CN106187746A - A kind of method preparing calcium citrate from fish scale and application thereof - Google Patents

A kind of method preparing calcium citrate from fish scale and application thereof Download PDF

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Publication number
CN106187746A
CN106187746A CN201610596810.7A CN201610596810A CN106187746A CN 106187746 A CN106187746 A CN 106187746A CN 201610596810 A CN201610596810 A CN 201610596810A CN 106187746 A CN106187746 A CN 106187746A
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fish scale
calcium citrate
calcium
suspension
citrate
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CN106187746B (en
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陈勉
陈磊
于林艳
刘飞
张天娇
张秀华
张晓元
郝荣华
袁超
张金华
朱希强
凌沛学
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Shandong Academy of Pharmaceutical Sciences
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention belongs to aquatic products processing technical field, be specifically related to a kind of method preparing calcium citrate from fish scale and application thereof.The invention provides a kind of method preparing calcium citrate from fish scale calcium: fish scale is cleaned by (1), pull fish scale out to weigh, (2) adding citric acid aqueous solution in fish scale, stirring, obtain calcium citrate suspension and decalcification fish scale, (3) the calcium citrate suspension obtained and decalcification fish scale are crossed screen filtration, obtain calcium citrate suspension, the calcium citrate suspension solid-liquid separation that (4) will obtain, collect precipitation, it is dried, obtains calcium citrate.The method can effectively be dissolved the calcium ion that fish scale calcium can make again to dissociate and be separated out and be converted into calcium citrate precipitation, it is only necessary to simple separation can be obtained by calcium citrate;The calcium citrate present invention prepared is used for preparing in treatment puerpera's arthralgia in puerperal preparation, and clinical efficacy is notable, and safety is high.

Description

A kind of method preparing calcium citrate from fish scale and application thereof
Technical field
The invention belongs to aquatic products processing technical field, be specifically related to a kind of method preparing calcium citrate from fish scale and Application.
Background technology
Calcium citrate, C12H10Ca3O14·4H2O, molecular weight 570.49, its calcium element content is 21.08%.It is that one has Machine is calcareous, can be as calsium supplement, it is easy to absorption of human body and utilization.Commercial production calcium citrate, general citric acid and hydroxide Calcium reaction obtains calcium citrate, and calcium carbonate is mainly taken from its calcium source.
Fish scale is the garbage of aquatic products processing, little processed utilization, forms the most corrupt solid refuse on the contrary and grows fly Worm.The main calcareous composition of fish scale is hydroxyapatite, and calcium content is different because fish scale kind is different.Fish scale Recent Advances of Chemical Constituents (Gu Yangjuan etc., Shanxi Agricultural science, volume 39 o. 11th page 1227 in 2011), in fresh-water fishes, calcium content is Squama Cyprinus carpio 3.585%, Ctenopharyngodon idellus squama 5.953%, Carassius auratus squama 7.237%, the calcium content of marine fish such as Cymbaria dahurica fish scale may be up to 31.91%.Work as fish Squama is calcareous when being completely converted into calcium citrate and entirely collected, corresponding calcium citrate recovery utilization rate is followed successively by 17.01%, 28.24%, 34.33% and 151.38%.Its value visible is different because of concrete fish scale source and composition, compares Fructus Citri Limoniae in isolation Acid calcium recycles rate score and is also not enough to differentiate the quality of calcium extraction process.
The technical study of citric acid method fish scale decalcification (Peng Yuanhuai etc., agricultural machinery, in July, 2012 page 132), passes through Fructus Citri Limoniae Calcareous in acid abjection fish scale, it is therefore an objective to after making decalcification process, total calcium content reduces in fish scale, pays close attention to the decalcification rate of fish scale, and not It is to collect calcium citrate.In the document, obtain decalcifying Fluid after using citric acid treatment fish scale, the calcium content energy in this decalcifying Fluid Detected by EDTA compleximetry, show that the calcium citrate in decalcifying Fluid is in the dissociated ion state of dissolving.And citric acid The dissolubility of calcium is the lowest (0.1g/100mL water, 25 degree), and dissolubility has increased when ph decreases, if will be from being dissolved in Fructus Citri Limoniae Extract calcium citrate solid in the calcium citrate solutions of aqueous acid, need separation of citric acid calcium and citric acid solution, and to lemon Lemon acid calcium solution carries out high enrichment and cured, and complex process, energy consumption are the highest.
The Chinese invention patent of Application No. 201210010943.3 discloses a kind of antioxidation fish scale peptide calcium of replenishing the calcium and is combined Chewable tablet and preparation method thereof, the method uses citric acid that calcium in fish scale is converted into calcium citrate.The method is done by fish scale Dry, pulverize and enzymolysis filter, the most backward filtering residue part add citric acid convert, collect sediment fraction obtain calcium citrate.Not only The loaded down with trivial details cost of technique is high and the sediment fraction composition complexity that obtains, both may comprise not by enzymolysis fish scale residue completely, also May comprise not with the hydroxyapatite of citric acid reactions, cause calcium citrate content in deposited components the highest.Single with regard to citric acid For calcium product, fish scale is dried and pulverizing etc. processes and too increases processing step.
Being found by retrieval, in removing fish scale, the method for calcium mainly has acid system and EDTA method at present, and its principle is with extracting Liquid is by hydroxyapatite Ca10(OH)2(PO4)6In calcium dissolve or complexation out, the calcium ion displaced be free on solution it In, recycle and bother very much, and the acid amount that these techniques commonly use is relatively big, wastes resource and adds production cost, It is unfavorable for the economical utilization of resource.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method preparing calcium citrate from fish scale, the method is grasped Making simple, the calcium citrate purity obtained is high, it is easy to industrialized production.
In addition present invention also offers a kind of above-mentioned calcium citrate answering in preparation treatment puerpera's arthralgia in puerperal preparation With,
For achieving the above object, the present invention is by the following technical solutions:
A kind of method preparing calcium citrate from fish scale calcium, employing following steps:
(1) fish scale is cleaned, pull fish scale out and weigh;
(2) adding citric acid aqueous solution in the fish scale described in step (1), stirring, obtain calcium citrate suspension and decalcification fish scale;
(3) calcium citrate suspension and decalcification fish scale step (2) obtained crosses screen filtration, obtains calcium citrate suspension;
(4) calcium citrate suspension solid-liquid separation step (3) obtained, collects precipitation, is dried, obtains calcium citrate.
A kind of method preparing calcium citrate from fish scale, preferred operational approach is:
(1) being cleaned by fish scale, pull wet fish scale out and weigh, wet fish scale water content is 50-75wt%;
(2) adding aqueous citric acid solution in the wet fish scale that step (1) obtains, regulation solution temperature is 15-35 DEG C, and stirring, when molten When liquid pH reaches 3.5-6.5, obtain the suspension containing calcium citrate and decalcification fish scale;Wherein the concentration of aqueous citric acid solution is 1.2-3.9wt%;The speed wherein stirred is 100-300rpm;Preferably, described regulation solution temperature is 20-30 DEG C, and pH is 4- 6, the concentration of aqueous citric acid solution is 2.0-3.8wt%;
(3) the calcium citrate suspension described in step (2) and decalcification fish scale are crossed the screen filtration that aperture is 50-100 mesh, obtain lemon Lemon acid calcium suspension;
(4) calcium citrate suspension solid-liquid separation step (3) obtained, collects calcium citrate precipitation, dry, pulverize, obtain lemon Lemon acid calcium;The method of described solid-liquid separation filters for centrifugal or plate and frame.
The calcium citrate that a kind of preparation method as above prepares.
The application in preparation treatment puerpera's arthralgia in puerperal preparation of a kind of calcium citrate as above.
A kind for the treatment of puerpera's arthralgia in puerperal preparation as above, the dosage form of described preparation is capsule.
The preparation method of the present invention without carrying out fish scale and being dried, the link such as pulverizing, make full use of the big lamellar of fish scale on the contrary Profile, starches formation profile contrast in vain, it is easy to can be achieved with fish scale residue and Fructus Citri Limoniae by common screen cloth with homodisperse decalcification The separation that acid calcium is starched in vain.On the other hand, hydroxyapatite is the ingredient of fish scale, and the part being only dissolved in citric acid just can Dissociating out in complete fish scale, undissolved hydroxyapatite remains in fish scale tissue, retains fish by screen cloth While squama, the most just block undissolved hydroxyapatite.Therefore this method method seems easy, and gained calcium citrate impurity Few.
Beneficial effect
(1) present invention is by controlling the pH of solution after adding the concentration of aqueous citric acid solution in wet fish scale and reacting, and both can have Effect dissolving fish scale calcium can make again the calcium ion dissociating separate out and be converted into precipitation, it is only necessary to simple separation can be obtained by Fructus Citri Limoniae Acid calcium, the aqueous citric acid solution concentration that the present invention uses is low, and consumption is few, and the calcium citrate purity obtained is high, calcium residual in fish scale Few, operational approach is simple, cost-effective, it is easy to industrialized production.
(2) calcium citrate prepared by the present invention is applied in preparation treatment puerpera's arthralgia in puerperal preparation, in the present invention Aqueous citric acid solution while effective dissolution calcium ion, it is also possible in appropriate dissolution fish scale, zinc, magnesium, phosphorus etc. are useful to human body Element, appropriate magnesium, phosphorus can strengthen puerpera to calcareous absorption;Zinc is one of trace element of needed by human, to puerpera Including the physical efficiency recovery process such as immunity, endocrine, there is important function, therefore the present invention prepare based on calcium citrate element Compound nutritional composition proportion be suitable for puerpera's health absorbing function demand, clinical efficacy is notable, and safety is high, is especially suitable for application In treatment puerpera's arthralgia in puerperal preparation.
Detailed description of the invention
The present invention is further illustrated with comparative example in conjunction with the embodiments, it should explanation, the description below be only for The explanation present invention, is not defined its content.
(1) rinsing fish scale with water, remove the foreign body such as blood stains, floating fish film, pull wet fish scale out and weigh 1kg, wet fish scale contains The water yield is 50-75wt%;
(2) adding aqueous citric acid solution in the wet fish scale that step (1) obtains, regulation solution temperature is 15-35 DEG C, and stirring, when molten When liquid pH reaches 3.5-6.5, obtain the suspension containing calcium citrate and decalcification fish scale;Wherein the concentration of aqueous citric acid solution is 1.2-3.9wt%;
(3) the calcium citrate suspension described in step (2) and decalcification fish scale are crossed the screen filtration that aperture is 50-100 mesh, obtain lemon Lemon acid calcium suspension;
(4) calcium citrate suspension solid-liquid separation step (3) obtained, collects calcium citrate precipitation, dry, pulverize, obtain lemon Lemon acid calcium.
Each embodiment and comparative example technological parameter are as shown in table 1:
Use calcium citrate that above-described embodiment and comparative example prepare and and decalcification fish scale, each index is detected, its In respectively refer to object detection method be:
The content of calcium citrate detects according to GB17203 1998 food additive citric acid calcium (prevailing for the time being in force) method;
Calcium extraction ratio %=(fish scale calcium citrate product amount * calcium citrate content * 21%/raw material fish scale TC) * 100%;Wherein In fish scale, total calcium catalyst method is: dry fish scale is cut into length and width and is the small pieces of 3 millimeters, accurately weigh a certain amount of broken Fish scale is in the hydrochloric acid solution of 1mol/L, and solid-liquid ratio is 1:20, reacts 24h, decalcifying Fluid is transferred to volumetric flask, with steaming under room temperature Distilled water washing fish scale, and cleaning mixture is transferred in the lump volumetric flask, with the total calcium content in EDTA standard solution titration fish scale;
Mg and Zn constituent content is detected by atomic absorption spectrophotometer;
P element content is detected by plasma emission spectrometer;
The testing result of each index is shown in Table 2:
As can be seen from Table 2: comparative example 1,2 fish scale calcium depletion is low, fluid is formed a small amount of calcium citrate and obtains white turbid liquid, It is unfavorable for that calcium citrate is collected;The pH of comparative example 3 is low shows that citric acid residual volume is big, not only wastes raw material citric acid, also increases The dissolubility of adding citric acid calcium and cause TL;The citric acid surplus of comparative example 4 is bigger, the solubilising work to calcium citrate With significantly, calcium citrate is caused can not effectively to separate out formation precipitation, it is impossible to a step precipitation is collected;Comparative example 5 is calcareous from hydroxyl phosphorus After dissolving in lime stone, a large amount of calcium citrates form compact deposits crystallization inside and outside fish scale, it is impossible to separate with fish scale and collect.And it is real Executing calcium citrate content 90-99% in calcium citrate prepared by example 1-5, in fish scale, calcium extraction ratio is 90-98%, content of magnesium 250- 950 mg/kg, Zn content 8-180 mg/kg, phosphorus content 0.2-1.5%, liquid fluid outward appearance is the thickest, and fish scale is transparent, and this is described The bright operational approach in embodiment can effectively decalcification, can precipitate further again and collect highly purified calcium citrate, lemon The few utilization rate of lemon acid surplus is high.
And the calcium citrate that embodiment 1-5 is extracted is the compound multiple nutritional components based on calcium citrate, and element is joined Than adapting to puerpera's health absorbing function demand;Appropriate magnesium, phosphorus can strengthen puerpera to calcareous absorption;Zinc is needed by human One of trace element, includes that to puerpera the physical efficiency recovery process such as immunity, endocrine has important function.
The preparation of embodiment 6 fish scale calcium citrate capsule
Powder body mixes:
Weigh 10g vitamin D3 and 90g fish scale calcium citrate (prepared by embodiment 2), mixed in the powder mixer of volume 0.1L Even, obtain mixed powder 1(vitamin D3 weight accounting 10.00%).Take 100g mixed powder 1, and 900g fish scale calcium citrate, Mix in volume 1L powder mixer, obtain mixed powder 2(vitamin D3 weight accounting 1.00%).Take 1kg mixed powder 2, With 9kg fish scale calcium citrate, mix in volume 10L powder mixer, obtain mixed powder 3(vitamin D3 weight accounting 0.10%).Take 10kg mixed powder 3, with 90kg fish scale calcium citrate, mix in volume 100L powder mixer, mixed Powder body 4(vitamin D3 weight accounting 0.01%).Taking 100kg mixed powder 4, and 900kg fish scale calcium citrate, at volume 1000L In powder mixer, mixing, obtains mixed powder 5(vitamin D3 weight accounting 0.001%).Take 100kg mixed powder 5, with 400kg fish scale calcium citrate, mixes in volume 600L powder mixer, obtains mixed powder 6(vitamin D3 weight accounting 2.0ppm).
Fish scale calcium citrate capsule is filled:
Select 0# capsule shells, by mixed powder 6 powder according to the loading amount of 800 ± 40mg/ grain, make with Autocapsulefillingmachine Fish scale calcium citrate capsule.
The preparation of embodiment 7 fish scale calcium citrate capsule
Powder body mixes:
Weigh 10g vitamin D3 and 90g fish scale calcium citrate (prepared by embodiment 1), mixed in the powder mixer of volume 0.1L Even, obtain mixed powder 1(vitamin D3 weight accounting 10.00%).Take 100g mixed powder 1, and 900g fish scale calcium citrate, Mix in volume 1L powder mixer, obtain mixed powder 2(vitamin D3 weight accounting 1.00%).Take 1kg mixed powder 2, With 9kg fish scale calcium citrate, mix in volume 10L powder mixer, obtain mixed powder 3(vitamin D3 weight accounting 0.10%).Take 10kg mixed powder 3, with 90kg fish scale calcium citrate, mix in volume 100L powder mixer, mixed Powder body 4(vitamin D3 weight accounting 0.01%).Taking 100kg mixed powder 4, and 900kg fish scale calcium citrate, at volume 1000L In powder mixer, mixing, obtains mixed powder 5(vitamin D3 weight accounting 0.001%).Take 100kg mixed powder 5, with 300kg fish scale calcium citrate, mixes in volume 500L powder mixer, obtains mixed powder 6(vitamin D3 weight accounting 2.5ppm).
Fish scale calcium citrate capsule is filled:
Select 0# capsule shells, by mixed powder 6 powder according to the loading amount of 800 ± 40mg/ grain, make with Autocapsulefillingmachine Fish scale calcium citrate capsule.
The preparation of embodiment 8 fish scale calcium citrate capsule
Powder body mixes:
Weigh 10g vitamin D3 and 90g fish scale calcium citrate (prepared by embodiment 3), mixed in the powder mixer of volume 0.1L Even, obtain mixed powder 1(vitamin D3 weight accounting 10.00%).Take 100g mixed powder 1, and 900g fish scale calcium citrate, Mix in volume 1L powder mixer, obtain mixed powder 2(vitamin D3 weight accounting 1.00%).Take 1kg mixed powder 2, With 9kg fish scale calcium citrate, mix in volume 10L powder mixer, obtain mixed powder 3(vitamin D3 weight accounting 0.10%).Take 10kg mixed powder 3, with 90kg fish scale calcium citrate, mix in volume 100L powder mixer, mixed Powder body 4(vitamin D3 weight accounting 0.01%).Taking 100kg mixed powder 4, and 900kg fish scale calcium citrate, at volume 1000L In powder mixer, mixing, obtains mixed powder 5(vitamin D3 weight accounting 0.001%).Take 100kg mixed powder 5, with 230kg fish scale calcium citrate, mixes in volume 400L powder mixer, obtains mixed powder 6(vitamin D3 weight accounting 3.0ppm).
Fish scale calcium citrate capsule is filled:
Select 0# capsule shells, by mixed powder 6 powder according to the loading amount of 800 ± 40mg/ grain, make with Autocapsulefillingmachine Fish scale calcium citrate capsule.
The preparation of comparative example 6 food stage calcium citrate capsule
Powder body mixes:
Weigh 10g vitamin D3 and 90g food stage calcium citrate (delicatessen food level calcium citrate, calcium citrate content > 99.9%), mix in the powder mixer of volume 0.1L, obtain mixed powder 1(vitamin D3 weight accounting 10.00%).Take 100g mixed powder 1, with 900g food stage calcium citrate, mixes in volume 1L powder mixer, obtains mixed powder 2(dimension Raw element D3 weight accounting 1.00%).Taking 1kg mixed powder 2, and 9kg food stage calcium citrate, in volume 10L powder mixer Mixing, obtains mixed powder 3(vitamin D3 weight accounting 0.10%).Take 10kg mixed powder 3, with 90kg food stage citric acid Calcium, mixes in volume 100L powder mixer, obtains mixed powder 4(vitamin D3 weight accounting 0.01%).Take 100kg to mix Close powder body 4, with 900kg food stage calcium citrate, mix in volume 1000L powder mixer, obtain mixed powder 5(dimension raw Element D3 weight accounting 0.001%).Take 100kg mixed powder 5, with 300kg food stage calcium citrate, mix at volume 500L powder body In machine, mixing, obtains mixed powder 6(vitamin D3 weight accounting 2.5ppm).
Fish scale calcium citrate capsule is filled:
Select 0# capsule shells, by mixed powder 6 powder according to the loading amount of 800 ± 40mg/ grain, make with Autocapsulefillingmachine Food stage calcium citrate capsule.
Efficacy test
Puerperal, arthralgia was common disease in women puerperal.Common traditional Chinese massage, the method such as stifling can effectively be alleviated and close puerperal Arthralgia, but this method needs professional to try for individual example, it is difficult to large scale application.Puerpera is changed shadow by hormone in vivo Ringing, when particularly having a product, severe loss of blood medical history in puerperal, bone-loss is more, through have a cold clammy after, easily occur that bone closes Save miserable, pain and the symptom of joint stuffiness.Here with supplement calcium nutrition, strengthen puerpera's sclerotin, improve joint pain in puerperal Shape.
1. subjects
Selecting arthralgic puerpera 160 example in eutocous puerperal, 22-38 age, course of disease year is the shortest 1 week, the longest 6 months, by it Be randomly divided into 4 groups, wherein 3 groups use respectively embodiment 6, embodiment 7 and embodiment 8 preparation fish scale calcium citrate capsule, 1 group For matched group, using calcium citrate capsule prepared by comparative example, age between each group and symptom are without significant difference.
2. using method
Embodiment group: 1 tablet/time, age of sucking 2 tablets/time, 2 times/day, serve on 8 weeks.
The same test group of matched group instructions of taking.
3. criterion of therapeutical effect
(1) effective: tender joint number reduces, and pain degree alleviates, the deadlock time in morning shortens
(2) invalid: tender joint number is constant or increases, and pain degree aggravates, the deadlock time in morning is constant or extends
4. result of the test:
(1) untoward reaction
All there is not the untoward reaction such as allergy, abdominal distention in test group and matched group.
(2) puerperal, arthralgia improved effect
The results are shown in Table 3
Fish scale calcium citrate using effect contrasts
As can be seen from Table 3, fish scale calcium citrate capsule improvement arthralgic to puerperal prepared by the present invention is effective, Ke Yiyou Effect alleviates post-partum pain related symptoms, and has no adverse reaction.It addition, experiment proves that, the fish scale calcium citrate of the present invention makes Arthralgia can be effectively improved, it is possible to achieve the rapid curing effect to joint in puerperal with 3-4 week.

Claims (8)

1. the method preparing calcium citrate from fish scale calcium, it is characterised in that employing following steps:
(1) fish scale is cleaned, pull fish scale out and weigh;
(2) adding citric acid aqueous solution in the fish scale described in step (1), stirring, obtain calcium citrate suspension and decalcification fish scale;
(3) calcium citrate suspension and decalcification fish scale step (2) obtained crosses screen filtration, obtains calcium citrate suspension;
(4) calcium citrate suspension solid-liquid separation step (3) obtained, collects precipitation, is dried, obtains calcium citrate.
A kind of method preparing calcium citrate from fish scale calcium the most according to claim 1, it is characterised in that concrete operations side Method is:
(1) being cleaned by fish scale, pull wet fish scale out and weigh, wet fish scale water content is 50-75wt%;
(2) adding aqueous citric acid solution in the wet fish scale that step (1) obtains, regulation solution temperature is 15-35 DEG C, and stirring, when molten When liquid pH reaches 3.5-6.5, obtain the suspension containing calcium citrate and decalcification fish scale;Wherein the concentration of aqueous citric acid solution is 1.2-3.9wt%;
(3) the calcium citrate suspension described in step (2) and decalcification fish scale are crossed the screen filtration that aperture is 50-100 mesh, obtain lemon Lemon acid calcium suspension;
(4) calcium citrate suspension solid-liquid separation step (3) obtained, collects calcium citrate precipitation, dry, pulverize, obtain lemon Lemon acid calcium.
A kind of method preparing calcium citrate from fish scale calcium the most according to claim 2, it is characterised in that step (2) institute The speed stating stirring is 100-300rpm.
A kind of method preparing calcium citrate from fish scale calcium the most according to claim 2, it is characterised in that step (2) institute The regulation solution temperature stated is 20-30 DEG C, and pH is 4-6, and the concentration of aqueous citric acid solution is 2.0-3.8wt%.
A kind of method preparing calcium citrate from fish scale calcium the most according to claim 2, it is characterised in that step (4) institute The method stating solid-liquid separation filters for centrifugal or plate and frame.
6. the calcium citrate that the preparation method described in an any one of claim 1-5 prepares.
7. the application in preparation treatment puerpera's arthralgia in puerperal preparation of the calcium citrate described in a claim 6.
8. treatment puerpera's arthralgia in the puerperal preparation described in a claim 7, it is characterised in that the dosage form of described preparation is glue Wafer.
CN201610596810.7A 2016-07-27 2016-07-27 Method for preparing calcium citrate from fish scales and application of calcium citrate Active CN106187746B (en)

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Publication number Priority date Publication date Assignee Title
US20050112211A1 (en) * 2003-08-21 2005-05-26 Eric Gervais Micronutrient supplement
CN101307348A (en) * 2008-06-13 2008-11-19 华中农业大学 Method for preparing undenatured collagen from fish scale of fresh water fish
CN103202419A (en) * 2012-01-15 2013-07-17 华中农业大学 A compound fish scale peptide and calcium compound chewable tablet for antioxidation and calcium supplementing and a preparation method thereof

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