KR880002033B1 - Process for producing zn-fe-cu-methionine ligand complex - Google Patents

Process for producing zn-fe-cu-methionine ligand complex

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KR880002033B1
KR880002033B1 KR1019860004324A KR860004324A KR880002033B1 KR 880002033 B1 KR880002033 B1 KR 880002033B1 KR 1019860004324 A KR1019860004324 A KR 1019860004324A KR 860004324 A KR860004324 A KR 860004324A KR 880002033 B1 KR880002033 B1 KR 880002033B1
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copper
iron
zinc
methionine
soln
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KR870010788A (en
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김희창
이종린
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주식회사 동양금속화학
이명교
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/30Oligoelements
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/142Amino acids; Derivatives thereof

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  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

A method for prepg. metal methionine ligand complex comprises (i) mixing each soln. of zinc (II), iron (II) and copper (II) or their resp. sulfate, chloride, acetate or oxide in the ratio of Zn 10-50%, Fe 1.0-20%, Cu 0.2-20% to form a soln., (ii) adding methionine soln. to the former soln. by the mole ratio of 1:1, (iii) heating for 0.5-3 hr at 60-90 deg.C and at pH 3.0-4.5 until to clear, (iv) adding EtOh to complete rxn. and cool in ambient temp. at pH 5.0-7.0 and (v) filtering and air-drying.

Description

아연, 철, 구리-메치오닌 컴플렉스의 제조방법Process for preparing zinc, iron, copper-methionine complex

제 1 도는 미량물질의 위장관내의 흡수관계를 도시한 것이다.1 shows the absorption relationship of trace substances in the gastrointestinal tract.

제 2 도는 미량물질 광물질간의 교호작용을 나타낸 것이다.2 shows the interaction between trace minerals.

본 발명은 가축 또는 가금의 사료첨가제로 유용한 아연, 철, 구리-메치오닌 컴플렉스의 제조방법에 관한 것이다.The present invention relates to a process for preparing zinc, iron, copper-methionine complexes useful as feed additives for livestock or poultry.

생명체의 유지 및 활동에 필요한 필수적인 26종의 원소들중에서 에너지와 단백질의 체내 이용 과정과 필수 영양소의 생화학적 합성에 관여하는 미량광물질로서는 아연, 철, 구리, 망간, 코발트, 요오드 등이 있다.Among the 26 essential elements required for the maintenance and activity of living organisms, zinc, iron, copper, manganese, cobalt, and iodine are trace minerals involved in the process of energy and protein use and biochemical synthesis of essential nutrients.

이들 중 생체내에서의 역할면에서나 그 필요량면에서 중요한 위치를 차지하는 것들중에는 아연, 철, 구리 등이 있는데 이들의 생체내에서의 작용은 이미 많은 사람들의 연구를 통해 밝혀졌다.Among them, zinc, iron, copper, etc. occupy an important position in terms of their role in vivo and their needs, and their in vivo activity has been found through many studies.

표 1의 아연, 철, 구리의 결핍증세에서 보는 바와같이 가축의 사료중에 주요 미네랄이 부족하게 되면 가축의 성장, 생식, 대사활동 등에서 현저한 저해를 받게 된다.As shown in the deficiency of zinc, iron, and copper in Table 1, the lack of major minerals in livestock feed impedes significant inhibition in livestock growth, reproduction, and metabolic activity.

[표 1. 아연, 철, 구리의 결핍 증세][Table 1. Zinc, Iron, Copper Deficiency]

Figure kpo00001
Figure kpo00001

Figure kpo00002
Figure kpo00002

사료 원료내에 함유되어 있는 미량광물질은 매우 안정된 공유 결합물질로서 체내 흡수과정에서 곡류내의 불용성 염(Ca-Mg 염)인 피테리트를 형성하기 때문에 체내의 이용률이 극히 낮고 양적으로도 불균형하며 불충분하여 인위적인 보충을 통하여 그 결핍을 막아야 한다.The trace minerals contained in the feed are very stable covalent bonds, which form phyrites, which are insoluble salts (Ca-Mg salts) in cereals during absorption in the body, resulting in very low utilization, unbalanced quantity, and inadequate capacity. Artificial replenishment should prevent the deficiency.

일반적인 미량광물질의 공급체로는 금속의 황산염(예 : ZnSO4, FeSO4, CuSO4등 도는 탄산염(예 : ZnCO3, FeCO3, CuCO3등)과 산화금속(예 : CuO, ZnO)의 상태로 사료에 첨가되거나 약제로서 투여되는데 이들 미량원소의 체내흡수과정은 위내에서 일차 염산염의 산태로 된 후 이온상태로 해리되어 아미노산, 단백질등의 유기화합물과 결합하여 흡수가능한 금속 결합리간드 복합체(Ligand Complex)를 형성하여 장점막세포를 통하여 혈장내로 흡수 전달된다. 이를 도식화한 것이 도면 1이다.Common sources of trace minerals include metal sulfates (eg ZnSO 4 , FeSO 4 , CuSO 4 , or carbonates (eg ZnCO 3 , FeCO 3 , CuCO 3, etc.) and metal oxides (eg CuO, ZnO). It is added to feed or administered as a drug. The body absorption process of these microelements is in the form of primary hydrochloride in the stomach, dissociated in ionic state and absorbed by binding to organic compounds such as amino acids and proteins. It is formed and transferred to the plasma through the mesenteric membrane cells, which is shown in Figure 1.

그런데 이렇게 공급된 광물질들의 상호간 양적인 불균형이 제2도와 같은 고호작용을 유발하여 흡수에 저해를 초래한다.However, the mutually quantitative imbalance of the supplied minerals causes the high interaction as shown in FIG. 2 and causes the inhibition of absorption.

즉, 광물질 공급제의 대부분이 무기 화합물의 형태로 체내에 투여되므로 어느 한 광물질의 과다 투여는 최소한 한가지 이상의 광물질의 위장관내에서 아미노산, 단백질 등 유기화합물과의 흡수태리간드 복합체를 이를때 발생하는 원소들간의 경쟁적 자리 다툼에 의한 것이다. 이를 도시한 것이 도면 2이다.That is, since most of the mineral supply agent is administered to the body in the form of an inorganic compound, an overdose of any one mineral is an element that occurs when the absorption tertiary complex with an organic compound such as amino acid or protein is in the gastrointestinal tract of at least one mineral. It is due to the competition between the competition. This is illustrated in FIG. 2.

따라서 미량원소 결핍증세의 발현시 그 치료를 신속 효과적으로 수행하기 위해서는 고호작용에 의한 흡수저해를 피할 수 있도록 근본적인 고려가 필요하다. 이에 대한 연구가 지속되어 왔다. 그러나 이제까지 만족할만한 성과는 없었다. 본 발명자들은 미량원소 결핍증세의 발현시 그 치료를 신속 효과적으로 수행하기 위하여 오랜연구를 행한 결과 제1도에서와 같이 금속과 유기화합물의 결합체인 흡수태리간드 복합체를 인위적으로 조성하여 투여한다면 제2도에서와 같이 금속간의 교호작용을 피할 수 있음을 발견하여 본 발명을 완성하게 되었다.Therefore, in order to perform the treatment quickly and effectively in the manifestation of trace element deficiency symptoms, it is necessary to consider fundamentally to avoid the absorption inhibition by hyperaction. Research on this has continued. However, no satisfactory results have been made. The present inventors have conducted a long study to quickly and effectively carry out the treatment upon the occurrence of trace element deficiency symptoms, and as shown in FIG. 1, if artificially formulated and administered the absorption tar ligand complex, which is a combination of a metal and an organic compound, FIG. The present invention was completed by discovering that the interaction between metals can be avoided as shown in FIG.

따라서 본 발명의 목적은 미량광물질중 그 결핍현상이 두드러지며, 사용량도 대체로 많은 아연, 철, 구리를 필수 아미노산의 1종인 메티오닌과 리간드 형태로 결합시킨 아연, 철, 구리-메치오닌 복합체를 제공하는 것이다.Accordingly, an object of the present invention is to provide a zinc, iron, copper-methionine complex in which the deficiency phenomenon of trace minerals is outstanding, and the amount of use of zinc, iron, and copper is generally combined with methionine, which is one of essential amino acids, in ligand form. .

아연, 철, 구리-메치오닌 복합체는 각각의 아연, 구리, 철 이온이 한분자의 아미노산과 각각 결합된 형태를 가지며, 그 결합이 리간드 형태를 취함으로써 다른 유기금속 유기화합물 즉 가수분해된 단백질이나 합성유기물에 착염상태로 결합된 금속 착화합물과는 다른 복합체이며, 더우기 이러한 금속 착화합물은 복용시 과량의 금속(특히 중금속)들을 신속하게 소변으로 배설시키는 역학을 할뿐 이들의 장내에서 흡수 이용되기 전에 다수의 아미노산에 결합되어 불용성으로 변한다.The zinc, iron, and copper-methionine complexes have a form in which each of zinc, copper, and iron ions are bonded to one molecule of amino acid, and the bond is in the form of a ligand, so that other organometallic organic compounds, ie, hydrolyzed proteins or synthetic organics. It is a complex different from metal complexes bound to salts, and moreover, these metal complexes have a dynamical function of rapidly excreting excess metals (especially heavy metals) into the urine when taken, as well as many amino acids before they are absorbed and used in the intestines. Bound to and becomes insoluble.

아연, 철, 구리-메치오닌 복합체는 위내에서 분해되지 않고 장에서 직접적으로 흡수되는 형태를 하고 있으므로 이러한 미량 원소의 결핍 중세의 신속하고 효과적인 치료효과를 가져올 수 있을 뿐만 아니라, 필수 아미노산인 메치오인을 동시에 투여하는 이점이 있다.The zinc, iron, and copper-methionine complexes do not decompose in the stomach and are absorbed directly by the intestine, which leads to the rapid and effective therapeutic effect of these trace elements. There is an advantage to administering at the same time.

아연, 철, 구리-메치오닌 복합체의 분자식은 일률적으로 표시하기에는 약간의 어려움이 있으나 대체로 아래의 그림과 같다.The molecular formulas of zinc, iron and copper-methionine complexes are somewhat difficult to express uniformly, but are generally as shown below.

Figure kpo00003
Figure kpo00003

다음에 본 발명은 실시예로서 상세히 설명한다.Next, the present invention will be described in detail by way of examples.

[실시예]EXAMPLE

가. 아연 용액의 제조 : 아연의 황산염, 염산염, 초산염, 질산염과 산화아연 등을 물에 용해한다. 이때 필요하다면 가열하면서 황산, 염산, 초산등을 가하여 완전히 용해시킨다.end. Preparation of zinc solution: Zinc sulfate, hydrochloride, acetate, nitrate and zinc oxide are dissolved in water. If necessary, dissolve completely by adding sulfuric acid, hydrochloric acid, acetic acid, etc. while heating.

나. 철 용액의 제조 : 철의 황산염, 초산염과 산화철등을 물에 용해시킨다. 이때 필요하다면 가열하면서 황산, 염산, 초산, 과산화수소등을 가하여 완전히 용해시킨다.I. Preparation of iron solution: Dissolve iron sulfate, acetate and iron oxide in water. If necessary, dissolve completely by adding sulfuric acid, hydrochloric acid, acetic acid, and hydrogen peroxide while heating.

다. 구리 용액의 제조 : 구리의 황산염, 염화염과 산화구리등을 물에 용해시킨다. 이때 필요하다면 가열하면서 황산, 염산, 초산등을 가하여 완전히 용해시킨다.All. Preparation of copper solution: Dissolve copper sulfate, chloride and copper oxide in water. If necessary, dissolve completely by adding sulfuric acid, hydrochloric acid, acetic acid, etc. while heating.

라. 각 용액의 일정 비율 혼합 : 각 용액중의 금속이온만의 농도를 계산하여 정체액중에 Zn++; 10-50%, Fe++; 1.0-20%, Cu++; 0.2-20%의 수준이 되도록 조정하여 혼합한다.la. Mixing a certain ratio of each solution: calculate the concentration of only metal ions in each solution, and then add Zn ++ into the stagnation solution; 10-50%, Fe ++ ; 1.0-20%, Cu ++ ; Mix to adjust to level of 0.2-20%.

마. 메치오닌 수용액의 제조 : 메치오닌 분말을 물에 용해시킨다.hemp. Preparation of Aqueous Methionine Solution: The methionine powder is dissolved in water.

바. 아연, 철, 구리-메치오닌 복합체의 제조 : (라)와 (마)에서 제조한 용액을 몰비율로 약 1: 1의 비율로 혼합하고 (사) 및 (바) 수용액을 산 및 알칼리를 이용하여 pH 약 3.04.5로 유지시키며 가열한 다음 60-90℃에서 0.5-3시간 반응시킨다. 반응액이 맑은 수용액이 되면 에탄올을 가하여 반응을 종료시킨다. 반응액을 다시 산 또는 알칼리 용액으로 pH 5.0-7.0으로 유지시키고 상온에서 방치 냉각한다. 생성된 반응물을 여과하여 풍건시킨다.bar. Preparation of zinc, iron and copper-methionine complexes: The solutions prepared in (D) and (E) are mixed in a molar ratio of about 1: 1, and the (A) and (F) aqueous solutions are mixed with acids and alkalis. The mixture is heated to maintain a pH of about 3.04.5 and then reacted at 60-90 ° C. for 0.5-3 hours. When the reaction solution is a clear aqueous solution, ethanol is added to terminate the reaction. The reaction solution is maintained at pH 5.0-7.0 again with acid or alkaline solution and left to cool at room temperature. The resulting reaction is filtered and air dried.

Claims (1)

아연의 무기산염 또는 산화물, 철의 무기산염 또는 그 산화물 및 구리의 무기산 또는 그 산화물을 용해하고 별도로 메치오닌을 용해시킨 용액을 각각 혼합하고 반응시켜서 아연, 철, 구리-메치오닌 복합체를 제조하는 방법.A method of preparing a zinc, iron, copper-methionine complex by mixing and reacting a solution of a mineral acid salt or oxide of zinc, an inorganic acid salt of iron or an oxide thereof, and an inorganic acid salt of copper or an oxide thereof and separately dissolving methionine.
KR1019860004324A 1986-05-31 1986-05-31 Process for producing zn-fe-cu-methionine ligand complex KR880002033B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100745569B1 (en) * 2005-12-06 2007-08-02 양태식 A feed containing a organic manganese and a organic zinc for duck, and it's breeding method
WO2010098632A3 (en) * 2009-02-27 2011-04-07 씨제이제일제당 주식회사 Method for increasing the solubility of methionine by mineral addition and acid treatment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114522807B (en) * 2022-03-03 2024-05-24 中南大学 Metal ion-organic ligand flotation reagent and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100745569B1 (en) * 2005-12-06 2007-08-02 양태식 A feed containing a organic manganese and a organic zinc for duck, and it's breeding method
WO2010098632A3 (en) * 2009-02-27 2011-04-07 씨제이제일제당 주식회사 Method for increasing the solubility of methionine by mineral addition and acid treatment

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