CN1403093A - Oral vanadium replenishing agent with bimetallic oxide as carrier and its prepn and usage - Google Patents
Oral vanadium replenishing agent with bimetallic oxide as carrier and its prepn and usage Download PDFInfo
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- CN1403093A CN1403093A CN 02137166 CN02137166A CN1403093A CN 1403093 A CN1403093 A CN 1403093A CN 02137166 CN02137166 CN 02137166 CN 02137166 A CN02137166 A CN 02137166A CN 1403093 A CN1403093 A CN 1403093A
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Abstract
The oral vanadium replenishing agent is one kind of bimetallic oxide containing active vanadium, and the vanadium content in the bimetallic oxide is 0.01-0.5 wt%. The preparation process includes heating hydrotalcite to 450-550 deg.c to obtain bimetallic oxide, planting vanadium anion into bimetallic oxide lattice via the adsorption of bimetallic oxide, drying and grinding or spray drying to obtain solid powder or pressed into tablet. The oral vanadium replenishing agent can provide people or animal with essential vanadium via slow release without the side effect of directly taking vanadium. Replenishing vanadium can promote growth and reproduction, prevent and treat vanadium deficiency diseases, treat diabetes, hemorrhagic anemia and other diseases.
Description
Technical field
The present invention relates to a kind of is oral vanadium replenishing agent and the preparation and the using method of carrier with the bimetallic oxide.
Background technology
Sweden chemist N.G.sefstrom had found v element (Vanadium) in iron mine in 1830.Gamyee in 1876 and Larmuth begin one's study vanadium to the physiological action of frog heart, indicate that vanadium enters the research field of life sciences.The seventies in 20th century, the essential of vanadium is the focus of vanadium research.When extracting commodity ATP in horse skeletal muscle, Cherney in 1975 etc. find the mortifier of Na-K-ATP enzyme.Josephosn in 1977 and Cantley have confirmed that this mortifier is a vanadate, after prove that again vanadate is the potent inhibitor of sodium pump.At the end of the seventies, vanadium just is confirmed as the essential trace element of humans and animals.Enter the eighties, people pay close attention to the pharmacological action of vanadium more, begin the chemical compound of vanadium is used for treatment of diseases such as diabetes, anemia, tuberculosis, neurasthenia and rheumatic fever.
Vanadium is a kind of transition metal, present-3 ,-1,0 ,+1 ,+2 ,+3 ,+4 ,+multiple valence states such as 5.Vanadium in the soil is tervalent, and the average content in the earth's crust is 135.0mg/Kg, substantially exceeds elements such as Cu, Zn, Co; Vanadium in the fresh water generally is a pentavalent, and content is 0.3～720.0 μ g/L; Vanadium is dense in marine sediment and the mud, is about 10.0～100.0mg/L; Vanadium in the air-borne dust mainly is V
2O
5Vanadium extensively exists in the animal body, but concentration is lower, content between 0.02～0.06mg/Kg, based on+4 ,+5, the extracellular exists with the form of vanadic acid root (+5), the form with vanadyl (+4) in the cell exists.Vanadium in the mammal mainly accumulates in skeleton, kidney, the liver; The intravital vanadium of people mainly is stored in fat and the serum lipid.Compare with other higher mammals, content of vanadium is higher in the chicken.
Vanadium has three kinds of biochemical properties: one, and vanadium is with the form of vanadic acid root and the avtive spot of phosphate radical competition phosphate transferrin, phosphohydrolase and phosphotransferase; Its two, vanadium with the binding site of other transition metal ions competition on metalloprotein, is fought for little ligand such as ATP with the ionic form of vanadyl; Its three, participate in intracellular redox reaction, can be as the contact agent of redox system retardance electron transport system, can also with glutathion generation oxidation reaction.These biochemical properties make vanadium produce inhibitory action to many enzymes, and they are bases of vanadium physiological function.Vanadium mainly contains following several respects to the important function of people and animal physiological function:
1) promotes animal growth: add an amount of vanadium in the feedstuff and can promote animal growth.Otherwise animal growth can be obstructed when lacking vanadium.For example, when chicken lacked vanadium, wing, tail feathers, bone growth were bad, the body poor growth; When goat lacks vanadium, the lost of life, 50% kid is in death lactation period.
2) be beneficial to animal reproduction: when lacking vanadium, the animal reproduction function descends.For example, conception rate descended when female animal lacked vanadium, and abortion ratio increases, and milk yield reduces.
3) hemopoietic function: vanadium can cause histanoxia to stimulate the hemopoietic function of bone marrow by oxidation-reduction system in the baffle, can also strengthen ferrum to erythrocytic regeneration.Mending vanadium can make hemoglobin, reticulocyte and erythrocytic quantity increase.
4) influence cholesterol metabolism: vanadium can promote lipid metabolism, and cholesterol is synthetic in the inhibition liver, reduces phospholipid and content of cholesterol in the liver.Scarce vanadium can cause that body inner cholesterol content increases growth retardation.
5) influence cardiovascular system: vanadate has the effect of similar cardiac glycoside/glycoside.The vanadate of higher concentration has inhibitory action to myocardial contraction, and low concentration (can make 0.05～1.00mmol/L) time ventricular systole power that exsomatizes strengthen, thereby atrial contractility is weakened.Vanadate can also increase the resistance of various vascular bedes, and blood vessel is had contraction.
6) anti-diabetic: vanadium has the para-insulin effect.Behind the oral vanadate of diabetics, obviously blood sugar lowering, glucose in urine concentration, weight increase and rate of growth promote histiocytic glucose transport, reduce the absorption of glucose, the decomposition of Profilin matter and fat promotes lipogenesis.These effects all are that vanadium is realized by the function of regulating carbohydrate metabolism enzyme, glucose transporter, lipid metabolism enzyme.In addition, vanadium can also improve the complication of diabetes such as cardiomyopathy, renomegaly.
The medicine of treatment diabetes commonly used is sodium vanadate, sodium metavanadate.These anion vanadium be difficult for to absorb, and directly take the pure product of vanadate and side effect such as diarrhoea, gastrointestinal upset and gastrointestinal mucosal be impaired can occur.
Summary of the invention
The purpose of this invention is to provide a kind of is oral vanadium replenishing agent and the preparation and the using method of carrier with the bimetallic oxide.
Vanadium replenishing agent of the present invention is a kind of anionic bimetallic oxide of commutative vanadium that contains, and by weight percentage, the content of v element in bimetallic oxide is 0.01～0.5%, and preferred content is 0.1%.
Of the present invention is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, may further comprise the steps:
1) brucite is heated under 450～550 ℃ of temperature, make bimetallic oxide;
2) bimetallic oxide is ground to less than 400 orders, adds water and stir, make concentration and be 10% suspension slurry;
3) be the vanadic salts of bimetallic oxide weight 0.01～0.5% with content of vanadium, be pre-configured to 0.1～0.5% solution, while stirring vanadic salts solution is slowly poured in the suspension slurry, fully reaction;
4) select methods such as precipitation, centrifugal or filtration for use, make the suspension slurry dehydration;
5) the step 4) gains are dried being lower than under 80 ℃ of temperature, be ground to less than 300 orders, obtain water content less than 10% carry the vanadium dual metal oxide powder, perhaps the step 4) gains are added maximum 5% dispersant, adding water stirs, make the ore pulp of 10-30%, with spray drying method obtain water content less than 10% carry the vanadium dual metal oxide powder.
The brucite that uses in the invention can be the commercial goods or be prepared from according to the following steps:
1) is mixed with the solution that concentration is 0.3M with aluminum salt is soluble in water, in solution, adds 2～4 times of mole numbers, stir, make saline solution A until molten entirely to the magnesium salt of aluminum salt;
2) Na that mole number is equated with magnesium salt
2CO
3Soluble in water, be made into the solution that concentration is 0.8M, in solution, add mole number and be three times in Na
2CO
3NaOH, stir until molten entirely, make aqueous slkali B;
3) adopt coprecipitation that two kinds of solution of above-mentioned A, B are dropwise splashed in the water that strong agitation simultaneously; Perhaps, obtain white suspension with two solution rapid mixing;
4) suspension is put into water-bath, under 80 ℃, stir crystallization; Perhaps suspension is placed pressure vessel, crystallization under 120～160 ℃ of conditions;
5) with step 4) products therefrom sucking filtration, be washed to neutrality.Put into baking oven,, obtain brucite 60～80 ℃ of oven dry down.
In the preparation method of the present invention, said vanadic salts can be positive vanadate, metavanadate, pyrovanadate and hydrate thereof.Dispersant can be a Sodium triphosphate, tetrasodium pyrophosphate, one or more in the sodium lignosulfonate.Said aluminum salt can be aluminum chloride, aluminum nitrate, aluminum sulfate and hydrate thereof.Magnesium salt can be magnesium chloride, magnesium nitrate, magnesium sulfate and hydrate thereof.
Usually, pulverous year vanadium dual metal oxide is pressed into the tablet that every weight is 0.01～0.05 gram.
Of the present invention is the using method of the oral vanadium replenishing agent of carrier with the bimetallic oxide:
1) is used for domestic animal, the oral benefit vitriol of poultry,, admixes in the domestic animal daily ration, admix in the poultry diet by the dosage of 0.05～0.5 milligram of v element of per kilogram feedstuff by the dosage of 0.5～5 milligram of v element of per kilogram feedstuff with pulverous year vanadium dual metal oxide.
2) be used for human orally, v element dosage is micrograms every days 10～100, divides three inferior to taking half an hour after meal.
Advantage of the present invention is:
1) character of utilizing bimetallic oxide to rebuild adsorpting anion by layer structure is carried the vanadium anion, and implementation method is easy, and production cost is lower;
2) slowly releasing effect of bimetallic oxide and improved the safety in utilization of inorganic vanadic salts with the gastric acid product has alleviated side effect such as the diarrhoea of directly taking the pure product of vanadate and bringing, gastrointestinal upset;
3) carrier bimetallic oxide and gastrointestinal tract mucous affinity height have improved the absorbance of vanadium greatly, have also reduced the environment residual quantity simultaneously;
4) easy to use, the scope of application is extensive.
The specific embodiment
Bimetallic oxide is a kind of synthetic material who is made up of the metal-oxide of two kinds of different valence state, is called for short LDO (Layered Double Oxides).It has the shepardite of being similar to (Mg (OH)
2) layer structure, its predecessor is a hydrotalcite-based compound, also is called as anionic clay.The chemical structure of general formula of brucite is:
[M
1-x IIM
x III(OH)
2]
X+[A
X/n N-MH
2O] M wherein
IIBe Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Ca
2+Deng divalent metal; M
IIIBe Al
3+, Fe
3+, Cr
3+, Co
3+, Mn
3+Deng trivalent metal cation; A
N-Be CO
3 2-, Cl
-, NO
3 -, SO
4 2-Etc. anion; X=0.5～0.17; M
II/ M
III=1～5.
Above structural formula can be regarded as divalent metal in the shepardite by the alternate product of trivalent metal cation part, is the positive charge of balanced structure layer, between structure sheaf again filling anion, also have hydrone in addition.Brucite promptly loses interlayer anion and hydrone 450 ℃～550 ℃ following calcinings, obtains corresponding bimetallic oxide (LDO).The general formula of bimetallic oxide is: M
IIMM
IIINOx, wherein x=m+3n/2.Bimetallic oxide can come the restoration and reconstruction hydrotalcite structure by anion and the hydrone in the absorption environment, and because of having bigger specific surface area and pore volume, acceptant object.So can be with bimetallic oxide as the anionic carrier of vanadium.With Mg-Al-O is the bimetallic oxide of main composition; on chemical property with magnesium oxide, alumina type seemingly; can react with gastric acid; its product is to gastrointestinal mucosal tool affinity and protectiveness; therefore bimetallic oxide can reduce side effect such as diarrhoea, gastrointestinal upset, gastrointestinal mucosal that inorganic vanadic salts causes be impaired, and increases its absorbance.
The double-metal hydroxide system that the present invention uses makes the intermediate product brucite earlier by coprecipitation or hydro-thermal method, and primary raw material is magnesium salt, aluminum salt, Caustic soda and carbonate.Wherein, magnesium salt and aluminum salt can adopt sulfate, nitrate and hydrochlorate and hydrate thereof.The mole ratio of magnesium salt and aluminum salt has considerable influence to the absorption property of product, generally should be controlled at 2: 1 to 4: 1 scopes, and recommendation is 3: 1.When obtain solution A, the dissolving of magnesium salt and aluminum salt order is unimportant.Solution B is formulated by sodium carbonate and Caustic soda, wherein sodium carbonate and magnesium salt equimolal, and the mole number of Caustic soda is three times of sodium carbonate, the dissolving order of the two is unimportant; Also can replace Caustic soda and carbonate with carbamide.
Coprecipitation is identical with the solution that hydro-thermal method is used, but with two kinds of blended modes of solution and crystallization condition difference.Coprecipitation adopts to instil mixes two kinds of solution, need longer instillation time and crystallization time, but equipment needed thereby is simple.The hydro-thermal method production procedure is short, but needs the working pressure container, and equipment investment is bigger.
Brucite is heated to 450～550 ℃ can obtains bimetallic oxide.
The reaction that v element is carried on the bimetallic oxide belongs to the selective absorption reaction.Its principle is that bimetallic oxide has the strong tendency of anion obtained and hydrone in aqueous solution, with the structure of restoration and reconstruction brucite.The saturated extent of adsorption that bimetallic oxide aligns vanadic acid root, metavanadic acid root and pyrovanadic acid radical ion can reach more than the 300mg/g.Be taking convenience and dosage safety, the consumption of vanadic salts should make v element weight be equivalent to 0.01～0.5% of bimetallic oxide weight, and recommendation is 0.1%.In this amount ranges, bimetallic oxide to the anionic adsorption rate of vanadium in the aqueous solution more than 98%.
The dewatering process of product, but treatment in accordance with local conditions select for use filter cloth filtration, precipitation, centrifugal or pressure filter to dewater.Can use conventional drying plant drying after the dehydration.The vanadium dual metal oxide that carries after the oven dry is block, can select for use conventional mining equiment crushing grinding to granularity to be not more than 300 orders.
As select spray drying for use, then need serosity slurrying again, and add dispersant having dewatered.Be applicable to that dispersant requirement of the present invention is not very strict.The dispersant of recommending to use is a Sodium triphosphate, one or more in tetrasodium pyrophosphate and the sodium lignosulfonate.The purpose that adds dispersant is the viscosity that reduces slurry, makes the spray drying of high concentration slurry become possibility, thereby reduces energy consumption for drying.Spray dried products is a kind of runny pressed powder.Be applicable to that spray drying device of the present invention is routinely, technical is well-known.
Need suppress in flakes for a human oral year vanadium dual metal oxide, mainly be to be taking convenience and grasp dosage.It is oral to be used for the mankind, and v element dosage is micrograms every days 10～100, divides three inferior to taking half an hour after meal.
The fowl poultry is mended vanadium should directly use powder product.Need in the different animals feed diet to add vanadium by various dose.In feed diet, the addition of v element is: chickling 0.1mg/Kg, and laying hen 0.5mg/Kg, the anti-vanadium ability of ruminant is stronger, and addition is 5mg/Kg.Animal vanadium replenishing agent amount should be grasped in above-mentioned scope.
Further specify the present invention below in conjunction with embodiment.
Embodiment 1: coprecipitation prepares brucite, and step is as follows:
1) with 0.225mol Mg (NO
3)
2With 0.075mol Al (NO
3)
2Be dissolved in and be made into Mg (NO in the 250mL water
3)
2And Al (NO
3)
2Saline solution A;
2) with 0.675mol NaOH and 0.225mol Na
2CO
3Be dissolved in and be made into NaOH and Na in the 250mL water
2CO
3Aqueous slkali B;
3) saline solution and alkali liquor are dropwise splashed into simultaneously in the 100mL distilled water that strong agitation, the dropping time is 4 hours;
4) suspension is put into water-bath, under 80 ℃ of temperature, stirred crystallization 24 hours;
5) with the product sucking filtration, be washed to neutrality.Under 80 ℃ of temperature, dry, obtain brucite.
Embodiment 2: the Hydrothermal Preparation brucite, and step is as follows:
1) with 0.225mol MgCl
2With 0.075mol AlCl
2Be dissolved in the 250mL water and be made into MgCl
2And AlCl
2Saline solution A;
2) with 0.675mol NaOH and 0.225mol Na
2CO
3Be dissolved in and be made into NaOH and Na in the 250mL water
2CO
3Aqueous slkali B;
3), get white serosity with above-mentioned two liquid rapid mixing.Rapidly serosity is put into autoclave, crystallization is 8 hours under 140 ℃ of conditions;
4) after the crystallization with the serosity sucking filtration, washing is to neutral.Under 80 ℃ of temperature, dry, obtain brucite.
Embodiment 3: with the bimetallic oxide is the preparation of the oral vanadium replenishing agent of carrier, may further comprise the steps:
1) brucite that will prepare voluntarily or buy is placed in the muffle furnace, calcines 3 hours down at 500 ℃, makes bimetallic oxide.
2) take by weighing the 1Kg bimetallic oxide, add water 9Kg, in agitator, stir and make suspension;
3) take by weighing 2.296g NH
4VO
3(containing v element 1g), dissolve in the 500mL water, stir until dissolving fully; When stirring, with NH
4VO
3Solution is slowly poured in the agitator that fills suspension; Allow mixed serum in agitator, react six hours, during stirred 3～5 minutes every one hour so that ore pulp keeps suspended state.
4) allow suspension slurry in agitator, leave standstill diel, make the bimetallic oxide natural sedimentation, absorb the supernatant, precipitate is poured on further dehydration on the filter cloth with siphonage.Serosity after the dehydration is divided into fritter with chipper or spades, is no more than under 80 ℃ of environment in temperature and dries.Broken, grinding make product granularity less than 300 orders, pack.V element content is 0.1% in the product at this moment.
The invention provides a kind of is oral vanadium replenishing agent and the preparation and the using method of carrier with the bimetallic oxide.The raw material sources that this invention relates to are extensive, and preparation method and technological process are simple, and production cost is lower, is easy to promotion and implementation.The oral vanadium replenishing agent that makes based on the present invention, can supply the mankind, poultry, domestic animal etc. to take,, have the growth of animal of promotion and breeding to provide humans and animals essential trace vanadium element, prevention, treatment animal vanadium deficiency disease, effects such as treatment human diabetes, hemorrhagic anemia, septicemia.
Claims (9)
1. one kind is the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that, it is a kind of anionic bimetallic oxide of commutative vanadium that contains, and by weight percentage, the content of vanadium in bimetallic oxide is 0.01～0.5%.
2. according to claim 1 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, may further comprise the steps:
1) brucite is heated under 450～550 ℃ of temperature, make bimetallic oxide;
2) bimetallic oxide is ground to less than 400 orders, adds water and stir, make concentration and be 10% suspension slurry;
3) be the vanadic salts of bimetallic oxide weight 0.01～0.5% with content of vanadium, be pre-configured to 0.1～0.5% solution, while stirring vanadic salts solution is slowly poured in the suspension slurry, fully reaction;
4) select methods such as precipitation, centrifugal or filtration for use, make the suspension slurry dehydration;
5) the step 4) gains are dried being lower than under 80 ℃ of temperature, be ground to less than 300 orders, obtain water content less than 10% carry the vanadium dual metal oxide powder, perhaps the step 4) gains are added maximum 5% dispersant, adding water stirs, make the ore pulp of 10-30%, with spray drying method obtain water content less than 10% carry the vanadium dual metal oxide powder.
3. according to claim 2 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that pulverous year vanadium dual metal oxide is pressed into the tablet that every weight is 0.01～0.05 gram.
4. according to claim 2 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that said vanadic salts is positive vanadate, metavanadate, pyrovanadate and hydrate thereof.
5. according to claim 2 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that said dispersant is one or more in Sodium triphosphate, tetrasodium pyrophosphate, the sodium lignosulfonate.
6. according to claim 2 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that said brucite is the commercial goods or is prepared from according to the following steps:
1) is mixed with the solution that concentration is 0.3M with aluminum salt is soluble in water, in solution, adds 2～4 times of mole numbers, stir, make saline solution A until molten entirely to the magnesium salt of aluminum salt;
2) Na that mole number is equated with magnesium salt
2CO
3Soluble in water, be made into the solution that concentration is 0.8M, in solution, add mole number and be three times in Na
2CO
3NaOH, stir until molten entirely, make aqueous slkali B;
3) adopt coprecipitation that two kinds of solution of above-mentioned A, B are dropwise splashed in the water that strong agitation simultaneously; Perhaps, obtain white suspension with two solution rapid mixing;
4) suspension is put into water-bath, under 80 ℃, stir crystallization; Perhaps suspension is placed pressure vessel, crystallization under 120～160 ℃ of conditions;
5) with step 4) products therefrom sucking filtration, be washed to neutrality.Put into baking oven,, obtain brucite 60～80 ℃ of oven dry down.
7. according to claim 6 is the preparation method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that said aluminum salt is aluminum chloride, aluminum nitrate, aluminum sulfate and hydrate thereof, said magnesium salt is magnesium chloride, magnesium nitrate, magnesium sulfate and hydrate thereof;
8. according to claim 1 is the using method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, it is characterized in that pulverous year vanadium dual metal oxide, admix in the domestic animal daily ration by the dosage of 0.5～5 milligram of v element of per kilogram feedstuff, admix in the poultry diet by the dosage of 0.05～0.5 milligram of v element of per kilogram feedstuff.
9. according to claim 1 is the using method of the oral vanadium replenishing agent of carrier with the bimetallic oxide, and it is oral to it is characterized in that being used for the mankind, and v element dosage is micrograms every days 10～100, divides three inferior to taking half an hour after meal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371660A CN1187091C (en) | 2002-09-24 | 2002-09-24 | Oral vanadium replenishing agent with bimetallic oxide as carrier and its prepn and usage |
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| Publication Number | Publication Date |
|---|---|
| CN1403093A true CN1403093A (en) | 2003-03-19 |
| CN1187091C CN1187091C (en) | 2005-02-02 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364547C (en) * | 2006-04-12 | 2008-01-30 | 浙江大学 | Load type molecular iodine complementary agent, and its prepn. method and use |
| CN100371312C (en) * | 2006-03-31 | 2008-02-27 | 浙江大学 | Controlled release type butyric acid, its preparation method and use |
| CN1911079B (en) * | 2006-08-24 | 2010-12-01 | 浙江大学 | Carried type, super-fine, active elemental arsenic, preparation method and use thereof |
| CN102309508A (en) * | 2010-06-24 | 2012-01-11 | 攀枝花兴辰钒钛有限公司 | Application of drug composition in preparation of drugs for treating anemia |
| CN107537071A (en) * | 2017-07-24 | 2018-01-05 | 中国科学院上海硅酸盐研究所 | A kind of surface carries medicine magnesium alloy materials and its preparation method and application |
-
2002
- 2002-09-24 CN CNB021371660A patent/CN1187091C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371312C (en) * | 2006-03-31 | 2008-02-27 | 浙江大学 | Controlled release type butyric acid, its preparation method and use |
| CN100364547C (en) * | 2006-04-12 | 2008-01-30 | 浙江大学 | Load type molecular iodine complementary agent, and its prepn. method and use |
| CN1911079B (en) * | 2006-08-24 | 2010-12-01 | 浙江大学 | Carried type, super-fine, active elemental arsenic, preparation method and use thereof |
| CN102309508A (en) * | 2010-06-24 | 2012-01-11 | 攀枝花兴辰钒钛有限公司 | Application of drug composition in preparation of drugs for treating anemia |
| CN107537071A (en) * | 2017-07-24 | 2018-01-05 | 中国科学院上海硅酸盐研究所 | A kind of surface carries medicine magnesium alloy materials and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1187091C (en) | 2005-02-02 |
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