Title of Invention

"A METAL CHELATED ADDITIVE FOR AGRO-ZOOTECHNICAL USE, AND METHOD FOR OBTAINING SAID ADDITIVE"

Abstract The present invention is for a metal chelated additive and method of preparing the same for agro-zootechnical use selected from the group of formula's consisting of formula: (CH3SCH2CH2CH2CHOHCO)2M.nH2O where M may be a bivalent metal and n is the number of water molecules. The reaction is free from undesirable by products and the product is stable and effective in improving the main growth factors of the animal.
Full Text Dogeriptien Chclafed feed additvefor agre
method for obtaining said additive
Technical Field The present invention relates to a.chelated additive for agro-zootechnical use in the broad sense, and in particular for alimentary use in the zootechnical sector, and the associated method for obtaining said additive. A chelate is a compound which is obtained from an organic molecule (in the case in question an amino acid or a peptide chain) and a metal, ion by means of strong coordination bonds. Background art
These compounds are widely used both in the agronomic field and in the zootechnical field .since their usefulness is derived from the biological action of the metal involved, which acts as activator in a great number of enzymatic reactions and as regulator in various metabolic functions in all living organisms. The presence of the bond with an amino acid material favours the absorption, availability and use of the metal since it is transported by the organic component to all

areas of the organism.
Within the zootechnical sector in particular, these
compounds are used in various breeding or rearing sectors
to increase and strengthen the normal metabolic and
functional activities of organs and apparatuses, with
considerable positive effects on the capacities for
productive growth of the animals.
The chelates currently present on the international
market may be classified in various categories.
The best known category is that which groups together the
metal ions which form a complex with specific single
amino acids. They are well .definable compounds in terms
of chemical composition and are easily assimilated and
available for the organism.
A second category is composed of micronutrients which
form a complex with single amino acids which, even though
not well definable in this case, possess characteristics
similar to those of the preceding group.
During production of these compounds, it was noted,
moreover, that some soluble metal salts are difficult to
chelate or leave undesirable residual products such as,
for example, phosphoric acid or hydrochloric acid.
A third category contains metal ions which form a complex

with several amino acids, preferably a maximum of three up to a molecular weight of 800 daltons.
The greater size of the molecule, however, results in a weaker bonding strength and greater difficulty of absorption.
A further category is composed of proteins which are obtained from the combination of a metal ion with a peptide chain. These compounds, the amino acid composition of which is not known, may interact with other substances contained in the food and therefore be of limited availability for the animal.
Finally, there are metals which form a complex with polysaccharide chains, in which the organic component has little effect on the real nutritional requirements of the animal and the metals are combined with organic acids, which are very soluble, but may easily dissociate in the intestines, with adverse effects in terms of lowering of the intestinal pH.
Statement of the Invention
According to the present invention there is provided a metal chelated additive for agro-
zootechnical use selected from the group of formulas consisting of: formula(Formula Removed)
where M may be a bivalent metal and n is the number of water molecules.
According to the present invention there is also provided a method for preparing a metal chelated additive as claimed in any of the preceding claims comprising the following steps:
a) dissolving of M carbonate in water;
b) slow and continuous addition of methionine hydroxy analogue, until the
stoichiometric ratio of two moles of methionine to one mole of M carbonate is
reached.
Disclosure of the Invention
The object of the present invention is to obtain an additive for agro-zootechnical use and in particular for alimentary use in the zootechnical sector, in which a metal, which may also be classified among the
micronutrients, is bonded to an amino acid via a strong
chelating bond, this product being not only effective,
but also stable and easily reproducible, and free from
undesirable reaction by-products.
The objects are achieved by using a methionine in
solution with an acid function (methionine hydroxy
analogue) and reacting it with a carbonate of a bivalent
metal, starting the reaction of the two components in
particular with less methionine, relative - to the
carbonate.
Experiments carried out using the product thus obtained
on dairy cattle have shown that the invention has
positive and important effects on the animals.
Two groups of animals were prepared, one test group
supplied with ordinary metal salts, and one experimental
group supplied with the same quantity of chelated metal
ions, but with the methionine hydroxy analogue according
to the invention, in doses of about 10 g per head of
cattle per day.
At the end of the test, the following results were
observed in the treated group: a significant improvement
in all the reproductive factors (fertility, succesful
pregnancies, more rapid return to heat and improved ovary

activity) and reduction in infections of the uterus and cases of mastitis following an improvement in the immune state of the animal, which allowed the latter to withstand effectively all the problems of an infective and metabolic nature which are typical of the postnatal period. Similar experiments were carried out on some meat cattle stock, distinguishing a test group from an analysis group and supplying the said groups with identical quantities of metal ions, one in salt form and the other in chelated form for about three months, in doses of about 10 g per head of cattle per day. In this latter test, too, surprisingly a greater resistance to environmental stresses on the part of the animals, in the form of improved productive performances (growth and conversion factors, body growth), was noted. A reduction in podalic pathologies (laminitis, ulcers and interdigital dermatitis) was also detected. The invention will emerge more clearly from the description of a working example illustrated below. Detailed description of the preferred embodiments Example No. 1
The structural formula of a chelate according to the invention, obtained from the reaction of a methionine

hydroxy analogue with the carbonate of a bivalent metal, in the presence of water, is shown: (Formula Removed)
where M may be a bivalent metal and is in general Zn2+,
Cu2+, Co2+, Mn2% Ca2+ or Mg2+.
Said compound was prepared using in particular zinc
carbonate; it is obtained from the reaction of two
molecules of methionine hydroxy analogue + one of ZnC03:
2CH3SCH2CH2CHOHCOOH+ZnC03→(CH3SCH2CH2CHOHCO) 2Zn+H20+C02
where, since the reaction takes place in an aqueous
solution, water of crystallization may be present in the
dried chelate.
The reaction takes place in the presence of a small
amount of demineralized water, at temperatures of between
25°C and 35°C and at ambient pressure, with the evolution
of CO,.
Although the reaction is slightly exothermic, slight
heating up to 40°C may be appropriate in order to
accelerate the process and facilitate the evaporation of
the excess water.
In the case described, the dried chelate is in the form
of a white powder, with a melting point of about 248°C
and a solubility in water of about 20g/l at ambient
temperature.
The infrared vibrational absorption spectrum indicates
that the chelating process has taken place: in fact, the
spectrum exhibits a series of characteristic bands, in
accordance with the structure described above. The
strongest bands are indicated below (values in cm'1) : 3219
(OH stretching); 2918 (CH stretching); 1591 (COO
asymmetrical stretching); 1422 (COO symmetrical
stretching + OH bending); 1307 (CH bending); 1088 (C-OH
stretching).
The method of preparation of the product is as follows:
One mole of zinc carbonate is poured, together with
demineralized water slightly heated to about 35°C, in a
sufficient quantity to dissolve the zinc carbonate, into
a mixer or a reactor provided with a mixer.
The optimum temperature range is in any case between 20°C
and 40°C.
The mixer is turned on and the methionine hydroxy
analogue is added slowly so as to avoid the undesirable
effects of a strong evolution of C02 and overheating of
the mixture. The stoichiometric ratio is two moles of
methionine hydroxy analogue to one mole of zinc
carbonate; said ratio being reached slowly by means of
successive additions of methionine while mixing is
continued for a duration of between one and two hours so
as to favour the generation of C02 and evaporation of the
excess water.
During the entire reac.tion, the methionine/metal
carbonate stoichiometric ratio is less than the
theoretical ratio, approaching the theoretical value
asymptotically at the end of the reaction.
Once the product has reached a paste-like consistency,
drying may be performed by means of the normal drying
processes which are known today, or by adding adsorbent
products (silica, corn-cob flour).
In this way a stable product, which is pure in that it is
devoid of reaction by-products, is obtained.
Moreover this modified amino acid offers considerable
advantages over other common amino acids in that:
* it can be more easily assimilated in the duodenum and
is less susceptible to degradation of the ruminal
bacterial flora;
* it may be rapidly detected in the blood and is
therefore available for production;
* it can be mixed uniformly without the risk of
compaction;
* it is compatible with vitamins, fats and minerals
present in the diet;
* it increases the efficiency of anti-mould produces
owing to its acid characteristics;
* absorption thereof in the intestines does not require
energy which is dissipated in the form of a dynamic
specific action.
The chelate obtained was prepared using simple apparatuses already present in any normal additive-manufacturing industry.
Finally the costs for these operations are very low. Possible variants:
The possible variants are obtained by simply exchanging the bivalent metal (cuprous ion, zinc, manganous ion, cobalt, ferrous ion) chelated in each case with the organic molecule.
For example, if, for the sake of brevity, HMetOH
designates the methionine hydroxy analogue where H is the
exchangeable acid, the solid products which can be
obtained by the process illustrated above may be
indicated by M(MetOH) 2.nH20 where M is the bivalent metal
cation of a carbonate.
When M is Co2+, a pink powder with a melting point > 310°C
is obtained.
When M is Mn2"1', a light brown powder with a melting point
> 310°C is obtained.
When M is Cu2+, a light green powder with a melting point
of 202°C is obtained.
Each metal ion has particular characteristics with regard
to given enzymatic and metabolic systems of the animal or
the plant to which it is administered, whereby the
advantages of administering it in the form of a chelate
bonded to a methionine hydroxy analogue remain
unaffected.
Illustrated with regard to applications in the
zootechnical sector, the additive according to the
invention may also find widespread application in the
agronomic sector, where the presence of the bond between
the bivalent metal and an amino acid material favours the
absorption, availability and use of the metal since it is transported by the organic component to the vegetable tissue.




We claim:
1. A metal chelated additive for agro-zootechnical use selected from the group of formulas consisting of: formula:
where M may be a bivalent metal and n is the number of water molecules.
2. The metal chelated additive as claimed in claim 1, wherein the formula
are(Formula Removed)
3. The metal chelated additive as claimed in any of the preceding claims,
wherein the formula is (Formula Removed)and has
characteristics selected from the following group:
i) white powder;
ii) with a melting point of about 248°C;
iii) solubility in water of about 20g/l at ambient temperature; and
iv) infrared vibrational absorption spectrum having a series of characteristic bands (values in cm"1): 3219 (OH stretching); 2918 (CH stretching); 1591 (COO asymmetrical stretching; 1422 (COO symmetrical stretching + OH bending); 1307 (CH bending); 1088 (C-OH stretching).
4. A composition comprising at least one of the metal chelated additives as
claimed in any of the preceding claims.
5. A method for preparing a metal chelated additive as claimed in any of the
preceding claims comprising the following steps:
a) dissolving of M carbonate in water;
b) slow and continuous addition of methionine hydroxy
analogue, until the stoichiometric ratio of two moles of
methionine to one mole of M carbonate is reached.

6. The method as claimed claimed in claim 5, wherein M is selected from the
group consisting of Zn2+, Cu2+, Co2+, Mn2+, Ca2+, Fe2+ or Mg2+.
7. The method as claimed in any of the preceding claims, wherein the
reaction is conducted at a temperature in the range of 20°C to 40°C.
8. The method as claimed in any of the preceding claims, wherein during the
entire reaction, the methionine/metal carbonate stoichiometric ratio is less
than the theoretical ratio, approaching the theoretical value asymptotically
at the end of the reaction.
9. A metal chelated additive as claimed in any of the preceding claims as and
when used for the preparation of a composition for use in the agro-
zootechnical sector.
40. The use as claimed in claim 9, wherein the composition is for alimentary use in zootechnical sector.
11. A metal chelated additive for agro-zootechnical use, substantially as
hereinbefore described with reference to the foregoing description.
12. A method for preparing a metal chelated additive, substantially as
hereinbefore described with reference to the foregoing description.

Documents:

in-pct-2001-00276-del-abstract.pdf

in-pct-2001-00276-del-claims.pdf

in-pct-2001-00276-del-correspondence-others.pdf

in-pct-2001-00276-del-correspondence-po.pdf

in-pct-2001-00276-del-description (complete).pdf

in-pct-2001-00276-del-form-1.pdf

in-pct-2001-00276-del-form-19.pdf

in-pct-2001-00276-del-form-2.pdf

in-pct-2001-00276-del-form-3.pdf

in-pct-2001-00276-del-form-5.pdf

in-pct-2001-00276-del-gpa.pdf

in-pct-2001-00276-del-pct-101.pdf

in-pct-2001-00276-del-pct-210.pdf

in-pct-2001-00276-del-pct-304.pdf

in-pct-2001-00276-del-pct-409.pdf

in-pct-2001-00276-del-pct-416.pdf

in-pct-2001-00276-del-petition-137.pdf


Patent Number 231978
Indian Patent Application Number IN/PCT/2001/00276/DEL
PG Journal Number 13/2009
Publication Date 27-Mar-2009
Grant Date 14-Mar-2009
Date of Filing 09-Apr-2001
Name of Patentee AGRISTUDIO S.R.L.
Applicant Address VIA GRAMSCI 104/F, I-42100 REGGIO EMILIA, ITALY.
Inventors:
# Inventor's Name Inventor's Address
1 CIRIBOLLA, ANTONIO VIA MARTIRI DELLA BETTOLA, 96, I-42100 REGGIO, EMILIA, ITALY.
PCT International Classification Number A23K 1/16
PCT International Application Number PCT/IT99/00225
PCT International Filing date 1999-07-19
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 RE99A000028 1999-03-05 Italy