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CN1248575A - Amino acid calcium and preparation method thereof - Google Patents

Amino acid calcium and preparation method thereof Download PDF

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Publication number
CN1248575A
CN1248575A CN 98120034 CN98120034A CN1248575A CN 1248575 A CN1248575 A CN 1248575A CN 98120034 CN98120034 CN 98120034 CN 98120034 A CN98120034 A CN 98120034A CN 1248575 A CN1248575 A CN 1248575A
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calcium
amino acid
wave
preparation
radon
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CN 98120034
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CN1093530C (en
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邓汉祥
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a method for chemically synthesizing amino acid calcium by ultrasonic wave, wherein the amino acid calcium is a calcium ammonia carboxyl chelating structure formed by combining calcium hydroxide in an ionic state and free radicals of radon acid or glutamic acid under a specific ultrasonic stress field, and is non-salt molecular organic calcium which has small internal energy and stable structure and is dissolved in water. It can be used in medicine and health promotion industry.

Description

A kind of amino acid calcium and preparation method thereof
The present invention relates to a kind of amino acid calcium that utilizes chemosynthesis, the method for this amino acid calcium of preparation is provided simultaneously, it belongs to the synthetic organic calcium technology of sonochemistry method.
Calcium is one of human body composition and metabolic bioelement.At occurring in nature, calcium exists with various inorganic mineral forms, can not directly be absorbed by human body, and the calcium that people's physical efficiency directly absorbs is the organic calcium of biologically active calcium lactate for example, amino acid calcium etc.
Organic calcium salt is that 50 years prehumans synthesize a class organic calcium successfully, and the organic calcium salt of molten water-based such as calglucon, calcium acetate and calcium lactate etc. can be absorbed by the body, but it is subjected to some conditionalities.Various salt contents are bigger in blood, and when crystal osmotic pressure was high, this class calcium salt just was not easy to absorb.In addition, this class organic calcium salt calcium ion Ca in absorption process 2+Influence is to the absorption of phosphorus.In organism, essential trace element does not often exist with the free ion form, but combines with ligand.This class organic calcium salt must combine with amino acid after entering in the body, adds the phosphorus part, is deposited in the bone under parathyroid hormone (thyrocalcitonin) effect, and bone density is increased.And take above-mentioned organic calcium salt, and can increase the calcium concn in the blood, but bone density is increased, the purpose of replenishing the calcium does not reach.Simultaneously, if blood calcium concentration is too high,, can make people's calcium intoxication because calcium ion can make blood coagulation.The solubleness of calcium salt in water is very little, and in the kidney filtration procedure, calcium salt concentration in kidney is excessive, just crystallizes into solid, and the time that solid salt stops in kidney has been grown, and forms calculus with regard to calcification, causes urinary stone disease and other disease easily.
The production technique of organic calcium salt generally has two kinds: a kind of is that glucose adds the lime carbonate fermentation, glucose oxidation during the fermentation becomes lactic acid, and accompany big calorimetric, simultaneously during the fermentation with the inorganic calcium synthesis of calcium lactate, calglucon, in this process, generally can make about 70% inorganic calcium transfer organic calcium salt to.This technology cost is low, but mass production, but product purity is low, and contain a large amount of alkaline inorganic calciums, taking for a long time to influence the normal gi system of human body.Another kind method is to use lactic acid neutralization calcium hydroxide, if but use too much lactic acid in the course of processing, make and contain more lactic acid in the product, can cause lactic acidosis, bigger to human body harm, therefore aborning must be with other material with residual acid neutralization, then will be in this and the material removal.Doing had so both increased production cost, was difficult to guarantee pharmaceutical purity again.The calcium lactate cost of this method preparation is very high.
The objective of the invention is to improve the deficiencies in the prior art, provide a kind of producing to have stable structure, human body is easy to absorb, and effectively improves the processing method of the salt-independent molecular organic calcium of bone density, and above-mentioned organic calcium product is provided simultaneously.
For achieving the above object, the present invention takes following design:
This production technique comprises: batching, dispersion, sonochemistry are synthetic, precipitate and separate and dehydrate operation.Described batching and dispersion process are that raw material is put into water after the proportioning in proportion, disperse.Dispersing apparatus can be with common stirrer or homogenizer.
The product of made be a kind of under neutrality or slight alkali environment the non-salt organic calcium-amino acid calcium of the constitutionally stable calcium amino carboxylic chelating combination that makes up voluntarily by calcium hydroxide and radon propylhomoserin radical or L-glutamic acid radical.The raw material of amino acid calcium is edible radon propylhomoserin or L-glutamic acid and calcium hydroxide.Radon propylhomoserin, L-glutamic acid and calcium hydroxide all are slightly soluble in water.For reaching the purpose of powder high dispersing in water, require material powder thin more good more, at least should be below 0.30 micron.Proportioning raw materials is that 2 mol radon propylhomoserins or L-glutamic acid add 1 molar calcium hydroxide.The ratio of raw material and water is 20-30: 70-80, or matched proportion density is 20-30%, the slurry for preparing just can carry out ultrasonic wave and synthesize with the abundant dispersed with stirring of stirrer, the back that disperses to finish.
The used equipment of sonochemistry building-up process of the present invention is that a kind of power-type high frequency hydraulic pressure can be changed ultrasonic energy equipment.Equipment is made up of two systems: high-pressure pump and vibration instrument.High-pressure pump adopts the unidirectional hydro-pump of plunger tpe more, and this is excited crystal forced oscillation power source.The vibration instrument is made of the brilliant plate of stauros passage and both sides.
The mixture of radon propylhomoserin or L-glutamic acid and calcium hydroxide and water produces pressure under the effect of the unidirectional hydro-pump of plunger tpe will reach 1000-1500Fkg/cm 2, after it entered the vibrator passage, channel cross-sectional area dwindled, enter the slurry behind the cross passage, fluid velocity can reach 285-840m/s, produces the velocity pulse plane shock in cross tunnel junction mode, the brilliant plate forced vibration in shock wave excitation both sides, the brilliant plate of high-frequency vibration just becomes the ultrasonic emitting source.Meanwhile, in liquid stream vertical direction, launch ultrasonic wave in opposite directions simultaneously, its objective is to make the ripple stack, stress is strengthened.It is 130-150 joule/milliliter to the wave energy that liquid slurry loads that the ultrasound waves frequency will reach 3.6-16.8 megahertz (MH) ultrasonic wave, generally is 132 joules/milliliter; The time that loads is 100,000/to 3/100000ths seconds.The flow velocity of slurry is if be lower than 285M/S, and ripple is frequently low, and the time of loading is a little long; Flow velocity height, ripple are high frequently, and the time of loading is a little short.At this moment wave power is 1202-2164KW, if comprise fluidic stretching ripple, wave power is 4400-13200KW, (sound intensity 1202-2164KW/CM).
The principle of the synthetic salt-independent molecular organic calcium-amino acid calcium provided by the invention of ultrasonic wave is such: material molecule is under the influence of ambient conditionss such as light, heat or ultrasonic wave, and its covalent linkage generation homolysis forms and contains not in pairs the atom of valence electron or atomic group-free radical (or radical) as ammonia free radical NH 3Or methyl CH 3Deng.Free radical generally has the intensive activity, and is most unstable under usual conditions, is difficult to Individual existence, can only have 0.001 second as methyl.Free radical tends to be combined into stable molecule voluntarily, or the dissociated ion of other material, and free radical reaction forms new more stable molecule.This new material is interior usually can be littler than former material.(not having other material to participate in free radical reaction as former material, isomerization often, isomer that can be little in the former material of same different constituent ratio).Not that ultrasonic wave can both make material molecule covalent linkage generation homolysis, form radical.Have only when the ultrasound waves frequency and reach or near the frequency of molecule, and make molecule under resonance or resonant condition, produce maximum strain, and, load the ultrasonic energy of certain stress in the time that free radical can exist, homolysis just takes place in the molecule covalent linkage, forms radical.
Therefore the above-mentioned loading time can not surpass described radon propylhomoserin or L-glutamic acid radical lifetime.
The slurry liquid fluid is the ultrasonic wave carrier, and with high-speed motion, so hyperacoustic waveform is the stretching ripple.The tensile stress of stretching ripple is very large.After the calcium hydroxide powder enters above-mentioned ultrasonic wave stress field, constantly pulverized (drawing broken), a large amount of calcium ions trips become the stable chelated molecule with amino acid radical Automatic Combined in the water in water.Certainly, ammonia free radical and carboxyl also help calcium ion to break away from from calcium hydroxide particle in the water.
Observe the calcium hydroxide powder with about 15 microns from process of the test, carry out ultrasonic wave building-up process of the present invention, first pass can make 60% dust be converted into amino acid calcium, can make 100% powder be converted into amino acid calcium second time.Because calcium hydroxide and amino acid are all water insoluble, and amino acid calcium is water-soluble, so with the naked eye can observe this reaction process.
Use sonochemistry synthesis method provided by the invention to prepare organic calcium transformation efficiency height.
Amino acid calcium after synthetic all is dissolved in the water, and the calcium hydroxide if any not participating in chemical reaction on a small quantity can leave standstill a moment, and natural subsidence is separated.If any the amino acid that does not participate in chemical reaction,, needn't painstakingly separate in the production amino acid calcium process because it is harmless.
Last procedure is dehydration.The aqueous solution of amino acid calcium generally adopts the spraying drying dehydration.If the finished product are liquid oral liquid or injection liquid, just need not dewater.Separation, the non-the present invention that dewaters are so seldom state.
The advantage of using sonochemistry synthesis method provided by the invention to prepare the method for organic calcium is the transformation efficiency height, the product purity height of producing.And the advantage of the amino acid calcium product of producing with method of the present invention is:
1, human body is easy to absorb.Amino acid calcium is a colloidalmaterial, osmotic pressure is little, entering blood is adsorbed by haemproteins, haemproteins enters when filtering in the kidney at blood, just has been recovered at renal glomerulus, and interior energy is low, on the formation that chemically is reflected at molecular structure, for example functional group is more close, can be low as cis-structure than in the transconfiguration, and the L type can be low than in the D type etc.Be reflected at characteristics such as low interior energy substance dissolves degree is big, boiling point is low, and decomposition temperature is low physically.In can hang down the material animal and absorb easily.With the amino acid calcium of method of the present invention preparation because be subjected to specific action of ultrasonic waves, belong to low in can a class, its have can material has in low character, be absorbed by the body especially easily.
2, sedimentation in bone easily, bone density improving.Bone is made up of gelatine (gelatin) and hydroxylapatite [(3Ca) (Po) ※ Ca (OH)].The gelatin hydrolysis composition is an amino acid, so be amino acid calcium near the calcium-enriching products of bone composition.
3, amino acid calcium is more much smaller than organic calcium salt toxicity.Amino acid in the amino acid calcium and the calcium ion in the blood are combined into title complex, prevent blood coagulation, it in addition form stable complex compound with some deleterious metal, make toxic metal all nontoxic to human body.
4, amino acid calcium solubleness in water is big, can not cause the generation of diseases such as urinary stone disease.
Radon propylhomoserin calcium molecular weight is 304.29, Calcium glutamate molecular weight 332.35, and the two is all water-soluble, and when meltage was big in water, viscosity increased reached 75% water white transparency of one-tenth when above solid gel, or the white solid powder.When its aqueous solution was neutrality or weakly alkaline, amino acid structure was stable, and in hydrochloric acid soln, calcium is easily pulled out the formation calcium chloride salt from complex molecule.When amino acid and calcium ion coordination, utilize in the molecule Sauerstoffatom and calcium generation covalent attachment on the carboxyl, provide lone-pair electron and ion to form coordinate bond by the nitrogen-atoms in the amino simultaneously, with the same five-membered ring structure that forms of most of biological title complexs in the human body.
The invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is a process flow sheet of the present invention
Fig. 2 is the chemical equation of radon amino acid adding calcium hydroxide synthesizing amino acid calcium
Fig. 3 is the chemical structural formula of amino acid calcium
Embodiment:
The method for preparing the amino acid calcium powder, its step comprises batching, dispersion, precipitate and separate and dehydrates.As shown in Figure 1.In the batching stage, 2 mol radon propylhomoserins are added that the ratio of the raw material of 1 molar calcium hydroxide and water is joined are 20-30: 70-80 that the material powder granularity is below 0.30 micron.The slurry for preparing just can carry out ultrasonic wave and synthesize with the abundant dispersed with stirring of stirrer, the back that disperses to finish.
Be the sonochemistry building-up process after dispersion process, its chemical equation as shown in Figure 2.Described sonochemistry building-up process can be changed in the ultrasonic energy equipment at power-type high frequency hydraulic pressure and carry out, and high-pressure pump wherein is forced into 1000-1500Fkg/cm with the mixture of raw material and water 2Pressure enters the vibration instrument of described sonochemistry synthesis device with the speed of 285-840m/s, produces the velocity pulse plane shock in cross tunnel junction mode, the brilliant plate in shock wave excitation stauros passage both sides; In liquid stream vertical direction, launch ultrasonic wave in opposite directions simultaneously, its wave frequency is 3.6-16.8MH, ultrasonic wave is 130-150 joule/milliliter to the wave energy that liquid slurry loads, the time that loads is 100,000/to 3/100000ths seconds, wave power is 1202-2164KW, comprises the stretching ripple that liquid motion produces, and total wave power is 4400-13200KW.
Amino acid calcium (its structural formula as shown in Figure 3) after synthetic all is dissolved in the water, and the calcium hydroxide if any not participating in chemical reaction on a small quantity can leave standstill a moment, and natural subsidence is separated.If any the amino acid that does not participate in chemical reaction,, needn't painstakingly separate in the production amino acid calcium process because it is harmless.
Last procedure is dehydration.The aqueous solution of amino acid calcium generally adopts the spraying drying dehydration.

Claims (5)

1, a kind of preparation method of amino acid calcium, its step comprises batching, dispersion and precipitate and separate, it is characterized in that: be the sonochemistry building-up process after dispersion process; Described proportioning raw materials is that 2 mol radon amino acid or paddy amino acid add 1 molar calcium hydroxide, the ratio of raw material and water is 20-30: 70-80, or matched proportion density is 20-30%, described sonochemistry building-up process can be changed in the ultrasonic energy equipment at power-type high frequency hydraulic pressure and carry out, and high-pressure pump wherein is forced into 1000-1500Fkg/cm with the mixture of raw material and water 2Pressure enters the vibration instrument of described sonochemistry synthesis device with the speed of 285-840m/s, produces the velocity pulse plane shock in cross tunnel junction mode, the brilliant plate in shock wave excitation stauros passage both sides; In liquid stream vertical direction, launch ultrasonic wave in opposite directions simultaneously, its wave frequency is 3.6-16.8MH, ultrasonic wave is 130-150 joule/milliliter to the wave energy that liquid slurry loads, the time that loads is no more than radon propylhomoserin or the L-glutamic acid radical lifetime that produces in the described raw material in reaction process, wave power is 1202-2164KW, comprises the stretching ripple that liquid motion produces, and total wave power is 4400-13200KW.
2, the amino acid calcium of method according to claim 1 preparation is characterized in that: it is that the proportioning with 20-30 part is that 2 mol radon amino acid or paddy amino acid add that the raw material of 1 molar calcium hydroxide adds water 70-80 and mixes afterwards at 1000-1500Fkg/cm 2Under the pressure, enter the vibration instrument of sonochemistry synthesis device, produce the velocity pulse plane shock, the brilliant plate in shock wave excitation stauros passage both sides in cross tunnel junction mode with the speed of 285-840m/s; Add at liquid and flow vertical direction while ultrasonic waves transmitted in opposite directions, its wave frequency is 3.6-16.8MH, wave energy is 130-150 joule/milliliter, the time that loads is 100,000/to 3/100000ths seconds, wave power is 1202-2164KW, comprise the stretching ripple that liquid motion produces, wave power be 4400-13200KW prepare a kind of constitutionally stable by calcium hydroxide and radon amino acid radical or the amino trip base of the paddy salt-independent molecular organic calcium of the calcium amino carboxylic chelating combination of combination voluntarily under neutrality or slight alkali environment.
3, the preparation method of amino acid calcium according to claim 1 is characterized in that: the powder of the calcium hydroxide in the described raw material is below 0.30 micron.
4, the preparation method of amino acid calcium according to claim 1 is characterized in that: described ultrasonic wave is 132 joules/milliliter to the wave energy that liquid slurry loads.
5, the preparation method of amino acid calcium according to claim 1 is characterized in that: the time of described loading is 100,000/and to 3/100000ths seconds.
CN98120034A 1998-09-24 1998-09-24 Amino acid calcium and preparation method thereof Expired - Fee Related CN1093530C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1305555C (en) * 2004-05-18 2007-03-21 浙江大学 Water-soluble ion liquid synthesizing method
CN101434555B (en) * 2008-12-09 2011-09-21 河南省科学院化学研究所有限公司 Method for synthesizing calcium glutamate
CN103626867A (en) * 2013-06-19 2014-03-12 中国海洋大学 Preparation process for zinc fish-skin collagen polypeptide chelate
CN104000191A (en) * 2014-02-07 2014-08-27 岳智广 A novel chelated calcium
CN115611759A (en) * 2022-12-08 2023-01-17 维卓(嘉兴)营养品有限公司 A kind of preparation method of (R)-3-aminobutyric acid chelated calcium

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102322269B1 (en) * 2019-06-28 2021-11-05 주식회사 리앤씨바이오 Calcium-collagen peptide chelate complex and method for preparing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154358A (en) * 1996-01-12 1997-07-16 常达正 Method for prepn. and application of calcium amino-acidic
CN1065128C (en) * 1996-05-07 2001-05-02 国家医药管理局上海医药工业研究所 Amino acid metal chelate and its preparation and preparing method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1305555C (en) * 2004-05-18 2007-03-21 浙江大学 Water-soluble ion liquid synthesizing method
CN101434555B (en) * 2008-12-09 2011-09-21 河南省科学院化学研究所有限公司 Method for synthesizing calcium glutamate
CN103626867A (en) * 2013-06-19 2014-03-12 中国海洋大学 Preparation process for zinc fish-skin collagen polypeptide chelate
CN103626867B (en) * 2013-06-19 2015-08-12 中国海洋大学 A kind of preparation technology of zinc fish-skin collagen polypeptide chelate
CN104000191A (en) * 2014-02-07 2014-08-27 岳智广 A novel chelated calcium
CN115611759A (en) * 2022-12-08 2023-01-17 维卓(嘉兴)营养品有限公司 A kind of preparation method of (R)-3-aminobutyric acid chelated calcium

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