CN100500860C - High activity golden mushroom polysaccharide-peptide-Fe chelate and its preparation - Google Patents

High activity golden mushroom polysaccharide-peptide-Fe chelate and its preparation Download PDF

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CN100500860C
CN100500860C CNB2006100366225A CN200610036622A CN100500860C CN 100500860 C CN100500860 C CN 100500860C CN B2006100366225 A CNB2006100366225 A CN B2006100366225A CN 200610036622 A CN200610036622 A CN 200610036622A CN 100500860 C CN100500860 C CN 100500860C
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peptide
enzyme
flammulina velutipes
compound
huge legendary
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CN1887912A (en
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郑建仙
王超
叶远寿
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South China University of Technology SCUT
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Abstract

The present invention is one kind of high activity golden mushroom polysaccharide-peptide- Fe2+ chelate, which has molecular weight of 20-50 KD, and contains polysaccharide in 69.9-70.2 wt%, peptide in 29.3-29.7 wt% and Fe2+ in 0.3-0.6 wt%. The golden mushroom polysaccharide-peptide- Fe2+ chelate is prepared with iron-rich sporophore as material and through the following steps: enzymolyzing with cellulose, hemicellulase or papain to break cell wall to raise the content of effective components, especially polysaccharide; the subsequent degradation of golden mushroom polysaccharide-peptide- Fe2+ chelate under the action of polysaccharidase; and final two-stage ultrafiltering membrane separation to obtain high activity golden mushroom polysaccharide-peptide- Fe2+ chelate with molecular weight of 20-50 KD. The high activity golden mushroom polysaccharide-peptide- Fe2+ chelate can improve systemic immune function, inhibit tumor and replenish iron effectively.

Description

A kind of high reactivity flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound and preparation method thereof
Technical field
The invention belongs to functional activity composition field, relate in particular to a kind of high reactivity flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound and preparation method thereof.
Background technology
Carbohydrate is the maximum organic compound of nature, also be important biological polymeric compound and important informational molecule, they have participated in the adjusting of the various vital movements of cell, active polysaccharide specially refers to have the active compound of polysaccharide of certain special physiological, because of it has stronger immunoregulation effect and anti-tumor activity enjoys attention.Polysaccharide wherein (polysaccharides), very obvious to promotion and the effect of recovery human body immune function.Fungus polysaccharide is the polysaccharide fraction that extracts from fungi, and it mainly is by host intermediary as a kind of wide spectrum immunomodulator, stimulate the various immunologically competent cell maturations of body, differentiation restores balance body immune system, is expelled and is engulfed tumour cell by the resistibility of body itself.The polysaccharide that extracts from fungi is better than the immunoglobulin (Ig) that extracts from the animal body inner blood, have bigger raising body immunity and anticancer effect.
Needle mushroom (Flammulina velutipes) belongs to Agaricales mouth mill section money Pseudomonas.It is a kind of traditional famous edible fungus.The foreign scholar from needle mushroom sporophore and mycelium the extraction separation purifying many glycoprotein, have stronger anti-tumor activity more.Flammulina velutipes-peptide is exactly a kind of glycoprotein that extracts from needle mushroom, is a kind of polysaccharide compound.Nineteen sixty-eight, people such as Japanese Kamasuka have reported that at first it is to murine sarcoma S 180The obvious suppression effect is arranged, have some this to be done comparatively deep research afterwards again.
Iron is the abundantest a kind of trace element of people's in-vivo content, is to constitute the indispensable important component of blood, and many vital movements all need iron to participate in.Sideropenia can cause hypoferric anemia, makes multiple metabolic process generation obstacle in the cell, causes immunity function to descend, and therefore, for iron undernutrition conditions among the improvement crowd, it is necessary conscientiously that Chinese people China Association for Promoting Democracy row generally, is reasonably mended iron.Safety, efficient, iron-fortified foods that economy is practical again and the development and the production of accessory substance have become China nutrition educational circles, the scientific worker's of food educational circles important topic.Solve the not enough problem of needed by human body ferro element at present both at home and abroad, generally all be that the micro-molysite of adding, iron deficiency severe patient are then taken the iron content medicine in food, ferrous-fortifier is done with ferric citrate amine, iron lactate, ferrous sulfate, Ferrous Gluconate etc. by for example many in the world countries, production irony fortified bread, cereal, flour, milk-product etc.; China produces enriched cracker, beverage iron-fortified foodss such as (baby's good fortune) with ferrous sulfate as ferrous-fortifier, the iron deficiency severe patient with ferrous sulfate, iron lactate etc. as drug administration.Because the inorganic salt of iron are as food fortifier, iron taste is heavy, after edible fishy smell is arranged, and to poor stability hot, light, in food-processing, the chance of being heated unavoidably light, food colour blackout, obfuscation often appear, produce precipitation sometimes, and molysite also can quicken becoming sour of fat, influence the quality of irony nutrient fortified food.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of high reactivity flammulina velutipes-peptide-Fe is provided 2+The huge legendary turtle compound.
Another object of the present invention is to provide this high reactivity flammulina velutipes-peptide-Fe 2+The preparation method of huge legendary turtle compound.The present invention is a raw material with the needle mushroom sporophore, adopt cellulase, hemicellulase or papoid to act on needle mushroom fungal cell wall constitute, make the needle mushroom fungal cell wall break, promote effective constituent to separate out, significantly improved content of effective in the extracting solution with respect to traditional technology, especially the content of polysaccharide.
High reactivity flammulina velutipes-peptide of the present invention-Fe 2+The huge legendary turtle compound is a kind of molecular weight at 2~50,000 compound, and wherein polysaccharide content is 69.9%~70.2%, and peptide content is 29.3%~29.7%, Fe 2+Content is 3~6mg/g.
High reactivity flammulina velutipes-peptide of the present invention-Fe 2+The preparation method of huge legendary turtle compound is as follows:
Step 1: in the process of cultivating flammulina velutipes, add soluble ferrite in the mushroom producing culture base, add-on is 6 * 10 of a mushroom producing culture matrix amount -4%~11 * 10 -4% treats in the mushroom producing culture base that the water quilting absorbs the back pack, and sterilization in sterilisable chamber, inserts original seed with respect to 3.6%~4.9% inoculum size of mushroom producing culture matrix amount, puts in 25 ℃ of sealing chambers and cultivates, and obtains rich iron needle mushroom sporophore;
Step 2: with rich iron needle mushroom sporophore is raw material, with its homogenate, weigh, and according to raw material (w): water (v)=1:10~1:40 adds entry, be warming up to 85~90 ℃, insulated and stirred 1~4h, add enzyme I by 0.05%~1% of raw materials quality, at 50~65 ℃, pH=4.5~8.5 time effect 80~100min utilizes whizzer to get rid of filter with 1000~3500r/min again, remove slag, obtain enzymolysis solution I, under 80 ℃~100 ℃ conditions the enzymolysis solution I enzyme that goes out is handled, this moment, the extraction yield of polysaccharide was 64~89%;
Step 3: through going out among the enzyme enzymolysis liquor I by ethanol (v): enzymolysis solution I (v)=to add concentration be 60%~95% ethanol to 2:1~4.5:1, leave standstill after-filtration and obtain flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound;
Step 4: press flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound (w): water (v)=1:20~1:50 ratio is flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound redissolves in water, adds flammulina velutipes-peptide-Fe 2+0.01%~0.3% compound enzyme II of huge legendary turtle compound aqueous solution quality, at 40~65 ℃, pH=2.4~8.2 time effect 50~75min, and then under 75~90 ℃ of conditions, the enzymolysis solution II enzyme that goes out is handled, this moment, the degradation rate of large molecular weight polysaccharides was 56~80%;
Step 5: will carry out the two-stage ultrafiltration membrane treatment through the enzyme enzymolysis liquor II that goes out, the two-stage ultra-filtration membrane model that is adopted is MWCO20000 and MWCO50000, the operational condition of one-level ultrafiltration membrane treatment: working pressure is 0.26~0.62MPa, and the ultrafiltration temperature is 45~60 ℃; The operational condition that the two-stage ultrafiltering film is handled: working pressure is 0.15~0.48MPa, and the ultrafiltration temperature is 45~60 ℃, obtains molecular weight ranges at high reactivity flammulina velutipes-peptide-Fe of 2~50,000 2+The huge legendary turtle compound.
Soluble ferrite described in the step 1 is ferrous sulfate or Ferrous Gluconate or iron lactate etc.
The adding method that adds soluble ferrite in the mushroom producing culture base described in the step 1 is that spice is executed iron processes or sprinkling and executed iron processes or immersion and execute in the iron processes any one.
Each component of mushroom producing culture base and quality percentage composition described in the step 1 is as follows:
Cotton seed hulls 90%~96%
Wheat bran 1%~6%
Sucrose 0.5%~2%
Water 2%~2.5%
Enzyme I described in the step 2 is any one or more than one the prozyme in cellulase, hemicellulase, the papoid.
Compound enzyme II described in the step 4 is the compound of beta-glucan enzyme and fungi zytase, and wherein the mass ratio of beta-glucan enzyme and fungi zytase is 4:1~1:1.
High reactivity flammulina velutipes-peptide of the present invention-Fe 2+The huge legendary turtle compound can effectively improve the general immunity function and more effectively suppress tumour, and benefit iron effect is obvious; And confirm as non-toxic substance through the toxicological assessment examining report, its stability is high after tested.
The present invention compared with prior art has following advantage and beneficial effect:
(1) the present invention is a raw material with rich iron needle mushroom sporophore, adopt cellulase, hemicellulase or papoid to act on the needle mushroom fungal cell wall, make the needle mushroom fungal cell wall break, promote effective constituent to separate out, significantly improved content of effective in the extracting solution with respect to traditional technology, especially the content of polysaccharide;
(2) needle mushroom has the gathering trace element, and converts it into the ability of organic composition, when adding soluble ferrite in the mushroom producing culture base, by the needle mushroom growth, can be translated into organic iron, and people eat high reactivity flammulina velutipes-peptide of the present invention-Fe 2+The huge legendary turtle compound; organic iron can slowly be absorbed by body; both replenished the iron that body lacks; can also prevent that excessive ferrous iron from causing iron poisoning and oxidation of divalent to become ferric iron; and metal ion is with after polysaccharide-peptide macromole (glycoprotein) combines; usually tangible biochemical effect can take place, high reactivity flammulina velutipes-peptide of the present invention-Fe 2+The huge legendary turtle compound is exactly Fe 2+With the huge legendary turtle compound of polysaccharide-peptide macromole (glycoprotein), integrate advantage and the biological activity of polysaccharide-peptide macromole and Fe, realize performance optimization and function synergy, Application Prospect is wide;
(3) studies show that flammulina velutipes-peptide, molecular weight is very strong at flammulina velutipes-peptide biological activity of 2~50,000, and the molecular weight of flammulina velutipes-peptide is generally about 23.6 ten thousand, so the present invention degrades to it by polysaccharidase, and adopts the two-stage ultra-filtration membrane to polysaccharide-peptide-Fe 2+The huge legendary turtle compound separates, the high reactivity flammulina velutipes-peptide-Fe that obtains 2+Huge legendary turtle adduct molecule amount is 2~50,000;
(4) the present invention adopts the two-stage ultra-filtration membrane to polysaccharide-peptide-Fe 2+The huge legendary turtle compound carries out the isolating while, can reach removal of impurities, decolouring and spissated purpose simultaneously, and not only preparation technology is simple, and the production cycle shortens greatly.
Embodiment
In order to understand the present invention better, below embodiment the present invention is done to describe further.
High reactivity flammulina velutipes-peptide of the present invention-Fe 2+The preparation method of huge legendary turtle compound is as follows:
Embodiment 1
Step 1: in the process of cultivating flammulina velutipes, adopt spice to execute iron processes in the mushroom producing culture base and add ferrous sulfate, add-on is 9 * 10 of a mushroom producing culture matrix amount -4% treats in the mushroom producing culture base that the water quilting absorbs the back pack, and sterilization in sterilisable chamber, inserts original seed with respect to 3.9% inoculum size of mushroom producing culture matrix amount, puts in 25 ℃ of sealing chambers and cultivates, and obtains rich iron needle mushroom sporophore;
Described each component of mushroom producing culture base and quality percentage composition are cotton seed hulls 94%, wheat bran 3%, sucrose 0.8%, water 2.2%;
Step 2: with rich iron needle mushroom sporophore is raw material, with its homogenate, weighs, and according to raw material (w): water (v)=1:30 adds entry, is warming up to 87 ℃, insulated and stirred 1h, the prozyme that adds cellulase and papoid by 1% of raw materials quality, at 50 ℃, pH=6 is effect 100min down, utilizes whizzer to get rid of filter with 3500r/min again, remove slag, obtain enzymolysis solution I, under 90 ℃ of conditions the enzymolysis solution I enzyme that goes out is handled, this moment, the extraction yield of polysaccharide was 89%;
Step 3: in that (v): enzymolysis solution I (v) is 70% ethanol for 3:1 adding concentration, leaves standstill after-filtration and obtain flammulina velutipes-peptide-Fe by ethanol through going out among the enzyme enzymolysis liquor I 2+The huge legendary turtle compound;
Step 4: press flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound (w): water (v) is that 1:20 is with flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound redissolves in water, adds flammulina velutipes-peptide-Fe 2+0.01% compound enzyme II of huge legendary turtle compound aqueous solution quality, compound enzyme II is the compound of beta-glucan enzyme and fungi zytase, wherein the mass ratio of beta-glucan enzyme and fungi zytase is 2:1; At 40 ℃, pH=2.4 is effect 75min down, and then under 90 ℃ of conditions the enzymolysis solution II enzyme that goes out is handled, and this moment, the degradation rate of large molecular weight polysaccharides was 74%;
Step 5: will carry out the two-stage ultrafiltration membrane treatment through the enzyme enzymolysis liquor II that goes out, the two-stage ultra-filtration membrane model that is adopted is MWCO20000 and MWCO50000, operational condition: the I and II working pressure is respectively 0.48MPa, 0.34MPa, the ultrafiltration temperature is 50 ℃ all, obtains molecular weight ranges at high reactivity flammulina velutipes-peptide-Fe of 2~50,000 2+The huge legendary turtle compound, wherein polysaccharide content is 69.9%, peptide content is 29.5%, Fe 2+Content is 6mg/g.
Embodiment 2
Step 1: in the process of cultivating flammulina velutipes, adopt to spray in the mushroom producing culture base and execute iron processes adding Ferrous Gluconate, add-on is 11 * 10 of a mushroom producing culture matrix amount -4% treats in the mushroom producing culture base that the water quilting absorbs the back pack, and sterilization in sterilisable chamber, inserts original seed with respect to 3.6% inoculum size of mushroom producing culture matrix amount, puts in 25 ℃ of sealing chambers and cultivates, and obtains rich iron needle mushroom sporophore;
Described each component of mushroom producing culture base and quality percentage composition are cotton seed hulls 90%, wheat bran 6%, sucrose 2%, water 2%;
Step 2: with rich iron needle mushroom sporophore is raw material, with its homogenate, weighs, and according to raw material (w): water (v)=1:10 adds entry, is warming up to 90 ℃, insulated and stirred 2h, add cellulase by 0.08% of raw materials quality, at 65 ℃, pH=4.5 is effect 95min down, utilizes whizzer to get rid of filter with 1000r/min again, remove slag, obtain enzymolysis solution I, under 80 ℃ of conditions the enzymolysis solution I enzyme that goes out is handled, this moment, the extraction yield of polysaccharide was 75%;
Step 3: in that (v): enzymolysis solution I (v) is 60% ethanol for 2:1 adding concentration, leaves standstill after-filtration and obtain flammulina velutipes-peptide-Fe by ethanol through going out among the enzyme enzymolysis liquor I 2+The huge legendary turtle compound;
Step 4: press flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound (w): water (v) is that 1:50 is with flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound redissolves in water, adds flammulina velutipes-peptide-Fe 2+0.3% compound enzyme II of huge legendary turtle compound aqueous solution quality, compound enzyme II is the compound of beta-glucan enzyme and fungi zytase, wherein the mass ratio of beta-glucan enzyme and fungi zytase is 1:1; At 65 ℃, pH=6.5 is effect 50min down, and then under 75 ℃ of conditions the enzymolysis solution II enzyme that goes out is handled, and this moment, the degradation rate of large molecular weight polysaccharides was 80%;
Step 5: will carry out the two-stage ultrafiltration membrane treatment through the enzyme enzymolysis liquor II that goes out, the two-stage ultra-filtration membrane model that is adopted is MWCO20000 and MWCO50000, operational condition: the I and II working pressure is 0.26MPa, 0.15MPa, the ultrafiltration temperature is 45 ℃ all, obtains molecular weight ranges at high reactivity flammulina velutipes-peptide-Fe of 2~50,000 2+The huge legendary turtle compound, wherein polysaccharide content is 70%, peptide content is 29.7%, Fe 2+Content is 3mg/g.
Embodiment 3
Step 1: in the process of cultivating flammulina velutipes, adopt to soak in the mushroom producing culture base and execute iron processes adding iron lactate, add-on is 6 * 10 of a mushroom producing culture matrix amount -4% treats in the mushroom producing culture base that the water quilting absorbs the back pack, and sterilization in sterilisable chamber, inserts original seed with respect to 4.9% inoculum size of mushroom producing culture matrix amount, puts in 25 ℃ of sealing chambers and cultivates, and obtains rich iron needle mushroom sporophore;
Described each component of mushroom producing culture base and quality percentage composition are cotton seed hulls 96%, wheat bran 1%, sucrose 0.5%, water 2.5%;
Step 2: with rich iron needle mushroom sporophore is raw material, with its homogenate, weighs, and according to raw material (w): water (v)=1:40 adds entry, is warming up to 85 ℃, insulated and stirred 4h, the prozyme that adds cellulase, hemicellulase and papoid by 0.05% of raw materials quality, at 58 ℃, pH=8.5 is effect 80min down, utilizes whizzer to get rid of filter with 2000r/min again, remove slag, obtain enzymolysis solution I, under 100 ℃ of conditions the enzymolysis solution I enzyme that goes out is handled, this moment, the extraction yield of polysaccharide was 64%;
Step 3: in that (v): enzymolysis solution I (v) is 95% ethanol for 4.5:1 adding concentration, leaves standstill after-filtration and obtain flammulina velutipes-peptide-Fe by ethanol through going out among the enzyme enzymolysis liquor I 2+The huge legendary turtle compound;
Step 4: press flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound (w): water (v) is that 1:30 is with flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound redissolves in water, adds flammulina velutipes-peptide-Fe 2+0.095% compound enzyme II of huge legendary turtle compound aqueous solution quality, compound enzyme II is the compound of beta-glucan enzyme and fungi zytase, wherein the mass ratio of beta-glucan enzyme and fungi zytase is 4:1; At 50 ℃, pH=8.2 is effect 60min down, and then under 80 ℃ of conditions the enzymolysis solution II enzyme that goes out is handled, and this moment, the degradation rate of large molecular weight polysaccharides was 56%;
Step 5: will carry out the two-stage ultrafiltration membrane treatment through the enzyme enzymolysis liquor II that goes out, the two-stage ultra-filtration membrane model that is adopted is MWCO20000 and MWCO50000, operational condition: the I and II working pressure is 0.62Mpa, 0.48MPa, the ultrafiltration temperature is 60 ℃ all, obtains molecular weight ranges at high reactivity flammulina velutipes-peptide-Fe of 2~50,000 2+The huge legendary turtle compound, wherein polysaccharide content is 70.2%, peptide content is 29.3%, Fe 2+Content is 5mg/g.
High reactivity flammulina velutipes-peptide of the present invention-Fe 2+The huge legendary turtle compound can be applied to the healthcare products aspect, as long as add starch, carries out just can obtaining dry product after the spraying drying, can obtain flammulina velutipes-peptide-Fe in incapsulating 2+Huge legendary turtle compound healthy capsule.

Claims (5)

1. flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound is characterized in that being a kind of molecular weight at 2~50,000 compound, and wherein polysaccharide content is 69.9%~70.2%, and peptide content is 29.3%~29.7%, Fe 2+Content is 3~6mg/g.
2. the described flammulina velutipes-peptide of claim 1-Fe 2+The preparation method of huge legendary turtle compound is characterized in that preparation process is as follows:
Step 1: in the process of cultivating flammulina velutipes, add soluble ferrite in the mushroom producing culture base, add-on is 6 * 10 of a mushroom producing culture matrix amount -4%~11 * 10 -4% treats in the mushroom producing culture base that the water quilting absorbs the back pack, and sterilization in sterilisable chamber, inserts original seed with respect to 3.6%~4.9% inoculum size of mushroom producing culture matrix amount, puts in 25 ℃ of sealing chambers and cultivates, and obtains rich iron needle mushroom sporophore;
Step 2: with rich iron needle mushroom sporophore is raw material, with its homogenate, weigh, and add entry according to by weight/volume raw material: water=1:10~1:40, be warming up to 85~90 ℃, insulated and stirred 1~4h, add enzyme I by 0.05%~1% of raw materials quality, at 50~65 ℃, pH=4.5~8.5 time effect 80~100min utilizes whizzer to get rid of filter with 1000~3500r/min again, remove slag, obtain enzymolysis solution I, under 80 ℃~100 ℃ conditions the enzymolysis solution I enzyme that goes out is handled, this moment, the extraction yield of polysaccharide was 64%~89%; Described enzyme I is any one or more than one the prozyme in cellulase, hemicellulase, the papoid;
Step 3: through the ethanol by volume that goes out among the enzyme enzymolysis liquor I: it is 60%~95% ethanol that enzymolysis solution I=2:1~4.5:1 adds concentration, leaves standstill after-filtration and obtains flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound;
Step 4: by weight/volume ratio flammulina velutipes-peptide-Fe 2+Huge legendary turtle compound: water=1:20~1:50 ratio is with flammulina velutipes-peptide-Fe 2+The huge legendary turtle compound redissolves in water, adds flammulina velutipes-peptide-Fe 2+0.01%~0.3% compound enzyme II of huge legendary turtle compound aqueous solution quality, at 40~65 ℃, pH=2.4~8.2 time effect 50~75min, and then under 75~90 ℃ of conditions, the enzymolysis solution II enzyme that goes out is handled, this moment, the degradation rate of large molecular weight polysaccharides was 56~80%; Described compound enzyme II is the compound of beta-glucan enzyme and fungi zytase, and wherein the mass ratio of beta-glucan enzyme and fungi zytase is 4:1~1:1;
Step 5: will carry out the two-stage ultrafiltration membrane treatment through the enzyme enzymolysis liquor II that goes out, the two-stage ultra-filtration membrane model that is adopted is MWCO20000 and MWCO50000, the operational condition of one-level ultrafiltration membrane treatment: working pressure is 0.26~0.62MPa, and the ultrafiltration temperature is 45~60 ℃; The operational condition that the two-stage ultrafiltering film is handled: working pressure is 0.15~0.48MPa, and the ultrafiltration temperature is 45~60 ℃, obtains molecular weight ranges at flammulina velutipes-peptide-Fe of 2~50,000 2+The huge legendary turtle compound.
3. flammulina velutipes-peptide according to claim 2-Fe 2+The preparation method of huge legendary turtle compound is characterized in that the soluble ferrite described in the step 1 is ferrous sulfate or Ferrous Gluconate or iron lactate.
4. flammulina velutipes-peptide according to claim 2-Fe 2+The preparation method of huge legendary turtle compound is characterized in that the adding method that adds soluble ferrite in the mushroom producing culture base described in the step 1 is that spice is executed iron processes or sprinkling and executed iron processes or immersion and execute in the iron processes any one.
5. flammulina velutipes-peptide according to claim 2-Fe 2+The preparation method of huge legendary turtle compound is characterized in that each component of mushroom producing culture base and the quality percentage composition described in the step 1 is as follows:
Cotton seed hulls 90%~96%
Wheat bran 1%~6%
Sucrose 0.5%~2%
Water 2%~2.5%.
CNB2006100366225A 2006-07-21 2006-07-21 High activity golden mushroom polysaccharide-peptide-Fe chelate and its preparation Expired - Fee Related CN100500860C (en)

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