CN106279461A - A kind of selenizing maca polysaccharide and its production and use - Google Patents

A kind of selenizing maca polysaccharide and its production and use Download PDF

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CN106279461A
CN106279461A CN201610772390.3A CN201610772390A CN106279461A CN 106279461 A CN106279461 A CN 106279461A CN 201610772390 A CN201610772390 A CN 201610772390A CN 106279461 A CN106279461 A CN 106279461A
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selenizing
maca polysaccharide
polysaccharide
maca
selenium
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CN106279461B (en
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赵兵
王丽卫
张利军
陈金金
赵庆生
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Institute of Process Engineering of CAS
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations

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Abstract

A kind of selenizing maca polysaccharide and its production and use.Described preparation method includes that maca polysaccharide is added in aqueous acid by (1), dissolves, and adds selenizing agent, reacting by heating, obtains selenylation reaction liquid;(2) step (1) gained selenylation reaction liquid is cooled down, then carry out solid-liquid separation, collect supernatant, carry out remove impurity;(3) by step (2) gained supernatant concentration, it is dried, obtains selenizing maca polysaccharide.Selenizing maca polysaccharide prepared by the method for the present invention has the double effects of maca polysaccharide and organic selenium concurrently, improves the added value of maca polysaccharide, is more conducive to be absorbed by organisms utilization, and product shows higher biological activity, has broad application prospects.

Description

A kind of selenizing maca polysaccharide and its production and use
Technical field
The present invention relates to a kind of chemical synthesis process, particularly relate to maca polysaccharide that a kind of selenizing modifies and preparation method thereof and Purposes, belongs to the field of deep of maca polysaccharide.
Background technology
Selenium is the trace element of needed by human, is the main active of glutathion peroxidase, can directly or Oxygen-derived free radicals in purged body indirectly, suppression lipid oxidation or peroxidating, block the pathogenic effects of reactive oxygen species and free radicals, protection is thin Born of the same parents exempt from the damage of peroxide, safeguard the stability of cell membrane, to the growth of animal, breeding, immunity, infection, anti-stress Etc. aspect play an important role.Investigation shows, in state-owned more than 2/3rds area half populations be in scarce selenium, low selenium band, The selenium amount taken in by ordinary meal does not reaches Minimum requirements amount so that the disease incidence relevant with scarce selenium is greatly improved.
The effective way that selenium is Selenium Supplement is strengthened in food.The selenium hardening agent of China includes inorganic selenium and organic selenium two Kind, inorganic selenium mainly have sodium selenite and sodium selenate, and organic selenium mainly has selenium protein, yeast rich in selenium, selenocarrageenan, selenium many Sugar, selenoamino acid, seleno nucleic acid etc..Although inorganic selenium selenium content is high and cheap, but absorbing undesirable, biological effectiveness is low, Toxicity is relatively big, thus is strictly limited its usage amount.Developed country need not simply inorganic salt form strong as the nutrition of selenium Agent, at present, the developed country such as Japan, the U.S. has forbidden adding the inorganic selenium such as sodium selenite in food.Organic selenium is then Safety is high, is not susceptible to poisoning, and be easily absorbed by the body utilization, and selenium supplement efficiency is high, and biological activity is high.Therefore, preparation safety, Efficient organic selenium compounds is an important content of selenium chemical research.
Selenium polysaccharide is the organic selenium compounds that selenium is bonded with active polysaccharide, has function of both polysaccharide and selenium, toxicity concurrently Be substantially reduced with side effect, therefore show more effective physiologically active, can as a kind of safely, effectively, healthy selemium nutrition Source.The activity of selenium polysaccharide is higher than selenium and polysaccharide, is more beneficial for being absorbed by organisms utilization, and it develops and causes the wide of the world General concern.It is demonstrated experimentally that selenium polysaccharide has anti-metal poisoning, antioxidation, inhibiting tumor cell and virus, immunomodulating, anti-ageing waits for a long time Pharmacological action.Along with the continuous progress of society, the living standard of people gradually steps up, and increasingly pays close attention to the health of self, this Need more selenium polysaccharide launch the most urgently.
At present, the preparation method of selenium polysaccharide mainly has two kinds, i.e. biological concentration method and chemical synthesis.Biological concentration legal system The standby cycle is long, and condition should not control, and produces feasibility difficulty in enormous quantities.In the chemical production processes of selenium polysaccharide, it is common to use pyrrole The toxic organic solvents such as pyridine, benzene, thionyl chloride, thus affect the application in food of the selenizing polysaccharide.
Lepidinm meyenii Walp is a kind of Cruciferae Lepidium plant with high nutritive value and pharmacology value, and maca polysaccharide is agate One of effective ingredient of coffee.Modern pharmacology research confirms that maca polysaccharide has a various biological activity, wherein with antioxidation, anti- Old and feeble and anti-fatigue active is studied more.(carboxymethyl maca polysaccharide preparation and Study of Antioxidation, Chinese food adds Chen Yanqing Agent, 2010,2:94-96) maca polysaccharide has carried out carboxy methylation modification, and after finding carboxy methylation, maca polysaccharide is to hydroxy radical Scavenging activity improves 2 times.CN103739729A discloses a kind of Indigowoad root selenium polysaccharide and preparation method thereof, in selenylation reaction Addition barium chloride is as catalyst, but barium ions is a kind of toxic material, affects its safety.
Different method of modifying is different to the activity influence of polysaccharide, and the selenizing of maca polysaccharide is modified and selenium after modifying There is not been reported in the research of change maca polysaccharide.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide the preparation method of a kind of selenizing maca polysaccharide, The pharmacological function making selenium and maca polysaccharide is optimized integration, and activity is apparently higher than selenium or maca polysaccharide, and is conducive to by body Absorb.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
The preparation method of a kind of selenizing maca polysaccharide, comprises the steps:
(1) maca polysaccharide is added in aqueous acid, dissolve, add selenizing agent, reacting by heating, obtain selenylation reaction liquid;
(2) step (1) gained selenylation reaction liquid is cooled down, then carry out solid-liquid separation, collect supernatant, carry out remove impurity;
(3) by step (2) gained supernatant concentration, it is dried, obtains selenizing maca polysaccharide.
The present invention uses acid solution to carry out catalytic reaction, greatly reduces the residual of later stage heavy metal barium ions, makes to prepare Product safer.
As preferably, the aqueous acid described in step (1) is salpeter solution, sulfuric acid solution, phosphoric acid solution, and perchloric acid is molten One or more combination in liquid.
Preferably, in described aqueous acid acid volumetric concentration be 0.5-5%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% etc., preferably 0.5-2%.
Preferably, described selenizing agent is sodium selenite and/or Monohydrated selenium dioxide.
Preferably, the mass ratio of described selenizing agent and maca polysaccharide is 1:5-30, for example, 1:7,1:9,1:12,1:15, 1:19,1:22,1:26,1:29 etc..
Preferably, the temperature of described reacting by heating is 30-90 DEG C, for example, 35 DEG C, 39 DEG C, 43 DEG C, 48 DEG C, 55 DEG C, 60 DEG C, 66 DEG C, 71 DEG C, 78 DEG C, 84 DEG C, 88 DEG C etc., the time is 1-9h, for example, 1.5h, 3h, 5h, 7h, 8.5h etc..
Preferably, described in step (2), chilling temperature is 10-35 DEG C.
Preferably, described remove impurity is dialysis and/or membrane filtration.Use dialysis and/or membrane filtration can be by the residuals of selenizing agent Reducing, the selenizing maca polysaccharide obtained has more safety;More save compared to alcohol precipitating method commonly used in the prior art simultaneously Operation, reduces cost.
As preferably, step (3) can also be following process: will add 3-5 times of volume of concentrated solution after supernatant concentration Dehydrated alcohol precipitates, and separates, by drying precipitate, obtains selenizing maca polysaccharide.Wherein separation can use commonly used in the art Technological means, such as centrifugal, filtration etc..
Preferably, being dried as vacuum drying and/or lyophilization in step (3).
The selenium content of the selenizing maca polysaccharide obtained by the present invention is 1-10 μ g/mg.The selenizing maca polysaccharide of gained is being protected On the basis of demonstrate,proving its biological activity, greatly reduce the content of selenium, advantageously reduce production cost, improve selenizing Lepidinm meyenii Walp many simultaneously The safety of sugar.
An object of the present invention also resides in the selenizing maca polysaccharide providing preparation method of the present invention to prepare.The present invention The antioxidant activity of the selenizing maca polysaccharide of preparation is higher than maca polysaccharide.
An object of the present invention also resides in provides the selenizing maca polysaccharide of the present invention in antioxidation and selenium supplement Application.
Preferably, can be using selenizing maca polysaccharide as phases such as auxiliary treatment aging, tumor, immunity degradation or dermatosiss Close medicine, health food and the raw material of cosmetics.
Preferably, selenizing maca polysaccharide can be used for bread and cheese, health food and feedstuff as organic selenium supplement In raw material.
The present invention compared with prior art, has a following technical advantage:
(1) selenium is incorporated into the sugar unit of maca polysaccharide by the present invention, prepares selenizing maca polysaccharide, effectively reduces sub-selenium The toxicity of acid groups, obtains selenizing maca polysaccharide soluble in water, improves the selenium content of polysaccharide, has free radical the most clear Except effect, it is more conducive to be absorbed by organisms utilization.
(2) residual of selenizing agent can be reduced, the selenizing Lepidinm meyenii Walp obtained by the present invention by dialysis or the method for membrane filtration Polysaccharide, has more safety.
(3) present invention does not use any organic solvent, it is to avoid pollution-free to environment and product.Selenylation reaction condition can Control, produces equipment requirements the highest, and production cost is low, easily realizes industrialized production.
(4) the selenizing maca polysaccharide that prepared by the present invention can be as the organic selenium supplement application of efficient, low toxicity to food, guarantor In strong product and feedstuff, it is provided that selenium element necessary to human body or animal.Live additionally, selenizing maca polysaccharide has good antioxidation Property, the exploitation to corresponding cosmetics has profound significance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of maca polysaccharide;
Fig. 2 is the infrared spectrogram of the selenizing maca polysaccharide of embodiment 1 preparation.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1: the preparation of selenizing maca polysaccharide
(1) being dissolved by the salpeter solution of 0.5g maca polysaccharide addition 0.5%, add 0.1g sodium selenite, 30 DEG C add Thermal response 9h, obtains selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 20 DEG C, centrifugal, collect supernatant, dialyse;
(3) being concentrated by the solution in bag filter, vacuum drying, obtain 0.1g selenizing maca polysaccharide, selenium content is 10 μ g/mg。
Embodiment 2: the preparation of selenizing maca polysaccharide
(1) sulfuric acid solution of 10g maca polysaccharide addition 2% is dissolved, add 1g Monohydrated selenium dioxide, 90 DEG C of reacting by heating 1h, obtains selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 10 DEG C, centrifugal, collect supernatant, join in ultrafilter membrane, carry out membrane filtration;
(3) being concentrated by the solution in ultrafilter membrane, lyophilization, obtain 2.8g selenizing maca polysaccharide, selenium content is 1 μ g/mg。
Embodiment 3: the preparation of selenizing maca polysaccharide
(1) being dissolved by the phosphoric acid solution of 5g maca polysaccharide addition 5%, add 0.33g sodium selenite, 60 DEG C of heating are anti- Answer 5h, obtain selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 35 DEG C, centrifugal, collect supernatant, dialyse;
(3) being concentrated by the solution in bag filter, lyophilization, obtain 1.5g selenizing maca polysaccharide, selenium content is 5 μ g/mg。
Embodiment 4: the preparation of selenizing maca polysaccharide
(1) being dissolved by the perchloric acid solution of 20g maca polysaccharide addition 3.5%, add 1g Monohydrated selenium dioxide, 45 DEG C of heating are anti- Answer 3h, obtain selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 15 DEG C, centrifugal, collect supernatant, be initially charged ultrafilter membrane and filter, add NF membrane, filters;
(3) being concentrated by the solution in nanofiltration, vacuum drying, obtain 5g selenizing maca polysaccharide, selenium content is 3 μ g/mg.
Embodiment 5: the preparation of selenizing maca polysaccharide
(1) being dissolved by the salpeter solution of 100g maca polysaccharide addition 4%, add 4g sodium selenite, 75 DEG C of heating are anti- Answer 7h, obtain selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 25 DEG C, centrifugal, collect supernatant, dialyse;
(3) being concentrated by the solution in bag filter, vacuum drying, obtain 26g selenizing maca polysaccharide, selenium content is 8 μ g/ mg。
Embodiment 6: the preparation of selenizing maca polysaccharide
(1) phosphoric acid solution of 1g maca polysaccharide addition 0.5% is dissolved, add 0.04g sodium selenite, 80 DEG C of heating Reaction 8h, obtains selenylation reaction liquid;
(2) selenylation reaction liquid is cooled to 18 DEG C, centrifugal, collect supernatant, dialyse;
(3) being concentrated by the solution in bag filter, vacuum drying, obtain 0.22g selenizing maca polysaccharide, selenium content is 6 μ g/mg。
Embodiment 7: the checking of selenizing maca polysaccharide
The selenizing maca polysaccharide taking maca polysaccharide and embodiment 1 preparation respectively is a little, carries out infrared after adding KBr tabletting Scanning, Fig. 1 and Fig. 2 is respectively maca polysaccharide and the infrared spectrogram of selenizing maca polysaccharide.
Fig. 2 with Fig. 1 is contrasted, it can be seen that selenizing maca polysaccharide is at 400-4000cm-1The infrared spectrum of scope with Maca polysaccharide is closely similar, shows that it still remains the structure of polysaccharide, i.e. at 3200-3600cm-1There is a broad peak, be polysaccharide The stretching vibration of upper-OH, at 2900cm-1There is the stretching vibration peak that C-H is more weak, at 1600-1700cm-1All there is C=O absworption peak, Fig. 2 is at 808cm-1And 668cm-1Place occurs in that Se=O key and the vibration absorption peak of selenic acid ester (Se-O-C), respectively in Fig. 1 then No, show that the selenizing of maca polysaccharide is modified successfully.
Embodiment 8: the reducing power of selenizing maca polysaccharide measures
The reducing power of selenizing maca polysaccharide and maca polysaccharide the results are shown in Table 1.There is the sample of reproducibility, can be by ferric iron Being converted into ferrous iron, the latter has stronger absorption at 700nm, and therefore, reducing power is the strongest, and its light absorption value is the highest.Visible, along with selenium Changing the rising of maca polysaccharide concentration, its absorption value detail at 700nm improves, and presents good linear relationship, selenizing is described Lepidinm meyenii Walp has higher reproducibility.
Table 1 selenizing maca polysaccharide reducing power experimental result
Embodiment 9: selenizing maca polysaccharide removes the experiment of DPPH free radical
The removing DPPH free radical of selenizing maca polysaccharide and maca polysaccharide the results are shown in Table 2.Many with the Lepidinm meyenii Walp of same concentrations Sugar is compared, and the clearance rate of DPPH free radical is significantly improved by selenizing maca polysaccharide, illustrates that selenizing maca polysaccharide has the most clear Activity except DPPH free radical.
Table 2 selenizing maca polysaccharide removes DPPH experimental result
Embodiment 10: selenizing maca polysaccharide removes the experiment of ABTS free radical
The removing ABTS free radical of selenizing maca polysaccharide and maca polysaccharide the results are shown in Table 3.Many with the Lepidinm meyenii Walp of same concentrations Sugar is compared, and the clearance rate of ABTS free radical is significantly improved by selenizing maca polysaccharide, and when concentration is 0.5mg/ml, selenizing Lepidinm meyenii Walp is many Sugar reaches 60.78% to the clearance rate of ABTS free radical, is 1.8 times of selenizing polysaccharide, illustrates that selenizing maca polysaccharide has preferably The activity of removing ABTS free radical.
Table 3 selenizing maca polysaccharide removes ABTS experimental result
Embodiment 11: the anti-tumor experiment of selenizing maca polysaccharide
The selenizing maca polysaccharide that maca polysaccharide and embodiment 3 obtain is made into respectively the solution of 6mg/ml, uses mtt assay to enter Row anti-tumor activity, two kinds of polysaccharide the results are shown in Table 4 to the suppression ratio of different tumor cells, compared with maca polysaccharide, selenizing Lepidinm meyenii Walp The suppression ratio of different tumor cells is significantly improved by polysaccharide.
Table 4 selenizing maca polysaccharide anti-tumor experiment result
Embodiment 12: selenizing maca polysaccharide improves immunity experiment
Selenizing maca polysaccharide embodiment 5 obtained carries out improving immunity experiment, recommends according to the people of tested material is oral Consumption sets basic, normal, high dosage group, respectively 500,1500,4500mg/kg bw, set 1 matched group simultaneously.Employing mtt assay is examined Surveying the mouse lymphocyte propagation transformation function of ConA induction, the delayed allergy of ear swelling method detection mice, result is shown in Table 5.
Table 5 selenizing maca polysaccharide improves immunity result
Group Dosage (mg/kg bw) Lymphopoiesis ability (OD) Left and right auricle weight difference
Matched group -- 0.27±0.06 10.76±3.11
Low dosage 500 0.32±0.04 11.07±4.02
Middle dosage 1500 0.35±0.08 13.62±3.76
High dose 4500 0.46±0.03* 18.35±2.53*
*: compared with matched group, significant difference, P < 0.05.
As shown in Table 5, compared with matched group, the mouse lymphocyte multiplication capacity of selenizing maca polysaccharide high dose group induction It is remarkably reinforced;The degree of the difference reflection delayed allergy of left and right auricle weight, the weight difference of given the test agent high dose group Value is apparently higher than matched group, it is possible to determine that this experimental result is positive, i.e. selenizing maca polysaccharide has and preferably improves immunity Power effect.
Embodiment 13: selenizing maca polysaccharide application in food
Selenizing maca polysaccharide embodiment 1 obtained makes Lepidinm meyenii Walp pressed candy, and formula is: selenizing maca polysaccharide 50g, agate Coffee powder 900g, xylitol 50g, play the effect of Selenium Supplement.
Embodiment 14: selenizing maca polysaccharide application in health food
Selenizing maca polysaccharide embodiment 2 obtained makes Maca capsule, and formula is: selenizing maca polysaccharide 100g, Lepidinm meyenii Walp Extract 800g, dextrin 50g, microcrystalline Cellulose 50g, play the effect of enhancing immunity.
Its application process is: after being mixed homogeneously with health food by selenizing maca polysaccharide, according to health food before mixing Using method uses, and compared with the health food being not added with selenizing maca polysaccharide, free radical scavenging activity improves 16.11%, plays Remove free radical, defying age, the effect of Selenium Supplement.
Embodiment 15: selenizing maca polysaccharide application in feedstuff
Selenizing maca polysaccharide embodiment 6 obtained is applied in feedstuff, in terms of the gross mass of feedstuff, and selenizing maca polysaccharide Accounting for the 1-5% of feedstuff gross mass, its application process is: after being mixed homogeneously with feedstuff by selenizing maca polysaccharide, making according to feedstuff With method feeding piglet, compared with matched group, the piglet of edible selenizing maca polysaccharide improves weightening finish 10.56%.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention have to rely on above-mentioned in detail Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, The equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's Within the scope of protection domain and disclosure.

Claims (10)

1. a preparation method for selenizing maca polysaccharide, comprises the steps:
(1) maca polysaccharide is added in aqueous acid, dissolve, add selenizing agent, reacting by heating, obtain selenylation reaction liquid;
(2) step (1) gained selenylation reaction liquid is cooled down, then carry out solid-liquid separation, collect supernatant, carry out remove impurity;
(3) by step (2) gained supernatant concentration, it is dried, obtains selenizing maca polysaccharide.
Preparation method the most according to claim 1, it is characterised in that the aqueous acid described in step (1) is that nitric acid is molten One or more combination in liquid, sulfuric acid solution, phosphoric acid solution, perchloric acid solution;
Preferably, in described aqueous acid, the volumetric concentration of acid is 0.5-5%, preferably 0.5-2%.
Preparation method the most according to claim 1 and 2, it is characterised in that described in step (1), selenizing agent is sodium selenite And/or Monohydrated selenium dioxide;
Preferably, described selenizing agent is 1:5-30 with the mass ratio of maca polysaccharide.
4. according to the preparation method described in any one of claim 1-3, it is characterised in that reacting by heating described in step (1) Temperature is 30-90 DEG C, and the time is 1-9h.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that described in step (2), chilling temperature is 10-35℃;
Preferably, described remove impurity is dialysis and/or membrane filtration.
6. according to the preparation method described in any one of claim 1-5, it is characterised in that step (3) can also be following process: The dehydrated alcohol adding 3-5 times of volume of concentrated solution after supernatant concentration is precipitated, separates, by drying precipitate, obtain selenium Change maca polysaccharide;
Preferably, being dried as vacuum drying and/or lyophilization in step (3).
7. the selenizing maca polysaccharide that prepared by preparation method described in an any one of claim 1-6.
8. the purposes in antioxidation and selenium supplement of the selenizing maca polysaccharide described in claim 7.
9. the purposes described in claim 8, it is characterised in that described selenizing maca polysaccharide is treated aging, tumor as auxiliary, exempted from Epidemic disease power declines or the raw material of dermatosis related drugs, health food and cosmetics.
10. the purposes described in claim 8 or 9, it is characterised in that described selenizing maca polysaccharide is used for as organic selenium supplement Raw material in bread and cheese, health food and feedstuff.
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