CN1688211A - Use of metal chelates in human or animal feeding - Google Patents

Abstract

The present invention relates to the use in human and animal nutrition ( monogastric and polygastric animals) of known chelates of bivalent metal Mg, Ca, Mn, Co, Cu, Zn and Fe with methionine hydroxy analogue. The present invention further relates to a method for preparing new chelates with methionine hydroxy analogue, both in solid form with iron (II), vanadium (iV) and (V) and molybdenum (V) and (VI), and in liquid form in aqueous solution with iron (II) and (III) and chrome (III). Eventually, the present invention relates to the use of said new chelates, both in solid form with iron (II), vanadium (IV) and (V) and molybdenum (V) and (VI), and in liquid form in aqueous solution with iron (II) and (III) and chrome (III), in human and animal nutrition.

Description

The application of metallo-chelate in human or animal's feed

The present invention relates to divalent metal Mg, Ca, Mn, Co, Cu, the purposes of the known chelate of Zn and Fe and methionine hydroxy analog in humans and animals nutrition (nonruminant and multistomachal animal).The invention further relates to preparation methionine hydroxy analog of solid form and iron (II), vanadium (IV) and (V) and molybdenum (V) and novel chelate (VI), and the liquid aqueous solution form with iron (II) and (III) and the method for the novel chelate of chromium (III).At last, the present invention relates to the iron (II), vanadium (IV) of described solid form and (V) and molybdenum (V) and novel chelate (VI), and the iron of liquid aqueous solution form (II) and (III) and the purposes of novel chelate in humans and animals nutrition of chromium (III).

Be known that metallo-chelate is the compound that is formed by strong coordinate bond by organic molecule (such as amino acid or peptide chain or 2-ketoacid or 'alpha '-hydroxy acids) and metal ion.Some known metallo-chelates are used for the field of human nutrition product.Their purposes is owing to the biological action by the performance of related metallic element, in several enzyme reactions as activator, and in the various metabolic functions of all living organisms as conditioning agent.The existence of chelating molecule has promoted absorption, utilization and the function of metallic element, because the latter is entrained by organic component at the All Ranges of organism.This has also caused the not loss of metal in excreta of usefulness to significantly reduce, and has therefore caused remarkable economical saving and environmental advantages.

The general features that characterizes high bioavailability metallo-chelate is: (a) neutrality of complex (positive charge of metal is by the negative electrical charge of part institute balance); (b) there are not negative counter ion counterionsl gegenions (chlorine root, sulfate radical); (c) low-molecular-weight of complex (＜1,500 dalton); (d) clear and definite metal/chelating agent (bidentate) ratio, can≤1: 2.

And metallo-chelate should obtain via the method that simply cleans with high yield by being begun by the raw material that can find easily.These features can utilize suitable part to realize, latter's deprotonation and carrying out having at least two donor atoms on this position of chelating easily.The example of part is suitably functionalized amino acid and other organic acid.

With regard to iron, the administration of its chelated forms is effective especially for anaemia.Anaemia is because the pathological state of the blood that the reduction of the amount of the minimizing of erythrocytic number, hemoglobin or these two shortage are caused.Iron is the basis of hemoglobin, because it is that wherein oxygen is fixed in the center of ferroheme.The crowd who needs relatively large iron has menstruation or conceived women, the child below two years old, vegetarian, the people who suffers from hemorrhoid, the people who suffers from ulcer and last blood donor.The symptom that anaemia person felt be tired, to cold than hypersensitivity, irritability, absent minded and palpitaition.

In addition, iron can prevent virus or bacterial infection, because it has promoted immune excitement.In addition, iron has promoted to belong to the metabolism of the vitamin of B family.The shortage that is known that these vitamins can cause disease such as dermatitis or even more serious disease such as pellagra (because shortage of vitamin B3).Iron is intervened the building-up process of adrenaline and norepinephrine.At last, the shortage of iron has caused the indolence of wound.

First purpose of the present invention is that proposition is used for the assimilation agent (integrator) in the administration of human nutrition product.Described assimilation agent also delivers medicine to suffers from the metal oligo-element such as Mg, Ca, Mn, Co, Cu, the patient that Zn and Fe lack.

Second purpose of the present invention is the assimilation agent that proposes to be used to deliver medicine to the agriculture livestock technology nutriment of simple stomach or multistomachal animal.Described assimilation agent also delivers medicine to and need give the metal oligo-element such as Mg, Ca, and Mn, Co, Cu, the simple stomach of Zn and Fe or multistomachal animal, and have a high bioavailability.

The 3rd purpose of the present invention is the metallo-chelate that proposes one of the methionine hydroxy analog of preparation solid form or their salt and iron (II), vanadium (IV) and/or vanadium (V) and molybdenum (V) and/or molybdenum (VI), with the liquid aqueous solution form with iron (II) and (III) and the method for the metallo-chelate of chromium (III), wherein said metal is bonded in the difunctionality organic ligand with strong coordinate bond, so that form stable metallo-chelate.

Another object of the present invention is iron (II), vanadium (IV) and/or vanadium (V) and molybdenum (V) and/or the novel chelate (VI) that proposes described solid form, and the iron of liquid aqueous solution form (II) and (III) and the novel chelate of chromium (III) be used to prepare the purposes of the metal assimilation agent of humans and animals nutriment.

In one embodiment of the invention, described first and second purposes realize by the purposes that proposition has the metallo-chelate [2: 1] of general formula (I):

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂M·nH ₂O?????????????(I)

Wherein this bifunctional chelants is the 2-hydroxy-4-methyl-thiobutanoic acid, and 'alpha '-hydroxy acids is called " methionine hydroxy analog " (MHA); M is selected from: Co, Ca, Mg, Zn, Fe, the divalent metal of Cu and Mn, and n is the number of hydrone, and this chelate suffers from patient that the metal oligo-element lacks or the metal assimilation agent that is used for delivering medicine in farming animals animal husbandry technical field simple stomach or multistomachal animal as the preparation treatment.In general formula (I), have 0-12 hydrone, preferred 0-6 hydrone, for example, 0-4 hydrone.2-hydroxy-4-methyl-thiobutanoic acid and iron ion have formed has clear and definite stoichiometric chelate, contains the chelating agent/iron atom of 2 molecules, according to it and divalent metal Mg, Ca, and Mn, Co, Cu and Zn form the same way as of chelate.

Be used for the method for metallo-chelate that preparation has general formula (I) and be described in International Patent Application PCT/IT99/00225, comprise MHA and divalent metal Mg, Ca, Mn, Co, the direct reaction of the corresponding carbonate of Cu and Zn.

In according to one embodiment of the invention, the applicant has improved the method that preparation has the metallo-chelate of general formula (I), and this method imagination MHA and metal (II) oxide be such as Mg, Ca, and Mn, Co, Cu, the oxide of Zn and Fe directly reacts.

In this novel embodiment, use the oxide of metal (II) to replace as applying for the carbonate described in the PCT/IT99/00225, technology and operating condition with in application PCT/IT99/00225, mention those do not compare and change, therefore described operating condition is considered to comprise in this application.

Advantageously, use following material: the mixture of magnesia and magnesium carbonate, perhaps magnesia substitutes magnesium carbonate fully, zinc oxide and zinc carbonate, perhaps zinc oxide replaces zinc carbonate fully, and the mixture of calcium oxide and calcium carbonate, and perhaps calcium oxide replaces calcium carbonate fully.

The applicant finds that it is favourable that following metallo-chelate is used for the human nutrition product:

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Zn·2H ₂O

These two hydrones are not bonded in this metal.

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Cu

It is not have hydrone to be bonded in the no water complex of metal.

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Co·2H ₂O

These two hydrones are by complexing.

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mn·2H ₂O

These two hydrones are by complexing.

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Ca·2H ₂O

These two hydrones are not bonded in this metal.

-(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mg·2H ₂O

These two hydrones are not bonded in this metal.

In another embodiment of the invention, described the 3rd purpose by proposing the preparation solid form methionine hydroxy analog or the metallo-chelate of one of its salt and iron (II), vanadium (IV) and/or vanadium (V) and molybdenum (V) and/or molybdenum (VI) and liquid aqueous solution form with iron (II) and (III) and the method for the metallo-chelate of chromium (III) realize.

Under the situation of vanadium and molybdenum, the method for preparing their chelate comprises their corresponding oxide and the reaction of methionine hydroxy analog.

In addition, under the situation of vanadium and molybdenum, the method for preparing their chelate comprises the reaction of their corresponding metal salt and methionine hydroxy analog.

For example, a certain amount of solid V ₂O ₅Or MoO ₃Solution with methionine hydroxy analog adds at high temperature with under stirring.The clear solution and the solid precipitation of the chelate of vanadium or molybdenum have been obtained by this reaction.In preferred embodiments, the applicant is with vanadium oxide V ₂O ₅Be arranged in the container with methionine hydroxy analog.Vanadium oxide and methionine hydroxy analog be with 1: 2 to 1: 8, and (mol ratio of vanadium/MHA) existed in preferred 1: 4 to 1: 6.

This container is equipped with agitating device, heater and reaction backflow device.This is reflected under mechanical agitation and the backflow and carried out the preferred 30 minutes time 20-60 minute.End in reaction has obtained dark green solution, has obtained the solid green precipitate by this solution after cooling.Confirmed that from sedimentary chemistry and physical analysis applicant it is to have chemical formula VOL ₂Vanadium (IV) complex, L=deprotonation methionine hydroxy analog wherein.

In course of reaction, vanadium oxide (V) is reduced to vanadium (IV).

Under the situation of iron (II), this preparation method carries out with the reaction of ferrous sulfate (or any other soluble iron (II) salt) in water environment by the sodium salt (or alkali metal or alkali salt) of MHA.

For reaction is reached fully, the mol ratio of MHA/ iron (II) is 2: 1.Ferrous chelate compound precipitates from reaction environment, filters and washes with water, so that remove formed solubility sodium sulphate.

After filtering and washing, dry then chelating product is so that reduce the amount of adsorbed water.This product is the buff powder with low aqueous solubility of following chemical formula:

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Fe·2H ₂O

Hydrone directly is bonded in iron (TGA data).

The infrared ray vibrational spectrum has shown the chelating that is taken place: in fact, this spectrum has the serial key band according to above structural formula.

Especially, 1,596cm ^-1Can find bands of a spectrum owing to the asymmetric companding of hydroxy-acid group, as estimating for deprotonation and coordination, with respect to free MHA (1,720cm ^-1), it shifts to low frequency significantly.Obtained pure and stable product like this.

In one embodiment of the invention, can pass through with 〉=2, preferred 3 MHA/M (III) ratio is dissolved in the soluble-salt and the MHA of iron or chromium (III) in the water environment, keep pH in suitable value, obtain the stabilizing solution of the chelate of iron (II) and chromium (III) and MHA to prevent corresponding precipitation of hydroxide.

In a preferred embodiment, the applicant has improved the preparation method of the stabilizing solution of chromium (III), wherein chromic salts, for example chromium sulfate Cr ₂(SO ₄) ₃MHA under agitation reacts with methionine hydroxy analog, for example by heating 20-120 minute, and preferred 30-60 minute time.Chromic salts and methionine hydroxy analog were with 1: 2 to 1: 30, and preferred 1: 2 to 1: 20 mol ratio exists.At the end of reaction, obtained the solution of chromium (III) with the complex of methionine hydroxy analog.

In another embodiment preferred of the present invention, described the 4th purpose be by proposing iron (II), vanadium (IV) and/or vanadium (V) and the molybdenum (V) and/or the molybdenum (VI) of solid form, and the iron of liquid aqueous solution form (II) and (III) and the described novel chelate of chromium (III) be used to prepare the purposes of the metal assimilation agent of humans and animals nutriment.

Described in the present invention metallo-chelate can be mixed for preparing metal assimilation agent mutually with various amount ratios.

Therefore, the assimilation agent that proposes to be used for the humans and animals nutriment can contain with good grounds one or more metallo-chelates of the present invention.

The applicant is to above-mentioned and carried out serial experiment according to metallo-chelate of the present invention.

In vitro test

For in vitro test, end user's colon adenocarcinoma cell (CACO-2), they are the vitro system that are most commonly used to study the intestines function, especially for the transepithelial transportation, because described cell (CACO-2) has formed ultra microstructure, function and the electrical property that is similar to small intestine.

The formation that iuntercellular connects can be monitored by the transepithelial electrical resistance (TEER) of measuring cell monolayer.Because connecting (the wearing cell) of having limited solute, moves iuntercellular, so TEER changes the permeability index that is used as described connection usually.

Figure 1 illustrates the equipment that is used for cell growth and differentiation.

The carrier that the described cell of representing with A among Fig. 1 is represented with B in Fig. 1 (permeable filter) is gone up growth and differentiation, between forming, connect by functioning cell institute in conjunction with the individual layer noble cells till.Described filter B has separated top environment C (AP) (simulation enteric cavity) and has simulated the base side environment D (BL) of chamber under mobile being positioned at of capillary blood.

Described cell was handled 3 hours down pH5.5 and 37 ℃ in cushioning liquid with Fe (the III)/MHA (1: 3) of two kinds of variable concentrations and Fe (III)/NTA (1: 2) (NTA is as the reference chelate).Described solution is put into top compartment C (AP), and base side compartment (D) (BL) contains the iron-free solution of the apotransferrin of the cushioning liquid that is arranged in pH7.4.In described experimentation, at interval down, measure TEER (Ω cm at the fixed time ²), the result is illustrated among Fig. 2 (in 3 hours process per 30 minutes once) and Fig. 3 (after 24 hours).

These results are shown in Figure 4, represented the content of iron in the cell after handling 3 hours with Fe (the III)/MHA of variable concentrations and Fe (III)/NTA.Data are represented with nmol iron/filter.

Can infer that from Fig. 4 iron/MHA chelate is higher than observed this amount tester from the amount of top environment C by cell.

And, can infer that from Fig. 5 (having represented at Fe (III)/MHA and the Railway transportation after Fe (III)/NTA processing defeated) concentration of the iron of transportation is comparable from top environment C to base side environment D with two kinds of variable concentrations.Data are represented with nmol iron/filter.

In the digital proof shown in the Figure 4 and 5, iron chelate is absorbed by the intestines microvillus consumingly and moves in blood flow.

Can infer that from Fig. 2 (showing the TEER measured value) iuntercellular does not connect and changes, and has therefore proved that the iron chelate pair cell is nontoxic, with non-chelated iron such as the situation of ferrous sulfate under what happens opposite.

Fig. 3 shown at the cushioning liquid of removing the pH5.5 that contains iron/MHA or iron/NTA, keep cell in culture medium after 24 hours the measured value of TEER.Described Fig. 3 has shown that iron/MHA chelate at cell inner stablity, does not cause poisonous effect.

At last, these test demonstration, and MHA/M chelate according to the present invention is effectively absorbed, and are stable in enterocyte, and are nontoxic.

More than shown in the result be iron (II), vanadium (IV) and/or vanadium (V) and the molybdenum (V) and/or the molybdenum (VI) of solid form, and the iron of liquid aqueous solution form (II) and (III) and the described novel chelate of chromium (III) purposes that is used to prepare the metal assimilation agent of humans and animals nutriment support is provided.

In vivo studies

Described test relates to nonruminant (such as pig) and multistomachal animal (such as calf).

A) nonruminant (pig)

35 ages in days give the only different food in zinc source with the pig (control group and test group) of two test group that weaned on 19th.

Described food contains every kilogram of food 3,500 kilocalories of ED, 1.15g lysine, zinc element with total amount 81mg (81ppm), its 31mg (31ppm) is provided by raw material, and 50mg (50ppm) provides with zinc sulfate (tester) with according to the form of the chelate (test) of zinc of the present invention and MHA respectively.

The animal of these two groups keeps balance by nest, live-weight and sex, and feeds 27 days.Other 4 animals are put to death immediately, according to following their sample of operation preparation.The animal of two groups is being weighed before on-test and after 27 days.When off-test, kill these pigs, take out stomach, intestines, left kidney and liver from each pig.Empty stomach and intestines, weigh once more, so that obtain the net weight of described organ.Get the sample of kidney, liver and brain, and freezing.Then stomach, intestines, left kidney and liver and remaining carcass (carcass) are put together, use the blender homogenizing.From the material of such acquisition, take a sample then, and freezing.These samples dewater with dehydration equipment then, and carry out chemical analysis.

By the level of atomic absorption spectrum to cryodesiccated sample determination zinc, copper and iron.Gentle this product of the total body water of zinc is relevant.

According in on-test with " only " weight of the body when finishing (, do not have gastral content) and its zinc content, can also measure zinc reservation every day amount.The chemico-analytic result that these samples are carried out has been shown in table 1.These pigs are condemned to death when the average weight of 16.2kg.Average weight increase every day is 324g.

From can inferring in the data shown in the table 2 of the zinc reservation every day amount that relates to two kinds of separate sources, the assimilation of the chelates of zinc that is kept by organism is than the assimilation of zinc sulfate high by 26% (P=0.07).Table 3 shown relate to the zinc source to the influence of the content of the zinc in liver, kidney and the brain, copper and iron and therefore to the interactional influence that is present in the described element in the diet with inorganic form.In fact, a kind of by reducing, absorb another kind of and be known by the interaction that described free ion applies.

The content of described three kinds of inorganic matters in liver is not subjected to the influence of diet, therefore is not subjected to the influence in zinc source.The mean value of zinc is 296mg/kg, and the value of copper is that the value of 6 3mg/kg and iron is 220mg/kg.On the contrary, kidney shown high level zinc (+18%, P=0.07), iron (+36%, P＜0.01) and copper (+36%, P=0.12), and have only a back value not reach the threshold value of statistical significance, but it has shown the tendentiousness of increase of the reservation amount of described metallic element.

In brain, has zinc (+13%), the copper (+20%) of high level, the tendentiousness of iron (+25%).Gained is the result point out, such as sulfate, the metallic element of chelated forms has higher bioavailability with respect to inorganic source, and lowers with the interaction of other ion, and this has caused the latter's higher reservation.

As everyone knows, pig is near one of animal model of people, so they are usually as the evaluation in human body field and the model of research.

B) multistomachal animal (stocker)

The two groups of female Charolaise calves (30 monthly age) that respectively comprise 6 animals with average starting weight of 567kg (contrast) and 565kg (test) were fed 90 days with identical diet.Unique difference is that tester gives zinc carbonate and test group gives according to chelates of zinc of the present invention.The 22kg/ animal that ingests every day, total day of supply of zinc element is 700mg.

Measure the live-weight when on-test and end of each animal, carcass weighs and butchers yield.Data are shown in the table 4.

With respect to feeding to those of zinc carbonate, (652kg is to 642kg to have obvious higher final weight feed for the animal of chelates of zinc, p＜0.05), obviously higher weight every day increases (1,039g is to 934g, p＜0.05), obviously (377kg is to 366kg for higher carcass weight, p＜0.01) and obviously higher yield (57.83% pair 57.03%, p＜0.01).Data are shown in the table 4.In table 5, illustrated because the effect that chelates of zinc brought with institute speed ratio rate existing in giving the diet of animal.

Described result has shown the remarkable improvement with respect to the above-mentioned livestock technology performance of the chelates of zinc in the inorganic source of described element.The stability constant of various Fe/MHA complexs is calculated with potentiometric titration.The stability of iron (III) complex is very high, and has also formed the chelating material under acid pH.The Fe of coordination not ³⁺Ion only exists only under the low-down pH value (＜2.5), and under higher pH, all iron (III) are as chelating material metal/part=cooperation in 1: 2.

Table 1

		Chelate	Sulfate	?E.M.S.
					Fate	n	?26.3	?26.4
Initial live-weight	kg	?7.54	?7.33	?0.50
					Final live-weight	kg	?16.14	?16.20	?0.55
Weightening finish every day	g	?327	?321	?11
					Diet	g	?544	?548	?1.9
Transformation index		?1.68	?1.72	?0.054
					Initial net weight	kg	?7.31	?7.49	?0.48
Final net weight	kg	?15.57	?15.76	?0.55
					Net gain every day	g	?314	?313	?11

Table 2

		Chelate	Sulfate	?E.M.S.
					Every day, Zn kept	mg	?5.40	?5.27	?0.37

Table 3

	Chelate	Sulfate	?E.M.S.	Statistical significance
					Liver
Zinc	292	?300	?21	?P＝0.80
					Copper	63.6	?62.5	?6.3	?P＝0.91
Iron	240	?199	?35	?P＝0.44
Kidney
					Zinc	97.5	?82.3	?5.5	?P＝0.07
Copper	55.0	?40.2	?6.4	?P＝0.12
					Iron	244	?179	?11.8	?P＜0.01
					Brain
Zinc	53.9	?47.6	?3.5	?P＝0.23
					Copper	28.1	?23.3	?3.5	?P＝0.35
Iron	100.9	?80.6	?9.9	?P＝0.17

Table 4

	Diet	Initial weight	?E.M.S.
					Contrast	567.700000	?31.845747
	Zn	565.633333	?31.845747
		Final weight	?E.M.S.
					Contrast	642.	?2.694781
	Zn	652.	?2.691923
				Contrast is to Zn p＜0.05
	Diet	Weightening finish every day	?E.M.S.
					Contrast	931	?29.94201
	Zn	1,039	?29.91025
				Contrast is to Zn p＜0.05
	Diet	Carcass is heavy	?E.M.S
					Contrast	366.	?1.812368
	Zn	377.	?1.810445
				Contrast is to Zn p＜0.01
	Diet	Butcher weight	?E.M.S.
					Contrast	57.03	?0.1132212
	Zn	57.85	?0.1131011
				Contrast is to Zn p＜0.01

Table 5

Control group	The calf numbering	Initial weight kg	Final weight kg	G increases weight every day	Total augment weight kg	The heavy kg of carcass	Butcher weight kg
								?1	?583.5	?670.75	?1,050	?94.50	?383	?0.578
	?2	?583.5	?670.75	?970	?87.30	?383	?0.571
								?3	?599.5	?675.96	?850	?76.50	?388	?0.574
	?4	?540.9	?623.67	?920	?82.80	?353	?0.566
								?5	?568.1	?649.12	?900	?81.00	?370	?0.570
	?6	?532.3	?624.13	?1,020	?91.80	?357	?0.572
								Test group	The calf numbering	Initial weight kg	Final weight kg	G increases weight every day	Total augment weight kg	The heavy kg of carcass	Butcher weight kg
?1	?625.6	?724.61	?1,100	?99.0	?421	?0.581
							?2		?676.8	?789.29	?1,250	?112.5	?457	?0.579
?3	?582.7	?686.21	?1,150	?103.5	?398	?0.580
							?4		?564.0	?653.98	?1,000	?90.00	?378	?0.578
?5	?476.5	?557.49	?900	?81.00	?320	?0.574
							?6		?468.2	?548.28	?890	?80.10	?318	?0.580

Claims (25)

1, be selected from the purposes of at least a metallo-chelate among those with following general formula (I):

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂M·nH ₂O????(I)

Wherein: M is selected from: Mg, and Ca, Mn, Co, Cu, the divalent metal among Zn and the Fe, and n is the number of hydrone; Be used for preparing assimilation agent in the administration of human nutrition product.

2, according to the purposes of claim 1, wherein this assimilation agent delivers medicine to and suffers from the metal oligo-element such as Mg, Ca, Mn, Co, Cu, the patient that Zn and Fe lack.

3, according to the purposes of claim 1, wherein said at least a metallo-chelate is selected from following group:

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Zn·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Cu；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Co·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mn·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Ca·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mg·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Fe·2H ₂O

Be used for preparing assimilation agent in the administration of human nutrition product.

4, according to the purposes of claim 3, wherein this assimilation agent delivers medicine to and suffers from the metal oligo-element such as Mg, Ca, Mn, Co, Cu, the patient that Zn and Fe lack.

5, be selected from the purposes of at least a metallo-chelate among those with following general formula (I):

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂M·nH ₂O????(I)

Wherein: M is selected from: Mg, and Ca, Mn, Co, Cu, the divalent metal of Zn and Fe, and n is the number of hydrone; Be used to prepare the assimilation agent of the farming animals animal husbandry technical nutrient product that deliver medicine to simple stomach or multistomachal animal.

6, according to the purposes of claim 5, wherein this assimilation agent delivers medicine to and suffers from the metal oligo-element such as Mg, Ca, Mn, Co, Cu, simple stomach or multistomachal animal that Zn and Fe lack.

7, according to the purposes of claim 5, wherein said at least a metallo-chelate is selected from following group:

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Zn·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Cu；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Co·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mn·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Ca·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Mg·2H ₂O；

(CH ₃SCH ₂CH ₂CH(OH)COO) ₂Fe·2H ₂O

Be used to prepare the assimilation agent of the farming animals animal husbandry technical nutrient product that deliver medicine to simple stomach or multistomachal animal.

8, according to the purposes of claim 7, wherein this assimilation agent delivers medicine to and suffers from the metal oligo-element such as Mg, Ca, Mn, Co, Cu, simple stomach or multistomachal animal that Zn and Fe lack.

9, preparation metallo-chelate (CH ₃SCH ₂CH ₂CH (OH) COO) ₂Fe2H ₂The method of O comprises the step that wherein allows the alkali metal salt of methionine hydroxy analog or alkali salt and soluble iron (II) salt react in water environment.

10, according to the method for claim 9, wherein this is reflected between the sodium salt of methionine hydroxy analog and the ferrous sulfate and carries out.

11,, wherein filter iron (II) chelate that obtains by this reaction and wash with water according to the method for claim 9 or 10.

12, the method for preparing the vanadium metal chelate comprises wherein allowing the step of solution reaction of vanadium (V) oxide or salt and methionine hydroxy analog.

13, according to the method for claim 12, wherein barium oxide is V ₂O ₅

14,, wherein be reflected under high temperature and the stirring and carry out according to the method for claim 12 or 13.

15, be used for preparing purposes according to the vanadium metal chelate of each preparation of claim 12-14 in the assimilation agent of human nutrition product administration.

16, be used to prepare the purposes of the assimilation agent of the farming animals animal husbandry technical nutrient product that deliver medicine to simple stomach or multistomachal animal according to the vanadium metal chelate of each preparation of claim 12-14.

17, the method for preparing the metal molybdenum chelate comprises wherein allowing the step of solution reaction of molybdenum (VI) oxide or salt and methionine hydroxy analog.

18, according to the method for claim 17, wherein molybdenum oxide is MoO ₃

19, according to the method for claim 17 or 18, wherein this is reflected under high temperature and the stirring and carries out.

20, be used for preparing purposes according to the metal molybdenum chelate of each preparation of claim 17-19 in the assimilation agent of human nutrition product administration.

21, be used to prepare the purposes of the assimilation agent of the agriculture livestock technology nutriment that delivers medicine to simple stomach or multistomachal animal according to the metal molybdenum chelate of each preparation of claim 17-19.

22, the stable, aqueous solution of the complex of iron (III) or chromium (III) and MHA, wherein mol ratio 〉=2 of MHA/M (III).

23, preparation is according to the method for the stable, aqueous solution of claim 22, comprises wherein allowing the step of reactant aqueous solution of methionine hydroxy analog MHA and soluble iron (III) or chromium (III) salt.

24, be used for preparing purposes according to the stabilizing solution of the iron (III) of claim 22 or chromium (III) complex in the assimilation agent of human nutrition product administration.

25, be used to prepare the purposes of the assimilation agent of the farming animals animal husbandry technical nutrient product that deliver medicine to simple stomach or multistomachal animal according to the iron (III) of claim 22 or the stabilizing solution of chromium (III) complex.

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