CN110051647B - Hericium erinaceus polysaccharide chelated zinc microcapsule and preparation method thereof - Google Patents

Hericium erinaceus polysaccharide chelated zinc microcapsule and preparation method thereof Download PDF

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CN110051647B
CN110051647B CN201910253349.9A CN201910253349A CN110051647B CN 110051647 B CN110051647 B CN 110051647B CN 201910253349 A CN201910253349 A CN 201910253349A CN 110051647 B CN110051647 B CN 110051647B
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hericium erinaceus
erinaceus polysaccharide
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陈义勇
冀宏
薛依婷
高荣
张泽
徐紫依
张子轶
丁霄
吴欣怡
蒋晗
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Changshu Institute of Technology
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Abstract

The invention discloses a hericium erinaceus polysaccharide chelated zinc microcapsule and a preparation method thereof, the hericium erinaceus polysaccharide chelated zinc microcapsule is prepared by taking hericium erinaceus polysaccharide as a raw material and chelating the hericium erinaceus polysaccharide with zinc ions to form a polysaccharide zinc chelate, and the hericium erinaceus polysaccharide chelated zinc microcapsule is prepared by taking carrageenan, namely chitosan and beta-cyclodextrin as wall materials, homogenizing, emulsifying, spraying and drying the wall materials and microencapsulating the wall materials, so that the problems that the traditional hericium erinaceus polysaccharide has poor antioxidant activity and the zinc content in the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) is not high are solved; the method has the advantages that the dispersibility, the emulsifying dispersibility and other capabilities of the hericium erinaceus polysaccharide can be improved, the easily-oxidized components in the polysaccharide are protected, the stability and the antioxidant activity of the polysaccharide are enhanced, the shelf life is prolonged, the prepared hericium erinaceus polysaccharide chelated zinc microcapsule has obvious antioxidant activity, immunity enhancing and anticancer effects, the preparation method is simple and convenient, the industrial continuous production can be realized, and the practical value is wide.

Description

Hericium erinaceus polysaccharide chelated zinc microcapsule and preparation method thereof
Technical Field
The invention belongs to the field of polysaccharide extraction and preparation, and particularly belongs to the technical field of hericium erinaceus polysaccharide chelated zinc microcapsules and a preparation method thereof.
Background
Hericium erinaceus (Hericium erinaceus), also known as Hericium erinaceus, belongs to Hericiaceae and Hericium, is a precious edible fungus growing in dense forests, and is a traditional edible material with homology of medicine and food. The Hericium erinaceus is white when fresh, and is light yellow or light brown after being dried. In China, the hericium erinaceus produced in Xiaoxingan Anlin and Wandashan are most popular, and currently, the hericium erinaceus are cultivated all over the country due to the development of artificial culture technology.
Hericium Erinaceus Polysaccharides (HEP) are important active substances in the fruiting body of Hericium erinaceus. Giardia, etc. separates 5 kinds of polysaccharide HEP-1-HEP-5 from fruiting body of Hericium erinaceus, and analyzes sugar component. The Hericium erinaceus polysaccharide has multiple physiological functions of improving immunity, resisting tumor, resisting aging, reducing blood lipid, etc., and can be widely applied to medicines and health products. The results of experiments on delayed allergic reaction and lymphocyte transformation on mice of Luozhen and the like on the immune function of hericium erinaceus prove that the hericium erinaceus sporophore polysaccharide and the hericium erinaceus mycelium polysaccharide have the effect of enhancing the immune function of the mice.
The zinc element is one of the trace elements necessary for human body, it is involved in maintaining the physiological function and normal metabolism of human body, and is closely related to growth, development, cell division, tissue repair and the like of human body, and at the same time, the zinc element is also an indispensable component or an activator for more than 80 enzymes such as carbonic anhydrase, lactic dehydrogenase and the like of the body. Research shows that children suffering from zinc deficiency can cause growth retardation, delayed sexual maturation and the like; if pregnant women suffer from zinc deficiency, the development of fetuses can be influenced to different degrees, and fetal deformity can be caused seriously; in addition, the lack of zinc in the body of both children and adults can cause the appearance of reduced taste, inappetence and pica, and the reduction of dark adaptation ability can also occur when the zinc deficiency is severe; acute zinc deficiency is manifested by skin damage and alopecia, and can also cause lethargy, diarrhea, depression, etc.
The development of polysaccharide biological activity is closely related to the structure, and the introduction of chemical groups often enhances the biological activity of polysaccharide or generates new activity, so that the proper modification of polysaccharide structure becomes a major focus in the field of polysaccharide research. The polysaccharide is chelated with some metal or nonmetal ions, so that the polysaccharide has more specific structure and biological activity. The technology is widely applied to a plurality of fields such as chemical industry, medicine, agriculture, food and the like at present, and chelates formed by polysaccharide and metal ions such as iron, calcium, copper, rare earth elements and the like are also developed to be used as clinical medicines and health care products for people in large quantities.
Microcapsules are micro-particles with semi-permeability or sealing property formed by encapsulating uniformly dispersed solid substance particles, liquid or gas in a micro-container or package with a specific polymer wall shell, and are a controlled release system widely used at present. The microcapsule technology has many advantages, is beneficial to protecting core materials from environmental influences, can effectively mask the color and smell of the core materials, change the volume, state or surface performance of the core materials, reduce the volatility or toxicity, control the sustainable release of the core materials and the like. The microcapsule technology has been widely applied to various fields of biological medicine, food, cosmetics and the like, and has wide application prospect.
At present, few research reports are reported on microcapsule coating after chemical modification of hericium erinaceus polysaccharide, and no research is reported on microcapsule preparation after a chelate is formed by the hericium erinaceus polysaccharide and zinc ions. The method for preparing the hericium erinaceus polysaccharide chelated zinc microcapsules efficiently and simply needs to be found out in an urgent way due to the combination of the biological activity characteristics of the hericium erinaceus polysaccharide, the blank of the research on the current hericium erinaceus polysaccharide and metal chelation, the single type of zinc nutritional supplements in the market and the easy oxidation of polysaccharide chelate intermediates. Provides a certain theoretical basis for the research of developing novel hericium erinaceus polysaccharide products.
Disclosure of Invention
The invention aims to provide a hericium erinaceus polysaccharide chelated zinc microcapsule and a preparation method thereof, the hericium erinaceus polysaccharide chelated zinc microcapsule is prepared by taking hericium erinaceus polysaccharide as a raw material and chelating the hericium erinaceus polysaccharide with zinc ions to form a polysaccharide zinc chelate, and the polysaccharide zinc chelate microcapsule is prepared by taking carrageenan, namely chitosan and beta-cyclodextrin as wall materials, homogenizing, emulsifying, spraying and drying the wall materials and microencapsulating the wall materials, so that the problems that the traditional hericium erinaceus polysaccharide has poor antioxidant activity and the zinc content in the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) is not high are solved; the method has the advantages that the dispersibility, the emulsifying dispersibility and other capabilities of the hericium erinaceus polysaccharide can be improved, the easily-oxidized components in the polysaccharide are protected, the stability and the antioxidant activity of the polysaccharide are enhanced, the shelf life is prolonged, the prepared hericium erinaceus polysaccharide chelated zinc microcapsule has obvious antioxidant activity, immunity enhancing and anticancer effects, the preparation method is simple and convenient, the industrial continuous production can be realized, and the practical value is wide.
The invention is realized by the following technical scheme:
the invention provides a preparation method of hericium erinaceus polysaccharide chelated zinc microcapsules, which specifically comprises the following technical steps:
(1) preparing hericium erinaceus polysaccharide chelated zinc (Zn-HEP): preparing 12.5g/L-17.5g/L hericium erinaceus polysaccharide solution, taking 20mL-30mL of polysaccharide solution, adding 20mL-30mL of ZnSO with concentration of 0.4mol/L-0.5mol/L4Stirring the solution at 30-50 ℃ for 2-4 h, dialyzing the reaction solution for 7-9 h by running water, and drying to obtain Hericium erinaceus polysaccharide chelated zinc (Zn-HEP), wherein the zinc content is 4-6 mg/g;
(2) preparing hericium erinaceus polysaccharide chelated zinc microcapsules: taking carrageenan, chitosan concentrate and beta-cyclodextrin as wall materials, adding 0.1-0.3% of potassium polyphosphate into the wall materials with the core-wall ratio of 1:9-1:11 and the solid content of 25-39%, stirring and homogenizing, wherein the homogenizing pressure is 25MPa, the homogenizing temperature is 60 ℃, the spray drying air inlet temperature is 190 ℃, the air outlet temperature is 60-80 ℃, the spray pressure is 25MPa, and drying is carried out in a constant-temperature drying box at 40-50 ℃ to prepare the hericium erinaceus polysaccharide chelated zinc microcapsule.
Preferably, the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) has the zinc content of 5.2 mg/g.
Preferably, the hericium erinaceus polysaccharide solution with the concentration of 15g/L is prepared, and 25mL of the polysaccharide solution is taken.
Preferably, 25mL of ZnSO with the concentration of 0.45mol/L is added in the invention4And (3) solution.
Preferably, the reaction solution is stirred and reacted for 3 hours at the temperature of 40 ℃, and the reaction solution is dialyzed for 8 hours by running water.
Preferably, the wall material comprises carrageenan, chitosan and beta-cyclodextrin in parts by weight, wherein the carrageenan, the chitosan and the beta-cyclodextrin are 1:2:2, the core-wall ratio is 1:10, the solid content is 27%, and 0.2% of potassium polyphosphate is added.
Preferably, the spray drying is carried out in a constant-temperature drying box at the air inlet temperature of 190 ℃, the air outlet temperature of 75 ℃ and the spray pressure of 25MPa at 45 ℃.
According to the invention, the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsules can reach 95.62%, and the yield is 89.43%; the average grain diameter of the obtained hericium erinaceus polysaccharide chelated zinc microcapsules is 6-8 mu m.
Meanwhile, the hericium erinaceus polysaccharide chelated zinc microcapsule prepared by the preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule is adopted.
Further, the invention provides an application of the hericium erinaceus polysaccharide chelated zinc microcapsule in preparation of anti-cancer drugs. The prepared hericium erinaceus polysaccharide chelated zinc microcapsule has no obvious cytotoxicity on AGS, DLD-1 and HeLa cancer cells, has strong activation effect on mouse macrophages, has immunological activity, can be used as an immunomodulator, can be applied to preparation of anti-cancer drugs, and can be widely applied to the fields of medicines, sanitation or health care products.
The new invention adopts the prior common general knowledge as the basis of the prior art. In fact, except for the original invention, any invention is not based on the prior art means and the technical elements, and is the result of further innovation on the basis of the prior art means. The technology of diluting, stirring, dialyzing, drying, homogenizing, spray drying and the like is the basis of the prior art, but how to fully chelate zinc ions in hericium erinaceus polysaccharide chelated zinc (Zn-HEP) and hericium erinaceus polysaccharide, how to coordinate the proportion between microcapsule wall materials and hericium erinaceus polysaccharide chelated zinc solution, how to maximize chelated zinc ions in a series of preparation of hericium erinaceus polysaccharide chelated zinc microcapsules, improve the characteristics of antioxidant activity and embedding rate of the microcapsules, how to exactly represent that the prepared hericium erinaceus polysaccharide chelated zinc microcapsules have strong activation effect on mouse macrophages, have immunological activity, can be used as an immunomodulator to be applied to preparation of anticancer drugs, and are obtained by repeated verification through a series of unforeseen scientific experiments. Due to the reasons, the application provides the hericium erinaceus polysaccharide chelated zinc microcapsule and the preparation method thereof by utilizing the conventional technical means as the basis and through scientific experiments on the basis, the technical steps in the provided preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule form a whole, the whole preparation method has inseparability and the technical steps cannot be randomly decomposed, the whole preparation method can achieve the highest zinc ion chelating rate, the better oxidation resistance effect and the better embedding rate, the preparation method is simple and convenient, the industrial continuous production can be realized, and the preparation method has wide practical value.
By implementing the technical scheme of the invention, the following beneficial effects can be achieved:
(1) according to the hericium erinaceus polysaccharide chelated zinc microcapsule provided by the invention, the zinc content in the hericium erinaceus polysaccharide chelated zinc is 5.2mg/g, and the hericium erinaceus polysaccharide chelated zinc microcapsule is in a granular shape with a concave surface through observation of a scanning electron microscope.
(2) The hericium erinaceus polysaccharide chelated zinc microcapsule and the preparation method thereof provided by the invention have the advantages that hericium erinaceus polysaccharide is used as a raw material, is chelated with zinc ions to form a polysaccharide zinc chelate, and is homogenized, emulsified and spray-dried by taking carrageenan, chitosan and beta-cyclodextrin as wall materials to carry out microencapsulation treatment, so that the hericium erinaceus polysaccharide chelated zinc microcapsule is prepared, the capacities of dispersibility, emulsifying dispersibility and the like of the hericium erinaceus polysaccharide chelated zinc microcapsule can be improved, the protection effect of easily-oxidized components in the polysaccharide can be enhanced, the stability of the polysaccharide is enhanced, the shelf life is prolonged, the preparation method is simple and convenient, the industrial continuous production can be realized, and the hericium erinaceus polysaccharide chelated zinc microcapsule.
(3) The hericium erinaceus polysaccharide chelated zinc microcapsule provided by the invention has a certain removing capacity, the removing capacity is increased along with the increase of concentration, and the removing capacity of the 1.0mg/mL hericium erinaceus polysaccharide chelated zinc microcapsule on DPPH free radicals reaches 70.24%, which is improved by 3.14% compared with that before chelation; 1.0mg/mL hericium erinaceus polysaccharide chelated zinc microcapsule to O2 -The scavenging capacity of free radicals reaches 55.74 percent and is improved by 12.12 percent compared with that before chelation, which shows that the antioxidation of the hericium erinaceus polysaccharide chelated zinc microcapsule after chelation is obviously improved compared with that of the Hericium Erinaceus Polysaccharide (HEP) before chelation.
(4) According to the hericium erinaceus polysaccharide chelated zinc microcapsule and the preparation method thereof, the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsule can reach 95.62%. The yield was 89.43%; the average grain diameter of the obtained hericium erinaceus polysaccharide chelated zinc microcapsules is 6-8 mu m.
(5) The hericium erinaceus polysaccharide chelated zinc microcapsule provided by the invention has obvious effects of enhancing the immune function and resisting cancer, and in-vitro experiments show that the hericium erinaceus polysaccharide chelated zinc microcapsule has no obvious cytotoxicity to AGS, DLD-1 and HeLa cancer cells, but has strong activation effect on mouse macrophages, has immunological activity, can be used as an immunomodulator, can be applied to preparation of anti-cancer drugs, and can be widely applied to the fields of medicines, sanitation or health care products.
Drawings
FIG. 1 is a graph showing the effect of polysaccharide concentration on the zinc content in Zn-HEP.
FIG. 2 is a graph showing the effect of reaction temperature on the zinc content in Zn-HEP.
FIG. 3 is a graph showing the effect of reaction time on the zinc content in Zn-HEP.
FIG. 4 shows a response plot of the effect of polysaccharide concentration and reaction time interaction on zinc content.
FIG. 5 is a graph showing the response of the interaction of polysaccharide concentration and reaction temperature on the effect of zinc content.
FIG. 6 is a graph showing the response of the interaction of reaction time and reaction temperature on the effect of zinc content.
FIG. 7 shows HEP and Zn-HEP infrared spectra.
Figure 8 shows the surface morphology of HEP at 25000 times.
FIG. 9 shows the surface morphology of Zn-HEP at 20000 times.
FIG. 10 is a graph showing the effect of HEP and Zn-HEP microcapsules on DPPH radical scavenging.
FIG. 11 shows HEP and Zn-HEP microcapsules vs. O2Graph of scavenging action of free radicals.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention, but the present invention is not limited to the following examples.
The invention adopts fresh Hericium erinaceus.
Reagents used in the invention: human gastric adenocarcinoma cells (AGS), colon adenocarcinoma cells (DLD-1), and cervical cancer cells (HeLa) were purchased from the American Standard Biometrics Collection center; DPPH, Tris, zinc standard solution, absolute ethyl alcohol, hydrogen peroxide, hydrochloric acid, sodium acetate, acetic acid, monopotassium phosphate, dipotassium phosphate, ferrous sulfate, salicylic acid and pyrogallol, wherein the reagents are analytically pure.
The apparatus and equipment used in the present invention: HK-20B swinging type high-speed traditional Chinese medicine pulverizer, HH-2 intelligent digital display constant-temperature water bath, RE-52A rotary evaporator, SHB-B95 circulating water type multipurpose vacuum pump, EL-800 enzyme linked detector, DF-101S constant-temperature heating magnetic stirrer, FTIR-650 Fourier transform infrared spectrometer, TAS-990 atomic absorption spectrophotometer and ZEISS Sigma IGMA thermal field emission scanning electron microscope.
In addition, in the following examples, unless otherwise specified, all reagents, materials and apparatuses used in the present invention are well known and used in the art, but the present invention is not limited to the practice thereof, and other reagents and apparatuses well known in the art may be applied to the practice of the following embodiments of the present invention.
The first embodiment is as follows: preparation of hericium erinaceus polysaccharide chelated zinc microcapsule
The invention provides a preparation method of hericium erinaceus polysaccharide chelated zinc microcapsules, which specifically comprises the following technical steps:
(1) preparing hericium erinaceus polysaccharide chelated zinc (Zn-HEP): preparing 12.5g/L-17.5g/L hericium erinaceus polysaccharide solution, taking 20mL-30mL of polysaccharide solution, adding 20mL-30mL of ZnSO with concentration of 0.4mol/L-0.5mol/L4Stirring the solution at 30-50 deg.C for 2-4 h, dialyzing the reaction solution with flowing water for 7-9 h, and drying to obtain Hericium erinaceus polysaccharide chelated zinc (Zn-HEP) with zinc content of 4-6 mg/g.
(2) Preparing hericium erinaceus polysaccharide chelated zinc microcapsules: taking carrageenan, chitosan concentrate and beta-cyclodextrin as wall materials, adding 0.1-0.3% of potassium polyphosphate into the wall materials with the core-wall ratio of 1:9-1:11 and the solid content of 25-39%, stirring and homogenizing, wherein the homogenizing pressure is 25MPa, the homogenizing temperature is 60 ℃, the spray drying air inlet temperature is 190 ℃, the air outlet temperature is 60-80 ℃, the spray pressure is 25MPa, and drying is carried out in a constant-temperature drying box at 40-50 ℃ to prepare the hericium erinaceus polysaccharide chelated zinc microcapsule.
Preferably, the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) has the zinc content of 5.2 mg/g.
Preferably, the hericium erinaceus polysaccharide solution with the concentration of 15g/L is prepared, and 25mL of the polysaccharide solution is taken.
Preferably, 25mL of ZnSO with the concentration of 0.45mol/L is added in the invention4And (3) solution.
Preferably, the reaction solution is stirred and reacted for 3 hours at the temperature of 40 ℃, and the reaction solution is dialyzed for 8 hours by running water.
Preferably, the wall material comprises carrageenan, chitosan and beta-cyclodextrin in parts by weight, wherein the carrageenan, the chitosan and the beta-cyclodextrin are 1:2:2, the core-wall ratio is 1:10, the solid content is 27%, and 0.2% of potassium polyphosphate is added.
Preferably, the spray drying is carried out in a constant-temperature drying box at the air inlet temperature of 190 ℃, the air outlet temperature of 75 ℃ and the spray pressure of 25MPa at 45 ℃.
According to the invention, the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsules can reach 95.62%, and the yield is 89.43%; the average grain diameter of the obtained hericium erinaceus polysaccharide chelated zinc microcapsules is 6-8 mu m.
Example two: preparation of Hericium Erinaceus Polysaccharide (HEP)
Drying and crushing the purchased hericium erinaceus, and sieving the crushed hericium erinaceus with a 60-mesh sieve to obtain dried hericium erinaceus powder. Extracting Hericium erinaceus powder with distilled water at 90 deg.C for 3 hr at a ratio of 1: 30. Centrifuging the leaching solution at 4000r/min for 10min, discarding the precipitate, and mixing the supernatants. And (3) performing rotary evaporation on the combined supernate to 1/3 of the original volume, adding 4 times of 95% ethanol for precipitating overnight, centrifuging, collecting precipitate, and drying to obtain the hericium erinaceus crude polysaccharide (HEP).
Redissolving the dried HEP with distilled water to remove proteins, adding Sevage reagent (n-butanol: chloroform: 1:4) in an amount of 1/4 vol of the concentrated solution, stirring at room temperature for 20min, centrifuging at 2600r/min, and mixing the supernatant. And (3) after the supernatant is subjected to reduced pressure concentration, adding 4 times volume of 95% ethanol for alcohol precipitation and drying to obtain purified HEP for later use.
And (3) measuring the polysaccharide content of the purified hericium erinaceus polysaccharide by adopting a phenol-sulfuric acid method. Drawing a standard curve by taking glucose as a standard sample and H2O as a blank test. 1.4mL of standard solutions of different concentrations were taken and water was added sequentially to a final volume of 2 mL. Adding 2mL of phenol solution with the mass fraction of 6% into each test tube, uniformly mixing, and sequentially and slowly adding 6mL of concentrated H2SO4Then, the mixture was cooled in cold water, mixed well and absorbance was measured at 490 nm. And (3) drawing a standard curve by taking the polysaccharide concentration as an abscissa and the absorbance as an ordinate to obtain a linear equation: a is 0.0036C +0.803, correlation coefficient r2＝0.9822。
Example three: preparation of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing Hericium erinaceus polysaccharide solution with concentration of 7.5g/L, taking 35mL of polysaccharide solution, adding 30mL of ZnSO with concentration of 0.35mol/L4The solution is stirred and reacted for 6 hours at the temperature of 30 ℃. Dialyzing the reaction solution for 6h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP).
Example four: preparation of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing 12.5g/L Hericium erinaceus polysaccharide solution, collecting 30mL polysaccharide solution, adding 35mL ZnSO with concentration of 0.4mol/L4The solution was stirred at 50 ℃ for 5 h. The reaction solution was dialyzed with running waterAnd 7h, drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP).
Example five: preparation of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing Hericium erinaceus polysaccharide solution with concentration of 15g/L, taking 25mL of polysaccharide solution, adding 25mL of ZnSO with concentration of 0.45mol/L4The solution was stirred at 40 ℃ for 3 h. Dialyzing the reaction solution for 8h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP).
Example six: preparation of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing 10g/L Hericium erinaceus polysaccharide solution, taking 20mL of polysaccharide solution, adding 15mL of ZnSO with concentration of 0.5mol/L4The solution was stirred at 60 ℃ for 4 h. Dialyzing the reaction solution for 9h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP).
Example seven: preparation of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing 17.5g/L Hericium erinaceus polysaccharide solution, taking 15mL of polysaccharide solution, adding 20mL of 0.55mol/L ZnSO4The solution was stirred at 70 ℃ for 2 h. Dialyzing the reaction solution for 10h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP).
Example eight: optimization of preparation process of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
Preparing hericium erinaceus polysaccharide chelated zinc (Zn-HEP) by the five different schemes provided in the third to seventh embodiments according to the preparation method provided in the second embodiment:
in order to determine the optimal preparation method of hericium erinaceus polysaccharide chelated zinc (Zn-HEP), the zinc content in the chelate is taken as an index, and single-factor experiments are carried out on the polysaccharide concentration, the reaction temperature and the reaction time. On the basis, according to a Box-Behnken center combination method, three-factor three-level test design is carried out, and response surface analysis is carried out.
1. Inspection method
Determination of zinc content in hericium erinaceus polysaccharide chelated zinc (Zn-HEP): zinc standard solutions of concentrations of 0, 0.4, 0.8, 1.2, 1.6, 2.0, 2.4, and 2.8mg/mL were prepared from 1mg/mL zinc standard solutions, and absorbance measurements were performed using an atomic absorption spectrophotometer. And drawing a standard curve by taking the zinc concentration as an abscissa and the absorbance as an ordinate to obtain an equation: Y0.2487X + 0.0549. Wherein: y is absorbance; x is the concentration of zinc ions, mg/L.
2. Single factor test
(1) Effect of HEP concentration on Zinc content
Taking 25mL of HEP solution (7.5, 10, 12.5, 15, 17.5g/L) with different concentrations, and adding 25mL of ZnSO with the concentration of 0.0.45mol/L4The reaction time of the solution is controlled at 50 ℃ for 3h to investigate the influence of different polysaccharide concentrations on the zinc content in Zn-HEP.
The effect of different polysaccharide concentrations on the zinc content in Zn-HEP is shown in figure 1. The influence of the polysaccharide concentration on the zinc content in the Zn-HEP after chelating zinc ions is studied by increasing the polysaccharide concentration from 7.5g/L by 2.5g/L, and as can be seen from figure 1, the zinc content in the Zn-HEP increases with the increase of the polysaccharide concentration, reaches the maximum at 17.5g/L, and the zinc content in the Zn-HEP begins to decrease after the polysaccharide concentration is continuously increased. With the continuous increase of the polysaccharide concentration in the reaction system, polysaccharide molecules reacting with zinc ions gradually increase, but with the continuous increase of the polysaccharide concentration, the polysaccharide molecules begin to be excessive, so that the zinc content in Zn-HEP is slightly reduced after the zinc content reaches the maximum. Therefore, the optimal polysaccharide concentration for Zn-HEP preparation is 17.5 g/L.
(2) Effect of reaction temperature on Zinc content
Taking 25mL of HEP solution with the concentration of 12.5g/L, adding 25L of ZnSO with the concentration of 0.45mol/L4The solution, the reaction temperature (30, 40, 50, 60, 70 ℃) is changed, and the reaction time is controlled for 3 hours, so as to investigate the influence of the reaction temperature on the zinc content in Zn-HEP.
The effect of reaction temperature on the zinc content of Zn-HEP is shown in FIG. 2. The effect of different reaction temperatures on the zinc content in Zn-HEP was investigated in 10 ℃ increments starting from 30 ℃. As can be seen from the attached figure 2, in the range of 30 ℃ to 40 ℃, the zinc content increases along with the increase of the temperature, reaches the maximum value at 40 ℃, and the zinc content gradually decreases when the temperature of the reaction system is continuously increased. Indicating that excessive temperatures are detrimental to the chelation of HEP with zinc ions. Therefore, the optimum temperature for Zn-HEP preparation is 40 ℃.
(3) Effect of reaction time on Zinc content
Taking 25mL of HEP solution with the concentration of 12.5g/L, adding 25L of ZnSO with the concentration of 0.45mol/L4Solution, reaction temperature 50 ℃, reaction time (2, 3, 4, 5, 6h) was varied to investigate the effect of reaction time on the zinc content in Zn-HEP.
The effect of reaction time on the zinc content of Zn-HEP is shown in FIG. 3. The effect of different reaction times on the zinc content in the Zn-HEP was investigated in 1h increments starting from 2 h. As can be seen from the attached FIG. 3, the reaction time gradually increases from 2h, and the zinc content in Zn-HEP also increases, reaching the maximum value when the reaction time is 4 h. However, the Zn content in Zn-HEP decreased rather after 4h with increasing reaction time, which may be due to too long reaction time promoting degradation of the polysaccharide, resulting in a decrease of the Zn content in Zn-HEP. Therefore, the reaction time for Zn-HEP preparation was 4 h.
3. Response surface optimization test
A three-factor three-level response surface test is designed by utilizing Design-Expert 8.0.6, the three selected factors are polysaccharide concentration, reaction time and reaction temperature respectively, the level determination of each factor is based on the result of a single-factor test, namely the polysaccharide concentration is 17.5g/L, the reaction time is 4h and the reaction temperature is 40 ℃. The response surface test design and the horizontal values are shown in table 1, and the Box-Behnken test design and the response values are shown in table 2.
Table 1: factor level coding table
Figure BDA0002012921780000141
Table 2: response surface test protocol and results
Figure BDA0002012921780000142
Analyzing the data in the table 4 by using Design-Expert 8.0.6, and performing regression analysis on all factors to obtain the zinc content versus polysaccharide concentration (A) and the reverseThe ternary quadratic regression equation of the reaction time (B) and the reaction temperature (C) is as follows: y is 4.92-0.41A-0.24B +0.091C +0.68AB-0.029AC-0.20BC-0.61A2-0.43B2-1.51C2
The results of the analysis of variance on the multiple regression equation of the above formula are shown in table 3. FModel (model)A value of 15.84, PModel (model)0.0007 < 0.05, indicating significance of the model. R of this model20.9532, which shows better fit; r2 Adj0.8930, the secondary regression model is said to be able to interpret changes in 89.3% response values; and 9.21% of C.V., the regression model is reliable and can be used for predicting test results. Performing regression equation coefficient significance test on the model, wherein the first term A and the second term A2、B2、C2The effect on the response value zinc content is significant.
Table 3: analysis of variance of the Y regression model
Figure BDA0002012921780000151
Note: p values less than 0.0001 are highly significant; p values less than 0.05 were significant.
4. Effect of Interfactor interactions on Zinc content
The three-dimensional response surface curves formed by the factors on the response value zinc content are shown in the attached figures 4, 5 and 6, the three-dimensional response surface curves can show the influence of the factors and the interaction thereof on the response value, and when the polysaccharide concentration is 15-17 g/L and the reaction time is 3-3.5 h, the zinc content in Zn-HEP is maintained at a high level; when the polysaccharide concentration was varied from 17g/L to 20g/L and the reaction time was varied from 3.5h to 5h, the zinc content began to decrease with increasing concentration and time.
5. Optimum process conditions for chelation
The optimal process conditions of HEP chelated zinc ions obtained by analyzing the response surface result by Design-Expert 8.0.6 software are as follows: the hericium erinaceus polysaccharide concentration is 15.29g/L, the reaction is carried out for 3 hours at the temperature of 41.04 ℃, and the zinc content in chelated Zn-HEP is 5.229 mg/g. And (3) carrying out verification tests according to experimental conditions obtained by software analysis, wherein in order to enable the tests to have higher feasibility, the process conditions are adjusted to be that the concentration of the hericium erinaceus polysaccharide is 15g/L, the reaction temperature is 40 ℃, the reaction time is 3 hours, and the reaction is repeated for 3 times. The zinc content in the finally obtained Zn-HEP is 5.2mg/g, the difference with the predicted value analyzed by software is small, and the model is accurate.
According to the optimization of the experiment, the preparation method of the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) comprises the steps of preparing a hericium erinaceus polysaccharide solution with the concentration of 12.5g/L-17.5g/L, taking 20mL-30mL of the polysaccharide solution, adding 20mL-30mL of ZnSO with the concentration of 0.4mol/L-0.5mol/L4The solution is stirred and reacts for 3 to 5 hours at the temperature of between 30 and 50 ℃. Dialyzing the reaction solution for 7-9 h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP). Through further series of experimental verification, the invention more preferably provides a preparation method of hericium erinaceus polysaccharide chelated zinc (Zn-HEP), which comprises the steps of preparing a hericium erinaceus polysaccharide solution with the concentration of 15g/L, taking 25mL of the polysaccharide solution, adding 25mL of ZnSO with the concentration of 0.45mol/L4The solution was stirred at 40 ℃ for 3 h. Dialyzing the reaction solution for 8h by running water, and drying to obtain the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) with the zinc content of 5.2 mg/g. The effects of the highest zinc ion chelating rate and better oxidation resistance can be achieved through the integral preparation method.
Example nine: hericium erinaceus polysaccharide chelated zinc (Zn-HEP) infrared spectrogram analysis
The hericium erinaceus polysaccharide chelated zinc (Zn-HEP) is obtained by the method for preparing the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) provided by the experiment and is subjected to infrared spectrogram analysis.
Taking a small amount of dried HEP and Zn-HEP samples, respectively mixing with KBr according to the ratio of 1:100, grinding and tabletting. Using a Fourier transform infrared spectrometer at 4000cm-1～400cm-1Infrared spectroscopy scans were performed over a range of wavelengths to compare the IR spectra of HEP and Zn-HEP, and the results are shown in FIG. 7.
The IR spectra of HEP and Zn-HEP are shown in FIG. 7. As can be seen from FIG. 7, HEPs before and after chelation are all at 4000-400cm-1And the polysaccharide shows characteristic absorption peaks, wherein blue is HEP infrared absorption, and red is Zn-HEP infrared absorption. The results show thatHEP at 1081cm-1The existence of a strong absorption peak indicates that the HEP contains a pyran type glycosidic bond; at 1600cm-1The absorption peak is C ═ O asymmetric vibration; at 3417cm-1The absorption peak is the stretching vibration between O-H. Chelated Zn-HEP is 1081cm-1Has a reduced absorption compared with HEP, and the O-H absorption peak is shifted to 3450cm-1Here, it is shown that zinc ions bind to HEP and mainly coordinate with hydroxyl groups in the glycosidic bond of HEP.
Example ten: scanning electron microscope analysis of hericium erinaceus polysaccharide chelated zinc (Zn-HEP)
The hericium erinaceus polysaccharide chelated zinc (Zn-HEP) obtained by the experimental method is analyzed by a scanning electron microscope.
A certain amount of dry HEP and Zn-HEP are adhered to a sample table, and appearance forms of the polysaccharide before and after chelation are observed by adopting a ZEISS thermal field emission electron microscope under the conditions of high voltage of 20.00kV and magnification of 20000 and 25000. The results are shown in FIGS. 8 and 9. Figure 8 shows that the HEP surface before chelation appears the flake of surface unevenness, and the observation of increase magnification, surface hole and fibrous protrusion are clear to be seen. Figure 9 shows that the HEP after chelating the zinc ions appeared as surface depressed grains, with no fibrous protrusions on the surface compared to the HEP, observed at increased magnification.
Example eleven: optimization of preparation process of hericium erinaceus polysaccharide chelated zinc microcapsules
The influence of the ratio of carrageenan to chitosan to beta-cyclodextrin, the core-wall ratio, the solid content and the addition amount of potassium polyphosphate on the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsules is respectively researched. A four-factor three-level orthogonal experiment is carried out on the basis of a single-factor experiment, and the factors and levels of the orthogonal experiment are shown in a table 4.
Table 4: orthogonal test factor and horizon
Figure BDA0002012921780000181
Microcapsule embedding rate experiment: weighing 10mg of self-made hericium erinaceus polysaccharide chelated zinc microcapsules, dissolving the self-made hericium erinaceus polysaccharide chelated zinc microcapsules in 20mL of 5% trisodium citrate solution, selecting glucose as a standard substance, precipitating with ethanol, measuring the polysaccharide content in the microcapsules by a phenol-sulfuric acid colorimetric method, and calculating the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsules:
Figure BDA0002012921780000182
the test results and analysis of the formula of the hericium erinaceus polysaccharide chelated zinc microencapsulation by orthogonal optimization are shown in table 5.
Table 5: results and analysis of orthogonal assays
Figure BDA0002012921780000183
Figure BDA0002012921780000191
By comparing the extreme differences of the indexes, the primary and secondary sequence of the influencing factors is B>D>C>A, namely influencing factors of the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsules, sequentially comprises the core-wall ratio, the addition amount of potassium polyphosphate, the solid content, carrageenan, chitosan and beta-cyclodextrin, and according to the results of k1, k2 and k3 values of indexes in the table 5, the optimal level combination of the factors is determined to be A1B2C2D2Namely, in the preparation process of the hericium erinaceus polysaccharide chelated zinc microcapsule: the embedding rate of the prepared hericium erinaceus polysaccharide chelated zinc microcapsules can reach 95.62 percent. The yield was 89.43%; the obtained Hericium erinaceus polysaccharide chelated zinc microcapsule has an average particle size of 6-8 μm, can improve the dispersibility, emulsifying dispersibility and other capabilities, can strengthen the protection effect of easily-oxidized components in the polysaccharide, enhance the stability and prolong the shelf life, has simple and convenient preparation method, and can realize industrial continuous productionIt has wide application.
Example twelve: antioxidant activity of hericium erinaceus polysaccharide chelated zinc microcapsule
The hericium erinaceus polysaccharide chelated zinc microcapsules prepared by the experiment are subjected to antioxidant activity determination.
(1) DPPH radical scavenging Capacity determination
Preparing a DPPH ethanol solution with the concentration of 0.1mmol/L, and storing in dark for later use. Adding HEP solution (0.2, 0.4, 0.6, 0.8, 1.0g/L)2.0mL and DPPH solution 2.0mL into test tube, mixing, reacting at room temperature in dark for 30min, measuring absorbance value at 517nm, and using distilled water instead of polysaccharide solution as blank control group. DPPH radical clearance is calculated as follows.
DPPH radical scavenging (%) ═ a0-A2)/A1×100
Wherein: a. the2-absorbance values of different concentrations of HEP and HEP-Zn microcapsules; a. the1-absorbance values of distilled water replacing HEP and HEP-Zn microcapsules; a. the0-absorbance values of distilled water instead of DPPH.
The effect of HEP and Zn-HEP microcapsules on DPPH radical scavenging is shown in FIG. 10. As can be seen from the attached figure 10, the scavenging capacity of the HEP and Zn-HEP microcapsules on DPPH free radicals is increased along with the increase of the concentration in the concentration range of 0.2-1.0 mg/mL, and the scavenging capacity reaches the maximum when the concentration is 1.0 mg/mL. The scavenging capacity of the Zn-HEP microcapsule to DPPH free radicals is obviously improved compared with that of HEP before preparation, and when the concentration is 1.0mg/mL, the scavenging capacity of the Zn-HEP microcapsule to DPPH free radicals reaches 70.24%, which is improved by 3.14% compared with that before preparation. This is related to the interaction between the zinc ion chelating sites, the polysaccharide reactive groups and the microencapsulation coating.
(2)O2 -Determination of the scavenging Capacity
50mmol/L of Tris-HCl buffer solution with the pH value of 8.2, 7mmol/L pyrogallol solution and 10mol/L HCl solution are prepared for later use. Into the tube, 4.5mL Tris-HCl buffer, 1mL HEP solutions of various concentrations (0.2, 0.4, 0.6, 0.8, 1.0 g) were addedL), 3.2mL of distilled water, mixing uniformly, and then carrying out water bath at 25 ℃ for 20 min. Then 0.3mL of pyrogallol is added, the mixture is uniformly mixed, 1 drop of 10mol/L HCl is immediately dropped to terminate the reaction after the reaction is carried out in a water bath at 25 ℃ for 3min, and then the absorbance value is measured at the wavelength of 325 nm. O is2 -The radical clearance is calculated as follows:
O2 -radical scavenging rate (%) ═ a0-A)/A0×100
Wherein: a- -absorbance values of different concentrations of HEP and HEP-Zn microcapsules; a. the0-replacing the absorbance values of different concentrations of HEP and HEP-Zn microcapsules with distilled water.
HEP and Zn-HEP microcapsule pair O2 -Free radical scavenging, see FIG. 11. As can be seen from the attached figure 11, the concentration range of 0.2-1.0 mg/mL of the HEP and Zn-HEP microcapsules is within the range of O2 -The scavenging capacity of free radicals increases with increasing polysaccharide concentration, both at 1.0mg/mL for O2 -The scavenging ability of free radicals is maximized. And chelated Zn-HEP microcapsule pair O2 -The scavenging effect of free radicals is obviously improved compared with HEP before chelation, and the Zn-HEP microcapsules can treat O at 1.0mg/mL2 -The scavenging capacity of free radicals reaches 55.74%, which is 12.12% higher than that before chelation. The reason is that the synergistic effect between the zinc ion binding site in the Zn-HEP microcapsule and the active group exposed on the surface of the polysaccharide and the microcapsule protection effect enhance the O-binding site to the polysaccharide2 -Scavenging of free radicals.
In conclusion, the hericium erinaceus polysaccharide chelated zinc microcapsule takes Hericium Erinaceus Polysaccharide (HEP) as a raw material, zinc sulfate is used for chelating metal ions of the Hericium Erinaceus Polysaccharide (HEP), the zinc content in the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) is 5.2mg/g, and spray drying is carried out by taking carrageenan, chitosan and beta-cyclodextrin as wall materials to prepare the hericium erinaceus polysaccharide chelated zinc microcapsule, wherein the hericium erinaceus polysaccharide chelated zinc microcapsule has certain cleaning capacity, the cleaning capacity is increased along with the increase of concentration, the DPPH free radical cleaning capacity of the 1.0mg/mL hericium erinaceus polysaccharide chelated zinc microcapsule reaches 70.24%, the DPPH free radical cleaning capacity is improved by 3.14% compared with that of the hericium erinaceus polysaccharide chelated zinc microcapsule before chelation, and the 1.Microcapsule pair O2 -The scavenging capacity of free radicals reaches 55.74 percent and is improved by 12.12 percent compared with that before chelation, which shows that the oxidation resistance of the hericium erinaceus polysaccharide chelated zinc microcapsule after chelation is obviously improved compared with that of Hericium Erinaceus Polysaccharide (HEP) before chelation.
Example thirteen: preliminary study on anticancer effect of hericium erinaceus polysaccharide chelated zinc microcapsules
(1) Influence on the excessive biting and swallowing capacity of the mouse
28 mice are randomly divided into 4 groups, each experimental group is intragastrically administered with 0.4 mL/mouse of hericium erinaceus polysaccharide chelated zinc microcapsule solution every day, the dosage is 50, 100 and 200mg/kg respectively, a control group is intragastrically administered with normal saline with the same volume, 7 days are continuously carried out, after 24 hours, 0.6mL of beef culture solution is injected into the abdominal cavity of each mouse, after 24 hours, 2% CRBC and 0.5 mL/mouse are injected into the abdominal cavity, after 30 minutes, cervical vertebra is removed and death is caused, 2 mL/mouse of sterile normal saline is injected into the abdominal cavity, the abdomen is slightly kneaded for 1min, 1mL of abdominal cavity solution is sucked out and respectively dripped on two glass sheets, the incubation is carried out for 20min at 37 ℃, nonadherent macrophages and free CRBC are rinsed by normal saline, after blow drying, the cells are fixed by methanol, Swiss staining is carried out, and.
Table 6: the effect of the hericium erinaceus polysaccharide chelated zinc microcapsule solution on phagocytosis of mouse abdominal cavity macrophages (n-7,
Figure BDA0002012921780000221
)
Figure BDA0002012921780000222
the test results are shown in table 6, the hericium erinaceus polysaccharide chelated zinc microcapsule solutions with the concentrations of 50 mg/kg, 100 mg/kg and 200mg/kg can enhance the phagocytic function of mouse abdominal cavity macrophages, and compared with a control group, the hericium erinaceus polysaccharide chelated zinc microcapsule solution has the advantages that the phagocytic rate and the phagocytic index are remarkably different and particularly the high-dose difference is more remarkable when the hericium erinaceus polysaccharide chelated zinc microcapsule solution is administered for 7 days.
(2) Effect on mouse immune organ weight
Grouping and administration of mice were performed in the same manner as in experiment 1, administration was continued for 7 days, animals of each group were bled and killed at orbit 24 hours after the last administration, thymus and spleen were taken, water was sucked off by filter paper and weighed, and organ coefficients were calculated.
Table 7: influence of hericium erinaceus polysaccharide chelated zinc microcapsule solution on weight of spleen and thymus of mouse
Figure BDA0002012921780000223
Figure BDA0002012921780000231
The test results are shown in table 7, the spleen index of the experimental group is improved to a different extent compared with that of the control group, particularly the spleen index is most obvious in the high-dose group, and the thymus index is obviously different from that of the control group, so that the spleen index and the thymus index of the mouse can be obviously enhanced by the hericium erinaceus polysaccharide chelated zinc microcapsule under a certain dose.
(3) Inhibiting effect on cancer cells
Taking human gastric adenocarcinoma cells (AGS), colon adenocarcinoma cells (DLD-1) and cervical cancer cells (HeLa) in logarithmic growth phase, and culturing in RPMI-1640 medium containing 10% fetal calf serum at a ratio of 1 × 105The cfu/mL cell suspension was inoculated in a 96-well plate at 150. mu.L/well, incubated at 37 ℃ with 5% CO2After 24 hours of culture in an incubator, absorbing supernatant fluid and discarding, washing for 1-2 times by using phosphoric acid buffer solution, adding 100, 500 and 1000 mu g/mL hericium erinaceus polysaccharide chelated zinc microcapsule diluent without fetal bovine serum, respectively, setting 3 parallel solutions for each concentration, continuously culturing for 48 hours, adding WST-1 reagent, culturing for 5 hours, measuring OD value under 450nm, and calculating the cancer cell inhibition rate according to the following formula:
cancer cell inhibition (%) was 100 × [1- (test group OD value/blank control group OD value) ]
Table 8: in-vitro inhibition rate of hericium erinaceus polysaccharide chelated zinc microcapsules on AGS, DLD-1 and HeLa cancer cells
Figure BDA0002012921780000232
The results of experiments on the in vitro inhibition rate of the hericium erinaceus polysaccharide chelated zinc microcapsules on AGS, DLD-1 and HeLa cancer cells are shown in Table 8, and the hericium erinaceus polysaccharide chelated zinc microcapsules with different concentrations have certain inhibition rates on AGS, DLD-1 and HeLa, but the inhibition effects are not obvious, and the inhibition rates are all less than 25%, which indicates that the hericium erinaceus polysaccharide chelated zinc microcapsules have no obvious cytotoxicity on the 3 cancer cells.
The experiment shows that the hericium erinaceus polysaccharide chelated zinc microcapsules have obvious effects of enhancing the immune function and resisting cancers, and the in vitro experiment shows that the hericium erinaceus polysaccharide chelated zinc microcapsules have no obvious cytotoxicity to AGS, DLD-1 and HeLa cancer cells, but have strong activation effect on mouse macrophages, have immune activity, can be used as an immunomodulator, can be used for preparing anticancer drugs, and can be widely applied to medicines, sanitation or health products.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention made by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the present invention.

Claims (10)

1. A preparation method of hericium erinaceus polysaccharide chelated zinc microcapsules is characterized by specifically adopting the following technical steps:
(1) preparing hericium erinaceus polysaccharide chelated zinc (Zn-HEP): preparing a hericium erinaceus polysaccharide solution with the concentration of 12.5-17.5 g/L, taking 20-30 mL of the polysaccharide solution, adding 20-30 mL of ZnSO 4 solution with the concentration of 0.4-0.5 mol/L, stirring and reacting for 2-4 h at the temperature of 30-50 ℃, dialyzing the reaction solution for 7-9 h through running water, and drying to obtain hericium erinaceus polysaccharide chelated zinc (Zn-HEP), wherein the zinc content is 4-6 mg/g;
(2) preparing hericium erinaceus polysaccharide chelated zinc microcapsules: taking carrageenan, chitosan concentrate and beta-cyclodextrin as wall materials, adding 0.1-0.3% of potassium polyphosphate into the wall materials with the core-wall ratio of 1:9-1:11 and the solid content of 25-39%, stirring and homogenizing, wherein the homogenizing pressure is 25MPa, the homogenizing temperature is 60 ℃, the spray drying air inlet temperature is 190 ℃, the air outlet temperature is 60-80 ℃, the spray pressure is 25MPa, and drying is carried out in a constant-temperature drying box at 40-50 ℃ to prepare the hericium erinaceus polysaccharide chelated zinc microcapsule.
2. The method for preparing hericium erinaceus polysaccharide chelated zinc microcapsules according to claim 1, wherein the hericium erinaceus polysaccharide chelated zinc (Zn-HEP) has a zinc content of 5.2 mg/g.
3. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 1, wherein a hericium erinaceus polysaccharide solution with a concentration of 15g/L is prepared, and 25mL of the polysaccharide solution is taken.
4. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 1, wherein 25mL of 0.45mol/L ZnSO 4 solution is added.
5. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 1, wherein the reaction is carried out under stirring at 40 ℃ for 3h, and the reaction solution is dialyzed by running water for 8 h.
6. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule according to claim 1, wherein the wall materials are carrageenan, chitosan concentrate and beta-cyclodextrin, the weight ratio of carrageenan to beta-cyclodextrin is 1:2:2, the core-wall ratio is 1:10, the solid content is 27%, and 0.2% of potassium polyphosphate is added.
7. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 1, wherein the drying is carried out in a constant temperature drying oven at 45 ℃ under the conditions of the air inlet temperature of spray drying of 190 ℃, the air outlet temperature of 75 ℃ and the spray pressure of 25 MPa.
8. The preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 1, wherein the embedding rate of the hericium erinaceus polysaccharide chelated zinc microcapsule is 95.62%, and the yield is 89.43%; the average grain diameter of the obtained hericium erinaceus polysaccharide chelated zinc microcapsules is 6-8 mu m.
9. The hericium erinaceus polysaccharide chelated zinc microcapsule prepared by the preparation method of the hericium erinaceus polysaccharide chelated zinc microcapsule according to any one of claims 1 to 8.
10. The hericium erinaceus polysaccharide chelated zinc microcapsule as claimed in claim 9, for use in preparing anti-gastric adenocarcinoma drugs, anti-colon adenocarcinoma drugs, or anti-cervical cancer drugs.
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