding a chitin solution, continuously stirring for reaction for 0.5-2 h, adding Tween-85, continuously stirring for reaction for 0.5-1 h, and obtaining a reaction product with solid microspheres;
step S20, heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, then adjusting the pH value to be neutral, and then cleaning and drying the solid microspheres to obtain chitin microspheres;
step S30, FeCl2·4H2Dissolving O in water, adding the chitin microspheres to form a suspension, adding a hydrogen peroxide solution into the suspension in an oxygen-isolated environment, and stirring for reaction until Fe2+Is completely oxidized into Fe3+To prepare chitin magnetic microspheres;
step S40, adding the chitin magnetic microspheres into a polyhydroxy compound solution, and reacting until polyhydroxy compounds are loaded on the surfaces of the chitin magnetic microspheres to prepare chitin magnetic microsphere adsorbents;
wherein the polyhydroxy compound comprises any one of tannin and tea polyphenol.
3. The method for preparing the chitin magnetic microsphere adsorbent of claim 2, wherein in step S40:
the mass concentration of the polyhydroxy compound in the polyhydroxy compound solution is 0.01-0.1 g/mL, and 3-7 g of chitin magnetic microspheres are added into every 50mL of the polyhydroxy compound solution.
4. The method of claim 2, wherein the polyol in step S40 is tannin, and step S40 comprises:
dissolving tannin in distilled water, and adjusting pH to neutral to obtain tannin solution as clear solution;
and adding the chitin magnetic microspheres into the tannin solution, reacting for 2-4 hours at 20-30 ℃, separating the microspheres after the reaction is finished, and washing the microspheres until the microspheres are neutral to prepare the chitin magnetic microsphere adsorbent.
5. The method of claim 2, wherein the polyol in step S40 is tea polyphenol, and step S40 comprises the steps of:
dissolving tea polyphenols in distilled water to obtain tea polyphenols solution;
adding the chitin magnetic microspheres into the tea polyphenol solution, stirring and reacting for 1-3 min at the temperature of 88-92 ℃ and the rotating speed of 300-600 rpm, and separating the microspheres after the reaction is finished to prepare the chitin magnetic microsphere adsorbent.
6. The method of claim 2, wherein before step S10, the method further comprises:
dispersing purified chitin powder in a mixed system of sodium hydroxide, urea and water to form suspension;
freezing the suspension for 4-8 h at-25 to-35 ℃, then stirring and thawing at room temperature, freezing and thawing again to prepare a transparent solution;
and centrifuging the transparent solution at the rotating speed of 6000-10000 rpm for 15-20 min at the temperature of 0-2 ℃ to obtain the chitin solution.
7. The method of claim 2, wherein step S20 comprises:
heating the reaction product to 60-95 ℃, preserving heat for 5-10 min until solid microspheres in the reaction product are solidified, adding dilute hydrochloric acid to adjust the pH value to be neutral, and separating out the solid microspheres;
firstly, washing the solid microspheres by using water and ethanol, then carrying out solvent replacement by using tert-butyl alcohol, and then carrying out freeze drying to obtain the chitin microspheres.
8. The method of claim 2, wherein step S30 comprises:
FeCl is added2·4H2Dissolving O in water to obtain FeCl2FeCl with the concentration of 15-45 mmol/L2After the solution, the following ratio (0.2-0.4): 100 mass ratio of feed liquid to the FeCl2Adding the chitin microspheres into the solution to form a suspension;
under the nitrogen atmosphere, according to the following formula (5-20): 100, adding hydrogen peroxide solution into the suspension and stirring for reaction until Fe2+Is completely oxidized into Fe3+And obtaining the chitin magnetic microspheres.
9. The application of chitin magnetic microsphere adsorbent in adsorbing vomitoxin in food and/or feed is characterized in that the chitin magnetic microsphere adsorbent is prepared by the preparation method of the chitin magnetic microsphere adsorbent according to any one of claims 2 to 8.
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