CN103224546B - Hydrated carbamyl glycine dipeptide chelated iron and preparation method thereof - Google Patents

Hydrated carbamyl glycine dipeptide chelated iron and preparation method thereof Download PDF

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CN103224546B
CN103224546B CN201310142525.4A CN201310142525A CN103224546B CN 103224546 B CN103224546 B CN 103224546B CN 201310142525 A CN201310142525 A CN 201310142525A CN 103224546 B CN103224546 B CN 103224546B
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carbamoylglycine
iron
dipeptide
carbamyl
dipeptides
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CN103224546A (en
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樊明智
吴春丽
舒绪刚
吴信
印遇龙
高均勇
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Guangzhou Jiuyi Bio Technology Co ltd
GUANGZHOU TANKE BIO-TECHNOLOGY CO LTD
Zhongkai University of Agriculture and Engineering
Institute of Subtropical Agriculture of CAS
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Guangzhou Jiuyi Bio Technology Co ltd
GUANGZHOU TANKE BIO-TECHNOLOGY CO LTD
Zhongkai University of Agriculture and Engineering
Institute of Subtropical Agriculture of CAS
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Abstract

The invention discloses hydrated carbamyl glycine dipeptide chelated iron and a preparation method thereof. The invention uses carbamyl glycine dipeptide and ferrous sulfate as main raw materials, and directly precipitates crystalline hydrated carbamyl glycine dipeptide chelated iron in aqueous solution without using organic solvent. The method has the advantages of easily available raw materials, simple process, low cost, high product purity, stable quality, convenient technology for industrial production and the like. The hydrated carbamyl glycine dipeptide chelated iron can be used as an animal feed additive, the production performance of weaned pigs is improved, the content of trace elements in serum is improved, the content of metal elements in excrement is reduced, and the oxidation resistance of organisms is improved.

Description

Hydration carbamoylglycine dipeptide iron chelate and preparation method thereof
Technical field
The invention belongs to field of feed additive technology, particularly hydration carbamoylglycine dipeptide iron chelate and preparation method thereof.
Background technology
Iron is one of the most necessary trace element of animal body.In animal body, the iron of nearly 2/3rds is present in the myohaemoglobin of erythrocytic oxyphorase and muscle, and the iron of 20% is present in liver, spleen and its hetero-organization in different forms.The main Physiological Function of iron transports oxygen and carbon dioxide by oxyphorase, and play a part fixing by myohaemoglobin and store oxygen.Modern study proves, iron and energy metabolism closely related because its biochemical action of competence exertion when having enzyme over half and factor iron content in tricarboxylic cycle or only have iron to exist, complete physiological function.Iron also affects protein synthesis in animal body and immunity function.
Utilizing of iron deficiency or iron is bad, and will cause the disturbed metabolic processes such as the transport of oxygen, storage, the transport of carbonic acid gas and redox, impact is grown and even the various diseases such as anaemia occurred.Piglet stores iron or takes the photograph iron deficiency, then occur hypoferric anemia.Children sucking pig in age (especially nascent) easily suffer from iron deficiency, this is because in its body, iron storage is relatively low.Piglet iron deficiency shows as poor appetite, and poor growth is day by day become thin, and burnout happiness is sleeping, and breathe urgent easily, rough coat, xerosis cutis lacks flexibility, sometimes laxativeness, and ight soil is lead, stench.Blood has obvious change, in incarnadine, thin in water, and this is the important evidence of diagnosis piglet anaemia disease.Piglet gently then forms cad pig after suffering from anemia, heavy then death in 3 ~ 4 weeks.
Animal supplements inorganic iron usage quantity greatly, easily causes a large amount of wastings of resources.The iron ion of feed intake and hydroxide ion easily form the polymkeric substance that insoluble hydroxyl closes complex compound, thus reduce its absorption rate.Therefore only have little part (5% ~ 8%) to be absorbed, remaining is then discharged with ight soil by enteron aisle, easily causes environmental pollution.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art, a kind of hydration carbamoylglycine dipeptide iron chelate and preparation method thereof is provided.
The technical solution used in the present invention is:
The preparation method of hydration carbamoylglycine dipeptide iron chelate, comprises the following steps:
1) by water-soluble for carbamoylglycine dipeptides, adjust pH to be 5.0 ~ 6.0, be heated to 50 ~ 70 DEG C;
2) add xitix and ferrous sulfate successively again, 60 ~ 80 DEG C are reacted 0.5 ~ 1 hour;
3) hydration carbamoylglycine dipeptide iron chelate is obtained after crystallisation by cooling, filtration, drying.
Preferably, the mol ratio of carbamoylglycine dipeptides and ferrous sulfate is (1.7 ~ 2.3): 1.
More excellent, carbamoylglycine dipeptides and ferrous sulfate mole be 2:1.
Preferably, the consumption of xitix be carbamoylglycine dipeptides, ferrous sulfate and water quality and 2 ‰ ~ 3 ‰.
Preferably, in step 1), the mass volume ratio of carbamoylglycine dipeptides and water is 1g:(2.0 ~ 3.0) ml.
More excellent, the mass volume ratio of carbamoylglycine dipeptides and water is 1g:2.5ml.
The invention has the beneficial effects as follows:
The present invention is direct crystallize out hydration carbamoylglycine dipeptide iron chelate in aqueous, do not need with an organic solvent, the inventive method has that raw material is easy to get, technique is simple, cost is low, product purity is high, steady quality, technology are convenient to the advantages such as suitability for industrialized production.
Hydration carbamoylglycine dipeptide iron chelate of the present invention can be used as animal feedstuff additive, improves the production performance of weanling pig, improves the content of Trace Elements In Serum, reduces the content of metallic element in ight soil, improves the antioxidant property of body.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of hydration carbamoylglycine dipeptide iron chelate;
Fig. 2 is the infrared spectrogram of carbamoylglycine dipeptides.
Embodiment
The present invention utilizes carbamoylglycine dipeptides, ferrous sulfate as main raw material, according to the difference of end product saturation solubility at different temperatures, by reducing temperature, makes end product directly crystallize out from inorganic aqueous solution.It is a kind of inner complex containing crystal water that the present invention obtains product, and namely hydration carbamoylglycine dipeptide iron chelate, at the uniform velocity discharges in animal body, little to intestines and stomach pungency, as organic molecule, is easy to directly be absorbed by animal.Owing to not containing organic solvent in production technique of the present invention, when dropping into suitability for industrialized production, decrease the infusion of financial resources of raw material and equipment, reduce the impact on production safety and environment.
Below in conjunction with embodiment, the present invention is further illustrated, but be not limited thereto.
embodiment 1
The preparation method of hydration carbamoylglycine dipeptide iron chelate, its concrete steps are as follows:
Take 23.6g(0.2mol) carbamoylglycine dipeptides, the 60ml that adds water dissolves, and regulates pH to 5.0, be heated to 60 DEG C with sodium hydroxide; Add 0.35g xitix again, 27.8g(0.1mol) iron vitriol, control temperature, at 60 DEG C, reacts 1.0 hours; Cooling and stirring crystallization, suction filtration, vacuum-drying under gained solid 60 DEG C of conditions, obtains hydration carbamoylglycine dipeptide iron chelate 29.2g.
Detecting iron level in dipeptide iron chelate is 13.72%, and nitrogen content is 13.84%.
embodiment 2
The preparation method of hydration carbamoylglycine dipeptide iron chelate, its concrete steps are as follows:
Take 40.12g(0.34mol) carbamoylglycine dipeptides, the 80ml that adds water dissolves, and regulates pH to 6.0, be heated to 50 DEG C with sodium hydroxide; Add 0.70g xitix again, 55.6g(0.2mol) iron vitriol, control temperature, at 70 DEG C, reacts 0.5 hour; Cooling and stirring crystallization, suction filtration, the vacuum-drying at 60 DEG C of gained solid, obtains hydration carbamoylglycine dipeptide iron chelate 59.4g.
Detecting iron level in dipeptide iron chelate is 13.88%, and nitrogen content is 13.76%.
embodiment 3
The preparation method of hydration carbamoylglycine dipeptide iron chelate, its concrete steps are as follows:
Take 74.34g(0.63mol) carbamoylglycine dipeptides, the 193ml that adds water dissolves, and regulates pH to 5.0, be heated to 55 DEG C with sodium hydroxide; Add 1.05g xitix again, 83.4g(0.3mol) iron vitriol, control temperature, at 80 DEG C, reacts 1.0 hours; Cooling and stirring crystallization, suction filtration, the vacuum-drying at 60 DEG C of gained solid, obtains hydration carbamoylglycine dipeptide iron chelate 85.8g.
Detecting iron level in dipeptide iron chelate is 13.81%, and nitrogen content is 13.79%.
embodiment 4
The preparation method of hydration carbamoylglycine dipeptide iron chelate, its concrete steps are as follows:
Take 108.56g(0.92mol) carbamoylglycine dipeptides, the 326ml that adds water dissolves, and regulates pH to 5.0, be heated to 70 DEG C with sodium hydroxide; Add 1.40g xitix again, 111.2g(0.4mol) iron vitriol, control temperature, at 80 DEG C, reacts 0.5 hour; Cooling and stirring crystallization, suction filtration, the vacuum-drying at 60 DEG C of gained solid, obtains hydration carbamoylglycine dipeptide iron chelate 116.8g.
Detecting iron level in dipeptide iron chelate is 13.87%, and nitrogen content is 13.82%.
Product absolute ethanol washing embodiment 1 obtained, dry, can obtain the hydration carbamoylglycine dipeptide iron chelate that purity is higher, be pale yellow crystals particle, soluble in water, is insoluble to ethanol, methyl alcohol, acetone and other organic solvent.Sample presentation surveys infrared spectra, and as shown in Figure 1, the infrared spectrogram of corresponding carbamoylglycine dipeptides as shown in Figure 2 for gained collection of illustrative plates.
Fig. 2 is the infrared spectrogram of carbamoylglycine dipeptides, and in carbamoylglycine dipeptides, amino and carboxyl are respectively with H 3n +and COO -state exist, carbamoylglycine dipeptides is at 3228.14cm -1there is wider absorption band at place, and this is amino charateristic avsorption band, and the antisymmetric stretching vibration of carboxylic acid ion in carbamoylglycine dipeptides and symmetrical stretching vibration are at 1541.81cm -1and 1241.55cm -1.Known by Fig. 1, at 3359.12cm -1there is wider absorption peak in place, shows to have the existence of water molecules or the existence of OH in inner complex.Another at 1596.74cm -1occur water in carboxyl stretching vibration absorb and at 1313.47cm -1the absorption of the O-H at place, shows the existence having water molecules in carbamoylglycine dipeptide iron chelate.
The infrared spectra of comparison diagram 1 and Fig. 2 is known, after formation inner complex, and H 3n +characteristic absorbance there occurs red shift, simultaneously the characteristic absorbance of carboxyl is blue shifted to 1596.74cm -1, 1313.47cm -1place, this is because the amino of carbamoylglycine dipeptides and carboxyl oxygen participate in the result that coordination forms inner complex.
The crystalline particle sample presentation of this dipeptide iron chelate is carried out ultimate analysis, according to measurement result, infers that the molecular formula of this chelated iron is for (C 6h 10n 4o 6fe) 6H 2o.The measurement result of ultimate analysis and calculated value contrast as shown in the table:
? Fe C H N
Theoretical value 14.03% 18.10% 5.57% 14.07%
Measured value 13.96% 18.16% 5.57% 13.92%
Examples of implementation 2 ~ 4 products obtained therefrom, through same way process, all obtains pale yellow crystals particle, soluble in water, is insoluble to ethanol, methyl alcohol, acetone and other organic solvent, and sample presentation detects, and gained infrared spectra and Fig. 1 are extremely similar, are characterized by same compound.The content of Fe, C, H, N is all close to above-mentioned theory value.
animal experiment:
The hydration carbamoylglycine dipeptide iron chelate prepared with embodiment 1 below carries out animal experiment.
1, test is arranged
The 21 age in days weanling pig 90 select close batch, body weight is close, being in a good state of health, raises one week in advance.Be divided at random 5 groups (1 negative control group, 1 positive control group, 3 test group), often organize 3 repetitions, each repetition 6 piglets.Test 21 d by a definite date.Duration of test, free choice feeding is drunk water; Natural lighting, temperature is at 22-28 DEG C, and humidity is at 60-70%.The crude protein content of basal diet is 18.0%, and metabolizable energy is 3400Kcal/kg, and calcium contents is 0.8%, and available phosphorus content is 0.35%.
Wherein, the feed of negative control group is corn bean pulp type basal diet, and mineral substance does not add iron, and iron is less than 3PPm; Based on the feed of positive control group, daily ration adds the iron vitriol of iron content 12ppm; Based on the feed of 3 test group, daily ration adds hydration carbamoylglycine dipeptide iron chelate, iron-holder is respectively 6,12,18ppm.
2, production performance test
Food consumption, the ight soil index of time recording every day every hurdle piglet; Measure weekly the individual weight of each piglet; Add up feedstuff-meat ratio weekly, calculate the production performances such as all food consumptions, day weight gain; The content of ight soil sampling determination iron, copper, zinc, manganese; Measure body Antioxidant Indexes SOD vigor and GSH-Px vigor.
3, test-results
The weanling pig average daily gain of 3 test group significantly improves (P < 0.05), and diarrhea rate significantly reduces (P < 0.05), and Iron in Serum content significantly improves (P < 0.05); In 12ppm, 18ppm interpolation group piglet ight soil, iron level significantly reduces (P < 0.05), and in ight soil, copper, zinc, Fe content are all lower than positive and negative control group, and reduces along with the increase of hydration carbamoylglycine dipeptide iron chelate addition; The feedstuff-meat ratio of 12ppm interpolation group piglet is minimum, and SOD vigor and GSH-Px vigor significantly improve (P < 0.05) than positive and negative control group.
Result shows: appropriate interpolation product hydration carbamoylglycine dipeptide iron chelate of the present invention in basal diet, the production performance of weanling pig can be improved to a certain extent, improve the content of Trace Elements In Serum, reduce the content of metallic element in ight soil, improve the antioxidant property of body.

Claims (3)

1. the preparation method of hydration carbamoylglycine dipeptide iron chelate, comprises the following steps:
1) by water-soluble for carbamoylglycine dipeptides, adjust pH to be 5.0 ~ 6.0, be heated to 50 ~ 70 DEG C;
2) add xitix and ferrous sulfate successively again, 60 ~ 80 DEG C are reacted 0.5 ~ 1 hour;
3) hydration carbamoylglycine dipeptide iron chelate is obtained after crystallisation by cooling, filtration, drying;
The mol ratio of carbamoylglycine dipeptides and ferrous sulfate is (1.7 ~ 2.3): 1;
The consumption of xitix be carbamoylglycine dipeptides, ferrous sulfate and water quality and 2 ‰ ~ 3 ‰;
In step 1), the mass volume ratio of carbamoylglycine dipeptides and water is 1g:(2.0 ~ 3.0) ml.
2. preparation method according to claim 1, is characterized in that: carbamoylglycine dipeptides and ferrous sulfate mole be 2:1.
3. preparation method according to claim 1, is characterized in that: the mass volume ratio of carbamoylglycine dipeptides and water is 1g:2.5ml.
CN201310142525.4A 2013-05-06 2013-05-06 Hydrated carbamyl glycine dipeptide chelated iron and preparation method thereof Active CN103224546B (en)

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CN106804893A (en) * 2016-06-14 2017-06-09 张品林 A kind of functional form pig feed additive and preparation method thereof
CN108651735B (en) * 2018-05-16 2022-02-01 大连三仪动物药品有限公司 Peptide chelated iron composite preparation for improving production performance of sows and piglets
CN109329607A (en) * 2018-11-07 2019-02-15 上海交通大学 A kind of small peptide microelement chelate combination agent improving piglet oxidation resistance
CN113678948A (en) * 2021-08-31 2021-11-23 广州康瑞德饲料科技有限公司 Preparation method of self-assembled small peptide chelated iron for feed additive

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CN101606715A (en) * 2008-06-17 2009-12-23 浙江科技学院 A kind of preparation method who disturbs anionic food-grade amino acid ferrous chelate compound that do not contain
CN102093467B (en) * 2010-11-02 2013-12-11 中国科学院亚热带农业生态研究所 Dipeptide iron chelate for feed additives and preparation method thereof
CN102860512B (en) * 2012-10-10 2014-07-02 中国食品发酵工业研究院 Preparation method of black-bone chicken peptide and iron chelated biological iron supplement

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