CN104258407A - Method for preparing sustained release vitamin E derivative preparation - Google Patents
Method for preparing sustained release vitamin E derivative preparation Download PDFInfo
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- CN104258407A CN104258407A CN201410483449.8A CN201410483449A CN104258407A CN 104258407 A CN104258407 A CN 104258407A CN 201410483449 A CN201410483449 A CN 201410483449A CN 104258407 A CN104258407 A CN 104258407A
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Abstract
The invention discloses a sustained release vitamin E derivative preparation and a preparation method thereof. The preparation method comprises the following steps: mixing dry base starch and water, adding concentrated hydrochloric acid, thereby obtaining partially hydrolyzed starch milk; adding octenyl succinic anhydride and sodium hydroxide into the partially hydrolyzed starch milk, thereby obtaining the esterified starch milk; filtering, mixing the filter cake and vitamin E derivatives, grinding, and performing high-temperature drying and low-temperature treatment, thereby finally obtaining the sustained release vitamin E derivative preparation. The vitamin E derivative preparation is prepared by taking low-cost native starch as a raw material, the cost of the raw material has the competitive advantage, the biocompatibility is obviously superior to that of silica, and because the content of resistant starch of a clad material is obviously increased, a sustained release effect is achieved.
Description
Technical field
The invention belongs to field of medicine and chemical technology, be specifically related to a kind of preparation method of spacetabs type vitamin e derivative preparation.
Background technology
Vitamin E (V
e) be just found as far back as nineteen twenty, because its function is relevant with fertility, so also known as tocopherol, it is the derivant of chroman, known 8 kinds at present, wherein the highest with the physiologically active of alpha-tocopherol.Vitamin E is that the mankind can not obtain scarce a kind of fatsoluble vitamin, has the functions such as antioxidation, antisterility, enhancing human body immunity power; It is when anaerobic agent exists, and stablizes heat, acid, alkali, on the contrary then oxidizable one-tenth quinones; Visible ray is stablized, but can by broken up with UV light; Comparatively stable after sour environment and esterification.
The vitamin E overwhelming majority is in the market alpha-tocopherol.Due to vitamin E unstable chemcial property, be all generally that its esterification is formed vitamin-e ester, thus protect phenolic hydroxyl group and make it not easily oxidized, some vitamin-e ester also possesses specific physiological function simultaneously.Vitamin e acetate can be used as the medicine of cosmetics additive and vitimin supplement E and the main component of nutriment, is thus most widely used.
For making vitamin E products application in every field, corresponding dosage form need be made into.Report both at home and abroad about this respect technology mainly contains following several:
Vitamin e derivative is generally needed to have good water solublity when being applied to food and medicine field.As CN101444495B with chitosan and maltodextrin be wall material, with soybean lecithin and Tween 80 for compound emulsifying agent, obtain Vitamin E contained micro capsule by spraying dry; CN101803741B is by the alcohol-water solution of emulsifying agent and the alcoholic solution of vitamin e derivative at high-gravity rotating bed middle mixing and emulsifying, and obtain transparent vitamin E emulsion, obtained microcapsule powder can be applicable to transparent beverage; CN101502326B take vitamin E as core, with lecithin, cholesterol and Tween 80 for wall material, adopts alcohol injection to prepare vitamin E liposome, and obtains vitamin E nano liposome through extra high pressure homogenize; CN101703243B utilizes the maltodextrin of special ratios and gelatin as wall material, using the mixture of glyceryl monostearate and sucrose ester as emulsifying agent, and obtained very easily water-soluble Vitamin E contained micro capsule.These methods need to use numerous emulsifiers above, significantly increase cost while improving vitamin E products application performance.
When vitamin E is applied as feed additive, because cost reason is not generally taked and technique like other domain class such as food, more is adopt the method with Silicon stone absorption at present.As CN1197553C proposes first to be mixed with Silicon stone by ative starch, then add liquid vitamin E derivant, the obtained vitamin E powder of mixing.They think that the method reduces by 10% than spray drying method cost; The vitamin e derivative that CN101346129A describes a kind of heating and Silicon stone reduce pressure and mix the method for obtained adsorbate in vacuum mixer; CN100527983C mentions and adds when utilizing Silicon stone to adsorb vitamin E the bioavailability that sorbitol ester emulsifier can improve vitamin e acetate.These methods reduce production cost really in a lot of above, but obviously the existence of Silicon stone is digested and assimilated organism is an obstacle.
In the production process of numerous vitamin products, starch octenyl succinate anhydride is a kind of comparatively conventional emulsifying embedding medium, and its preparation principle can carry out under the alkali condition of gentleness based on esterification.This product was listed in U.S. food additive category in 1972 by U.S. food and FAD (FDA), was also the starch alkenyl succinate ester product being uniquely allowed for food additive at present by FDA.Starch octenyl succinate anhydride has now been included China and has used in the approval of interior Main Countries, and when its quality index is production food stage starch octenyl succinate anhydride, the maximum permission use amount of octenyl succinic acid anhydride is 3%.The business starch octenyl succinate anhydride of current application is generally by after esterification, hydrolysis is obtained again, and most kind is completely water-soluble.
Compare Silicon stone, starch octenyl succinate anhydride has multiple advantages such as emulsifiability is good, good biocompatibility, but the price of business-like starch octenyl succinate anhydride is significantly higher than Silicon stone, greatly limit its application on feed additive.
But, described in CN1197553C, ative starch, because with low cost, itself is again nutrient substance, has a lot of innate advantage in various fields application.As we the patent CN102796398A of previously application just mentions the beta-carotene microcapsule utilizing the fused mass original position emulsifying of the starch milk of enzymolysis in advance and beta-carotene, vegetable oil and octenyl succinic acid anhydride to obtain low cost.
Research shows, after the nutrient substance such as Vitamin E preparation enter organism, and need through the digestion program of multiple tracks complexity.For human body, vitamin E and derivant thereof are entering digestive tract and after discharging from preparation, are generally needing to be dissolved in the oleophilic substances such as oils and fats, after through bile emulsifying, mainly absorb at small intestinal place, be brought into each organ in body by lymphatic circulation.Vitamin E and derivant thereof discharge the stable existence and effectively absorption that are unfavorable for vitamin E too early or too much in digestive tract front end, so ideal condition is the few release as far as possible in gastric juice of this type of material, discharge completely again after entering intestinal, and under the assistance of oils and fats, by human body is digested and assimilated.But from published patented technology, not yet find the report with the spacetabs type Vitamin E preparation technology that business promotion is worth.
In fact, the resistant starch containing different content in some ative starch, this starch has resistance to enzymolysis because molecular structure changes, and thus digestion slowly, just can be completely absorbed in a long time and enter blood in vivo.The method improving resistance starch content has a lot, and heating cools rapidly again can impel its accelerated ageing, also can promote resistance starch content by the method adding the specific compounds such as fat, debranching enzyme or phosphoric acid in addition.Have not yet to see the report that resistant starch is applied to vitamin E production.
Summary of the invention
The object of the invention is for above-mentioned Problems existing, a kind of preparation method of spacetabs type vitamin e derivative preparation is provided, the spacetabs type vitamin e derivative preparation that this preparation method obtains can reduce the release of vitamin e derivative in gastric juice, vitamin e derivative can be made to discharge completely in intestinal simultaneously, improve the utilization rate of vitamin e derivative.
A preparation method for spacetabs type vitamin e derivative preparation, comprises the steps:
(1) by after butt starch and water mixing, be warming up to 40 ~ 70 DEG C, add hydrochloric acid under abundant stirring condition and to be hydrolyzed reaction, react the starch milk obtaining partial hydrolysis after 15 ~ 60 minutes;
(2) it is 7.5 ~ 9.0 that the starch milk sodium hydrate aqueous solution after partial hydrolysis step (1) obtained is neutralized to pH value, then under 30 ~ 50 DEG C of abundant stirring conditions, add octenyl succinic acid anhydride and carry out esterification, obtain the starch milk after esterification;
By adding sodium hydrate aqueous solution control pH between 7.5 ~ 9.0 in esterification reaction process;
3) starch milk after esterification step (2) obtained filters, after the filter cake obtained mix with vitamin e derivative, successively through grinding, oven dry, freezing, pulverize and sieve and obtain described spacetabs type vitamin e derivative preparation.
The present invention carries out partial hydrolysis by concentrated hydrochloric acid to butt starch, containing a certain amount of resistant starch in the starch milk obtained, then after carrying out esterification with octenyl succinic acid anhydride, after making preparation with vitamin e derivative further, contained resistant starch has certain resistance to enzymolysis, slow down the release of active component in gastric juice in said preparation, thus there is slow release effect; Meanwhile, avoid the shortcoming that Silicon stone is unfavorable for digesting, can discharge completely in intestinal juice, be conducive to absorbing; And dryness starch price used is lower, significantly reduces cost.
As preferably, in step (1), starch is potato starch, corn starch, waxy corn starch, pea starch or sweet potato starch.
The amount ratio of each material can have an impact to the degree that the condition of reaction is carried out, thus have influence on the content of resistant starch further, as preferably, in step (1), the mass concentration of described concentrated hydrochloric acid is 36 ~ 37.5%, and the mass concentration of described sodium hydroxide is 1 ~ 5%;
The mass ratio of described butt starch, water and concentrated hydrochloric acid is 100:150 ~ 200:1 ~ 10.
The length in response time also can the content of antagonism starch have an impact, and as preferably, in step (1), stir speed (S.S.) is 100 ~ 200 revs/min, and the response time is 15 ~ 60 minutes.
Different types of starch component has certain difference, by controlling different hydrolysis temperatures and hydrolysis time, product can be made to obtain optimum slow release effect, as further preferred, in step (1), described butt starch is butt corn starch, and the temperature of hydrolysis is 60 ~ 70 DEG C, and hydrolysis time is 10 ~ 20 minutes; Or
Described butt starch is butt potato starch, and the temperature of hydrolysis is 40 ~ 50 DEG C, and hydrolysis time is 50 ~ 60 minutes; Or
Described butt starch is butt waxy corn starch, and the temperature of hydrolysis is 40 ~ 50 DEG C, and hydrolysis time is 30 ~ 40 minutes.
As preferably, in step (2), speed of agitator is 100 ~ 200 revs/min, and the response time is 60 ~ 120 minutes;
Described butt starch and the mass ratio of octenyl succinic acid anhydride are 1:0.5 ~ 3.
As preferably, in step (3), the mass ratio of butt starch used in described vitamin e derivative and step (1) is 100 ~ 350:100, now, in the vitamin e derivative preparation obtained, vitamin e derivative content is higher, and slow release effect is better.
As preferably, in step (3), described vitamin e derivative is vitamin e acetate or vitamin e succinate.
As preferably, in step (3), milling time is 0.5 ~ 2 hour;
Bake out temperature is 120 ~ 170 DEG C, and drying time is 0.5 ~ 5 hour;
Cryogenic temperature is-45 ~ 0 DEG C, cooling time 1 ~ 12 hour.
Compared with prior art, the invention has the advantages that:
1) business starch octenyl succinate anhydride in preparation process except completing the esterification of starch and octenyl succinic acid anhydride, also need afterwards to control molecular weight distribution by hydrolytic processes such as the enzymolysis of complexity and reach water miscible requirement, thus cost is higher; The present invention utilizes the starch of partial hydrolysis to obtain starch ester, is directly used in coated vitamin E derivant, not only reduces production cost, the resistant starch component simultaneously remained to greatest extent in starch because of non-complete hydrolysis.
2) starch octenyl succinate anhydride that the present invention obtains is the natural product that can be absorbed by organism catapepsis, and can effective coated vitamin E derivant by the effect such as emulsifying, grinding, producing, playing in transportation the effect of protection vitamin e derivative, can digested and assimilated by organism together with vitamin e derivative again entering after in organism; Silicon stone of the prior art is the carrier becoming vitamin e derivative by adsorbing; vitamin e derivative can not be protected completely in production, transportation; and enter Silicon stone after in organism and cannot be digested and assimilated by organism, the vitamin e derivative adsorbed can not ensure to discharge completely.
3) the vitamin e derivative preparation that business starch octenyl succinate anhydride is coated because of its clad material in the production process of himself by complete hydrolysis, can discharge rapidly after entering organism, thus cause vitamin e derivative to discharge too early or too much in digestive tract front end, affect organism fully digesting and assimilating vitamin e derivative.The clad material that the present invention selects with the starch of partial hydrolysis for raw material, inherently there is certain resistant starch component, the content of resistant starch in clad material is improved again in follow-up high temperature and the freezing course of processing, thus can slow release effect be reached after making vitamin e derivative preparation enter organism, promote that vitamin e derivative is is fully digested and assimilated by organism.
In sum, the present invention with the ative starch of low cost for raw material prepares vitamin e derivative preparation, not only cost of material has competitive advantage and biocompatibility is significantly better than Silicon stone, and enlarges markedly and reach slow release effect because of the resistance starch content of clad material.
Detailed description of the invention
Embodiment 1
1) join in reactor by 100kg butt corn starch and 150kg water, controlling jacket temperature is 70 DEG C, and speed of agitator is 200 revs/min, controls to add 10kg 37% concentrated hydrochloric acid, be hydrolyzed 15 minutes, obtain the starch milk after partial hydrolysis with metering valve.
2) by step 1) starch milk after the partial hydrolysis that obtains with 1% sodium hydrate aqueous solution to neutralize pH value be 7.5, then adjusting jacket temperature is 30 DEG C, speed of agitator is 100 revs/min, control to add 3kg octenyl succinic acid anhydride with metering valve, and the sodium hydrate aqueous solution automatically controlling to add 1% makes the pH value of reactant liquor in still control 7.5, react 120 minutes, obtain the starch milk after esterification.
3) filter, filter cake is mixed with 100kg vitamin e acetate, then grind 2 hours, then transfer in drying device.
4) in drying device, pass into steam, grinding product is dried 0.5 hour at 170 DEG C; Then material is transferred in refrigerating plant ,-45 DEG C of freezing processing 1 hour.
5) by step 4) described in material take out, then through pulverize, sieve, obtain spacetabs type vitamin e acetate preparation.
Embodiment 2
1) join in reactor by 100kg butt potato starch and 200kg water, controlling jacket temperature is 40 DEG C, and speed of agitator is 100 revs/min, controls to add 1kg37% concentrated hydrochloric acid, be hydrolyzed 60 minutes, obtain the starch milk after partial hydrolysis with metering valve.
2) by step 1) to neutralize pH value be 9.0 for starch milk sodium hydroxide after the partial hydrolysis that obtains, then adjusting jacket temperature is 50 DEG C, speed of agitator is 200 revs/min, control to add 0.5kg octenyl succinic acid anhydride with metering valve, and automatically control to add sodium hydroxide and make the pH value of reactant liquor in still control 9.0, react 60 minutes, obtain the starch milk after esterification.
3) filter, filter cake is mixed with 100kg vitamin e acetate, then grind 0.5 hour, then transfer in drying device.
4) in drying device, pass into steam, grinding product is dried 5 hours at 120 DEG C; Then material is transferred in refrigerating plant, 0 DEG C of freezing processing 12 hours.
5) by step 4) described in material take out, then through pulverize, sieve, obtain spacetabs type vitamin e acetate preparation.
Embodiment 3
1) join in reactor by 100kg butt waxy corn starch and 160kg water, controlling jacket temperature is 50 DEG C, and speed of agitator is 150 revs/min, controls to add 2kg37% concentrated hydrochloric acid, be hydrolyzed 30 minutes, obtain the starch milk after partial hydrolysis with metering valve.
2) by step 1) to neutralize pH value be 8.0 for starch milk sodium hydroxide after the partial hydrolysis that obtains, then adjusting jacket temperature is 40 DEG C, speed of agitator is 150 revs/min, control to add 2.5kg octenyl succinic acid anhydride with metering valve, and automatically control to add sodium hydroxide and make the pH value of reactant liquor in series connection still control 8.0, react 90 minutes, obtain the starch milk after esterification.
3) filter, filter cake is mixed with 100kg vitamin e acetate, then grind 1.5 hours, then transfer in drying device.
4) in drying device, pass into steam, grinding product is dried 1 hour at 160 DEG C; Then material is transferred in refrigerating plant ,-20 DEG C of freezing processing 6 hours.
5) by step 4) described in material take out, then through pulverize, sieve, obtain spacetabs type vitamin e acetate preparation.
Embodiment 4
1) join in reactor by 200kg butt pea starch and 340kg water, controlling jacket temperature is 60 DEG C, and speed of agitator is 150 revs/min, controls to add 5kg37% concentrated hydrochloric acid, be hydrolyzed 40 minutes, obtain the starch milk after partial hydrolysis with metering valve.
2) by step 1) to neutralize pH value be 8.2 for starch milk sodium hydroxide after the partial hydrolysis that obtains, then adjusting jacket temperature is 40 DEG C, speed of agitator is 170 revs/min, control to add 2kg octenyl succinic acid anhydride with metering valve, and automatically control to add sodium hydroxide and make the pH value of reactant liquor in still control 8.2, react 100 minutes, obtain the starch milk after esterification.
3) filter, filter cake is mixed with 400kg vitamin e succinate, then grind 1 hour, then transfer in drying device.
4) in drying device, pass into steam, grinding product is dried 2 hours at 130 DEG C; Then material is transferred in refrigerating plant ,-10 DEG C of freezing processing 8 hours.
5) by step 4) described in material take out, then through pulverize, sieve, obtain spacetabs type vitamin e succinate preparation.
Embodiment 5
1) join in reactor by 100kg butt sweet potato starch and 180kg water, controlling jacket temperature is 55 DEG C, and speed of agitator is 120 revs/min, controls to add 7kg37% concentrated hydrochloric acid, be hydrolyzed 20 minutes, obtain the starch milk after partial hydrolysis with metering valve.
2) by step 1) to neutralize pH value be 7.8 for starch milk sodium hydroxide after the partial hydrolysis that obtains, then adjusting jacket temperature is 45 DEG C, speed of agitator is 120 revs/min, control to add 2kg octenyl succinic acid anhydride with metering valve, and automatically control to add sodium hydroxide and make the pH value of reactant liquor in still control 7.8, react 110 minutes, obtain the starch milk after esterification.
3) filter, filter cake is mixed with 350kg vitamin e succinate, then grind 1 hour, then transfer in drying device.
4) in drying device, pass into steam, grinding product is dried 1.5 hours at 140 DEG C; Then material is transferred in refrigerating plant ,-30 DEG C of freezing processing 10 hours.
5) by step 4) described in material take out, then through pulverize, sieve, obtain spacetabs type vitamin e succinate preparation.
Extracorporeal releasing test contrasts:
Sample (sample 1 prepared by Example 1, vitamin e acetate content is about 50%), sample (sample 2 prepared by embodiment 2, vitamin e acetate content is about 50%), sample (sample 3 prepared by embodiment 3, vitamin e acetate content is about 50%), utilize vitamin e acetate microcapsule (sample 4 prepared by business starch octenyl succinate anhydride Hicap100, vitamin e acetate indicates content 50%) and the vitamin e acetate preparation (sample 5 that utilizes silicon dioxide to adsorb, vitamin e acetate indicates content 50%) carry out extracorporeal releasing test contrast, wherein sample 4 and sample 5 are commercial sample, purchased from newly with become limited company.
1g sample is joined in 100ml simulated gastric fluid, at 37 DEG C, stir 0.5 hour with the rotating speed of 100rpm, measure the dissolution rate of vitamin e acetate; By above-mentioned solution left standstill 5 minutes, then adjust ph to 7.0, then add 400ml simulated intestinal fluid, stir with the rotating speed of 100rpm at 37 DEG C, measure the dissolution rate of vitamin e acetate every 1 hour.
The vitamin e acetate total content of the content/sample of vitamin e acetate in the dissolution rate=solution of vitamin e acetate
Wherein in solution, the content of vitamin e acetate is centrifugal by getting part test solution, utilizes HPLC to detect supernatant, with quantified by external standard method.Testing conditions is C
18chromatographic column, with pure methanol for mobile phase, flow velocity is 1.0ml/min, detects under 285nm.
Actual release in vitro result is as shown in table 1.
The dissolution rate of the different Vitamin E preparation of table 1
Table 1 result shows, and in the vitamin e acetate preparation that the present invention obtains, sample 1 only releases the working substance of 27.2% under gastric juice environment, then to 5h, working substance is discharged completely substantially under intestinal juice environment; Sample 2 only releases the working substance of 42.1% under gastric juice environment, then to 3h, working substance is discharged completely substantially under intestinal juice environment; Sample 3 only releases the working substance of 31.5% under gastric juice environment, then to 3 ~ 5h, working substance is discharged completely (surveying complete release time is 3.5h) substantially under intestinal juice environment;
Utilize the vitamin e acetate preparation (sample 4) that business starch octenyl succinate anhydride is obtained, discharge completely under gastric juice environment, so do not have a slow release effect; The vitamin e acetate preparation (sample 5) utilizing Silicon stone to adsorb to obtain releases the working substance of 36.3% after gastric juice environment is issued to adsorption equilibrium, but be also reach adsorption equilibrium in the short time under intestinal juice environment, the working substance of about 63% can only be discharged at most, cause the working substance of about 37% to residue in Silicon stone always.
Claims (9)
1. a preparation method for spacetabs type vitamin e derivative preparation, is characterized in that, comprises the following steps:
(1) by after butt starch and water mixing, be warming up to 40 ~ 70 DEG C, add hydrochloric acid under abundant stirring condition and to be hydrolyzed reaction, react the starch milk obtaining partial hydrolysis after 15 ~ 60 minutes;
(2) it is 7.5 ~ 9.0 that the starch milk sodium hydrate aqueous solution after partial hydrolysis step (1) obtained is neutralized to pH value, then under 30 ~ 50 DEG C of abundant stirring conditions, add octenyl succinic acid anhydride and carry out esterification, obtain the starch milk after esterification;
By adding sodium hydrate aqueous solution control pH between 7.5 ~ 9.0 in esterification reaction process;
3) starch milk after esterification step (2) obtained filters, after the filter cake obtained mix with vitamin e derivative, successively through grinding, oven dry, freezing, pulverize and sieve and obtain described spacetabs type vitamin e derivative preparation.
2. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, is characterized in that, in step (1), starch is potato starch, corn starch, waxy corn starch, pea starch or sweet potato starch.
3. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, is characterized in that, in step (1), the mass concentration of described hydrochloric acid is 36 ~ 37.5%, and the mass concentration of described sodium hydroxide is 1 ~ 5%;
The mass ratio of described butt starch, water and hydrochloric acid is 100:150 ~ 200:1 ~ 10.
4. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, is characterized in that, in step (1), stir speed (S.S.) is 100 ~ 200 revs/min.
5. the preparation method of spacetabs type vitamin e derivative preparation according to claim 2, is characterized in that, in step (1), described starch is corn starch, and the temperature of hydrolysis is 60 ~ 70 DEG C, and hydrolysis time is 10 ~ 20 minutes; Or
Described starch is potato starch, and the temperature of hydrolysis is 40 ~ 50 DEG C, and hydrolysis time is 50 ~ 60 minutes; Or
Described starch is waxy corn starch, and the temperature of hydrolysis is 40 ~ 50 DEG C, and hydrolysis time is 30 ~ 40 minutes.
6. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, is characterized in that, in step (2), speed of agitator is 100 ~ 200 revs/min, and the response time is 60 ~ 120 minutes;
Described butt starch and the mass ratio of octenyl succinic acid anhydride are 1:0.5 ~ 3.
7. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, it is characterized in that, in step (3), the mass ratio of butt starch used in described vitamin e derivative and step (1) is 100 ~ 350:100.
8. the preparation method of spacetabs type vitamin e derivative preparation according to claim 1, is characterized in that, in step (3), described vitamin e derivative is vitamin e acetate or vitamin e succinate.
9. spacetabs type vitamin e derivative preparation according to claim 1, it is characterized in that, in step (3), milling time is 0.5 ~ 2 hour;
Bake out temperature is 120 ~ 170 DEG C, and drying time is 0.5 ~ 5 hour;
Cryogenic temperature is-45 ~ 0 DEG C, cooling time 1 ~ 12 hour.
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| CN115363982A (en) * | 2021-12-14 | 2022-11-22 | 广州花出见生物科技有限公司 | Modified silicon powder prepared by supergravity acceleration process and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020093919A1 (en) * | 2018-11-06 | 2020-05-14 | 浙江新和成股份有限公司 | Adsorptive starch and adsorptive starch agglomerate, preparation method and application thereof, and nutrient formulation comprising same |
| CN115363982A (en) * | 2021-12-14 | 2022-11-22 | 广州花出见生物科技有限公司 | Modified silicon powder prepared by supergravity acceleration process and application thereof |
| CN115363982B (en) * | 2021-12-14 | 2023-07-25 | 广州花出见生物科技有限公司 | Modified silicon powder prepared by supergravity acceleration process and application thereof |
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