CA1325014C - Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids - Google Patents
Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acidsInfo
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- CA1325014C CA1325014C CA000616315A CA616315A CA1325014C CA 1325014 C CA1325014 C CA 1325014C CA 000616315 A CA000616315 A CA 000616315A CA 616315 A CA616315 A CA 616315A CA 1325014 C CA1325014 C CA 1325014C
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- manganese
- zinc
- alpha amino
- salt
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Abstract
ABSTRACT OF THE DISCLOSURE
A method of making 1:1 complex salts of alpha amino acids and a metal ion which is either zinc or manganese, having the use-ful feature of being highly body absorbable nutritional supple-ments, the method comprising reacting a water soluble zinc salt or manganese salt with an alpha amino acid in the presence of catalytically effective amount of ferric ion which aids in solubilizing the metal salt while simultaneously enhancing the formation of 1:1 complexes between the selected zinc or manganese salt and the desired alpha amino acid, particularly methionine.
A method of making 1:1 complex salts of alpha amino acids and a metal ion which is either zinc or manganese, having the use-ful feature of being highly body absorbable nutritional supple-ments, the method comprising reacting a water soluble zinc salt or manganese salt with an alpha amino acid in the presence of catalytically effective amount of ferric ion which aids in solubilizing the metal salt while simultaneously enhancing the formation of 1:1 complexes between the selected zinc or manganese salt and the desired alpha amino acid, particularly methionine.
Description
13~501~
. . :
~
,. ''', BACKGROUND OF THE DISCLOSURE
. : , This invention relates to an improvement in the process of making l l zinc and l l manganese complexes with alpha amino acid~, part~cularly methionine In that ense, it represents an improvement over the proce~ses disclosed in commonly owned United States Letters Patents 3,941,818 issued March 2, 1976, entitled ~l~l ZINC METHIONINE COMPLEXES"
and United State~ Letters Patent 3,950,372 issued April 13, 1976, and entitled ~1 1 MANGANESE ALPHA AMINO ACID CC~IPLEXESn. :
Both of the previously issued patents relate to the 1 1 complexed 8alt8 per e, and to general proc-sses for preparing the same The novel s~lt~ have a8 expres~e~ in the earller issued patents, the u-eful --ture~of being highly body absorbable nutritional uppl-ments for both 1~ animals and humans to provide readlly avail~ble sources of zinc ions on the one hand, and mang-ne-e ions on the other hand In the commercial preparation of the~e l l metal amino acid complexes, there have been from~t~ime~to time certain problems in solubilizing the precursor sa1ts and the alpha amino acid, both of which exist ln solid powdered form As a result, even though the salts are theoretically highly soluble in water, the amount of necessary mixing to assure substantial dissolving teven at elevated temperatures) in order to provide the necessary intimate contact for adequate reae~ing between the two to form l l complexes of~ the zinc ~nd/or manganese and the alpha amino;acid is quite excessive ¦ Thus, there has been an inherent problem in the preparation I ~ :, ~' ~
1 technique, both from the standpoint of the very practical problem of adequate dissolving even in hot water, and also the problem of assuring that the product i8 subQtantially all the desired 1:1 complexes.
Accordingly, there has been ~ roal and a continuing need -~
for the di~covery of proce3s improvement~ which allow~ the ready dissolving of ~he in~t~al precur~or reactants or ingredients, and which wlll simultaneously assur- product yield in high amounts of the de~irod 1:1 complexes of the metal ions and the alpha amino salts.
This invention hDs as it~ primary objective the fulfillment of this need ln order that the 1:1 manganese alpha amino acid complexes of United St-to~ Letter- Patent 3,950,372 and the 1:1 zinc alpha amino acid complexe~ of United States Letters Patent 3,941,818, may be prep~red ea8ily without long process delays and in high yield of the desired 1:1 complexes.
For details of desirability and utility of l:l manganese alpha amino acid complexe~, see the previously referred to U.S Patent 3,950,372 which is incorporated hereln by reference. For details of desirability and utility of 1:1 ~inc alpha amino acid complexes, see United States Letters Patent 3,941,818 which is incorporated herein by reference.
The method of accomplish~ng each of the objectives of -~5 I this nvention will become apparent from the detailed decription of the invention which follows hereinafter.
SU~1MARY OF THE INVENTION
l This invention relates to a process improvement which 3~ 1~ -3-1 ~ llo~ increased eAae Df pr-paratlon in high ~lelds of 1 ¦ c plexes of zinc and mnngane3e wlth ~lpha amino acida to ¦
provide in high yield the desired 1:1 complexes in a form which can be readily absorbed biochemically after ingestion by animals and humans to provido adequate and proper dietary levels of zinc ~nd methionine as necessary for proper health, weight gain and dietary balance. The reaction is a straightforward reaction between the respective zinc salt and the respective manganess ~alt and the alpha amino acid, which are both at least partially di~solved in water. It is significantly catalyzed, both from~the standpointof solùb~lD7rlsn of the respective salts and from the standpoint of producing the desired 1:1 complexes between the re~pective zinc ion and manganese ion and the desired alpha amino acid, preferably methionine, by conducting the reactlon in the presence of catalytically effective amount of ferric ~on, preferably in the form of ferric ~ulfate. -~
. - ~ , ~ . ':'.
DETAILED DESC~IPTION OF T~lE INVE~lTION
It is important to note that the respective zinc and manganess compounds which are prepared in accordance with this in~ention are referred to as complexed salts. These salts are to be carefully distinguished from conventional salts such as~ for example, zinc chloride or manganese chloride. 5uch conventional salts such as zinc chloride or manganes~ chloride contain only an electrostatic attraction ¦~
between th~ cation and the anion. The 1:1 complexed salts prepared by this invention differ from conventional salts in --~
~hat while they have an electrostatic attraction bstween the -f ~1 -4-ll ,,"
~ .'.' 1 1 c ion and the ~nion, there io also a coordinltion bond between ~
the cation and the amino moiety of the alpha amino acid. -The preferred alpha amino acid for use in this invention is methionine. From the ~tandpoint of both zinc complex salts and the manganese complex 8alt8, however, it should be understood that other alpha amino acids may be employed as well. Preferably those are es ential alpha amino acids.
Those essenti~l alpha amino acids which are preferred for utilization in forming the 1:1 complex salts of this invention are arginine, hi~tidine, isoleucine, leucine, lysine, methionîne, phenyl~lanine, threonine, tryptophane, and valine. Glycine, while not an essential amino cid, is also a preferred alpha amino acid in that it is readily available --and can be utilized for synthesi~ of the complex salts of this invention. The two mo~t pref-rred natural alpha amino acids are methionine and glycine.
With regard to the preferred zinc methionine complexed salts which are prepared in accordance with the improved process of this invention, they have~the general Eormula:
20 ~ ~ ++
~CH3-S-CH2-CH2-CH-~-OZn lwX ~;
wherein X is an anion and w is an integer equal to the anion-c charge of X. The cation of these complexed salts is represented by the bracketed material in the above formula and represents a 1:1 complex of zinc and methionlne.
Wi~h regard to the manganess alpha amino acid complex salts of ~he present invention, they have the formula:
I LR C ~ O Mn ++~ X
3 0 ¦ N112 W
l -5-~, .
1 3250 1 4 ~: :
1 wherein R i5 an alpha moiety of alpha amino acid, preferably methionine or glycine, X is an anion, and W is an integer equal to the anion charge of X The cat$on of these complexed salts i8 represented by the bracketed material in the above formula and represents a 1:1 complex of manganese and alpha amino acid The proces of preparing the deslr-d zlnc and methionine 1 1 complex salts of the alpha amino aclds~referred to herein, in each instance as the~ -arlier p-tent- mention, ls straightforward and direct Co _ only lt~begin- wlth the use of a water soluble zinc salt and/or o w-ter~-oluble manganese salt, respectively Sultable zlnc solt~ ~hioh c~n be ~-employed are the halides, the sulfates, and the~phosphate6 The desired weight ratio of zinc alt~to methionine is ~
within the range of 1:1 to 2sl, pref-rably 3 2. ~Suitable manganese salts which con be mployed are llkewise halides, sulfates and phosphates. The deslr-d w-ight ratlo of manganese -~
to methionine is 1 1 to 2 1, preferably~4:3 In~each ~
instance, the sulfate salts are~preferr-d from~tbe standpoint of availability and, at least currently-, oost In the general proce~s, these~salts are at least partially water dissolved, preferably at elevated temp-ratures Temperatures within the range of from~abQut 180F~ to about ~-205~ have been found desirable,;most preferably temperatures with the range of 190F to about 205F In actu~al practice, one common tec~nique is to stlr the salt into a water solution while simultaneously injecting steam to elevate the temperature within the desired range In the most preferred embodiment of the present invention ~0 . ' 1 the catalytic ferric ion is next added. It should be under-stood, however, that the catalytic amount of ferric ion can be added both before the addition of the alpha amino acid or after, with before belng modestly preferred.
As previously m~ntioned, it ha~ been di~covered that when the react$on between the water soluble metal salt and the alpha amino acid ~s conductsd in the pre~ence of R
catalytically effective amount of ferric ion, two desirable things occur. In the first in3tance, the dissolving of the salt and the amino acid in the water appears to be significantly enhanced from the standpoint of rapidity and in the second instance, there i5 an increased yield of the desirabl4 1:1 complexes formed. _ It is not known prscisely why the ferric ion catalyzes the process, but it nevertheles~ does~ The ferric ion may be added in the form of any water soluble salt such as ferric chloride, ferric sulfate, ferric phosphate, ferric acetate or any other suitable water ~oluble ferri~c salt.
~he most preferred are ferric chloride and ferric sulfate.
The amount added can be from about 2% to about 10% based upon the dry weight of alpha amino acid, preferably from about 4% to about 8~ based upon the dry weight of alpha amino acid employed. For the most preferred alpha amino acid o~ this invention, methionine, 4% by weight has been ~ound best in experimentation to date. However, it should be understood that any amount within the range from about 2~ up to about 10% by weight of the alpha amino acid will work.
¦ The lower limit expressed herein, i.e., 2~, is about the 3~ ¦ ~inimum quantity needed for any sign~ficant improvement.
_~... I
1 ~he upper level is a practical and economic level, since amounts in excess do not ~eem to add anything except expense.
After the preferred c~talyti~ amount of ferric ion i5 added to the water ~oluble salt of either zinc or manganese, and S mixed therein, the desired alpha amino acid fs then stirred into the reaction mixture ~long with increa~ed injection of steam in order to elevate the temper~ture again to within the desired temperature range.
It is noted in the rcaction proc-~3 that where the ferric ion i8 used, almost immed~ately the solution becomes clear, lumping does not occur-, and in the c~e of zinc methionine complexes, it immediately turns to a clear reddi h brown ~olution. In the c~se of manganese methionine complexes, the reaction immediately turns to a d~istinct clear ~olution of similar color. In both instances, there is no problem of "lumping~ and the re~ction becomes straightforward ;
and direct to the desired lsl complexe .
~fter the re~ction i~ completed, which i8 ordinarily a ~atter of minutes, but may be up to an hour or longer if desired, the product is ready for fini~hing.
If product concentrate is d-sired, it may be spray dried -in each instance. On the other hand, if the product is to be -mixed with a carrier, such as a cereal product, it may be mixed together at varying ratios, put into drying drums, and dry coated on the cereal product.
The following examples are of~ered to further illus-l tr~te the improved process of this invention.
~
'''~"
ll .
(Preparation of 1:1 Z~nc Meth~onine Complexes) Thi3 proces~ prepares in batch form a 1,010 pound batch _ of product. ~
Flve hundred pound~ of water are he~ted to ~ithin the range of frsm 200F. to 205F. by ln~:ecting steam into a batch holding stainle~s steel vessel. Three hundred pounds of reagent grade zlnc sulfate are added to th- ve~ el, while continually ~tirring the same. S~multan-ously lO~ounds of ferric sulfate are added and st-am i9 continuously injected in order to maintain the temperature withln the~range of 200F. to 205F. ~hereafter, 200 poundQ of methionine is ~ -added, whils continuously stirri~g.
Immediately, the reaction product turn~ clear, all 1~ lumping i8 elminated, and the product appears to be a true solution, redd~h brown in color. When lt is roadlly apparent that everything i8 d1ssolved and nothing i~ in suspension, the-product i~ then passed to a spray dryer and spray dried -~
to provide a 1:1 zinc methionine complex. ~
The formation of the 1:1 complex is confirmed by infra-red ana1ysis, titration curve analysis, and quantitative -l analysisO Such was found to be present ln excess of a 90%
i yield of the desired product.
25 ¦ EXAMPLE 2 (Formation of 1:1 Manganese Alpha Amino Acid Complexes) A substantially similar process as used in Example 1 is done with the following changes. In this instance again the ¦1 am~unt of the batch was 1,010 pounds, 500 pounds of water, _g_ , I
I , 1 and 500 pounds of ~olids. In the -olid~, the mangane~e ~alt employed was man~ane~e sulfate, and the ferric catalyst employed was again ferric ~ulfat~. ~he ount of mangane~e sulfate employed wa~ 286 pounds, and the amount of methionine employed was 214 pounds. The ratio of these *as 4:3. The amount of catalyst employed wa~ 10 pounds.
Agaln, it wa~ evident that no lumping occurred, that there was a true solution formed, and that the reaction was nearly instantaneously complete upon stirring with the reactants present. Again, the desired 1:1 manganèso methionine complex was formed in a-yield in excess of 904.
It therefore can be ~een that the invention accomplishes at least all of its ~tated objectives.
. . :
~
,. ''', BACKGROUND OF THE DISCLOSURE
. : , This invention relates to an improvement in the process of making l l zinc and l l manganese complexes with alpha amino acid~, part~cularly methionine In that ense, it represents an improvement over the proce~ses disclosed in commonly owned United States Letters Patents 3,941,818 issued March 2, 1976, entitled ~l~l ZINC METHIONINE COMPLEXES"
and United State~ Letters Patent 3,950,372 issued April 13, 1976, and entitled ~1 1 MANGANESE ALPHA AMINO ACID CC~IPLEXESn. :
Both of the previously issued patents relate to the 1 1 complexed 8alt8 per e, and to general proc-sses for preparing the same The novel s~lt~ have a8 expres~e~ in the earller issued patents, the u-eful --ture~of being highly body absorbable nutritional uppl-ments for both 1~ animals and humans to provide readlly avail~ble sources of zinc ions on the one hand, and mang-ne-e ions on the other hand In the commercial preparation of the~e l l metal amino acid complexes, there have been from~t~ime~to time certain problems in solubilizing the precursor sa1ts and the alpha amino acid, both of which exist ln solid powdered form As a result, even though the salts are theoretically highly soluble in water, the amount of necessary mixing to assure substantial dissolving teven at elevated temperatures) in order to provide the necessary intimate contact for adequate reae~ing between the two to form l l complexes of~ the zinc ~nd/or manganese and the alpha amino;acid is quite excessive ¦ Thus, there has been an inherent problem in the preparation I ~ :, ~' ~
1 technique, both from the standpoint of the very practical problem of adequate dissolving even in hot water, and also the problem of assuring that the product i8 subQtantially all the desired 1:1 complexes.
Accordingly, there has been ~ roal and a continuing need -~
for the di~covery of proce3s improvement~ which allow~ the ready dissolving of ~he in~t~al precur~or reactants or ingredients, and which wlll simultaneously assur- product yield in high amounts of the de~irod 1:1 complexes of the metal ions and the alpha amino salts.
This invention hDs as it~ primary objective the fulfillment of this need ln order that the 1:1 manganese alpha amino acid complexes of United St-to~ Letter- Patent 3,950,372 and the 1:1 zinc alpha amino acid complexe~ of United States Letters Patent 3,941,818, may be prep~red ea8ily without long process delays and in high yield of the desired 1:1 complexes.
For details of desirability and utility of l:l manganese alpha amino acid complexe~, see the previously referred to U.S Patent 3,950,372 which is incorporated hereln by reference. For details of desirability and utility of 1:1 ~inc alpha amino acid complexes, see United States Letters Patent 3,941,818 which is incorporated herein by reference.
The method of accomplish~ng each of the objectives of -~5 I this nvention will become apparent from the detailed decription of the invention which follows hereinafter.
SU~1MARY OF THE INVENTION
l This invention relates to a process improvement which 3~ 1~ -3-1 ~ llo~ increased eAae Df pr-paratlon in high ~lelds of 1 ¦ c plexes of zinc and mnngane3e wlth ~lpha amino acida to ¦
provide in high yield the desired 1:1 complexes in a form which can be readily absorbed biochemically after ingestion by animals and humans to provido adequate and proper dietary levels of zinc ~nd methionine as necessary for proper health, weight gain and dietary balance. The reaction is a straightforward reaction between the respective zinc salt and the respective manganess ~alt and the alpha amino acid, which are both at least partially di~solved in water. It is significantly catalyzed, both from~the standpointof solùb~lD7rlsn of the respective salts and from the standpoint of producing the desired 1:1 complexes between the re~pective zinc ion and manganese ion and the desired alpha amino acid, preferably methionine, by conducting the reactlon in the presence of catalytically effective amount of ferric ~on, preferably in the form of ferric ~ulfate. -~
. - ~ , ~ . ':'.
DETAILED DESC~IPTION OF T~lE INVE~lTION
It is important to note that the respective zinc and manganess compounds which are prepared in accordance with this in~ention are referred to as complexed salts. These salts are to be carefully distinguished from conventional salts such as~ for example, zinc chloride or manganese chloride. 5uch conventional salts such as zinc chloride or manganes~ chloride contain only an electrostatic attraction ¦~
between th~ cation and the anion. The 1:1 complexed salts prepared by this invention differ from conventional salts in --~
~hat while they have an electrostatic attraction bstween the -f ~1 -4-ll ,,"
~ .'.' 1 1 c ion and the ~nion, there io also a coordinltion bond between ~
the cation and the amino moiety of the alpha amino acid. -The preferred alpha amino acid for use in this invention is methionine. From the ~tandpoint of both zinc complex salts and the manganese complex 8alt8, however, it should be understood that other alpha amino acids may be employed as well. Preferably those are es ential alpha amino acids.
Those essenti~l alpha amino acids which are preferred for utilization in forming the 1:1 complex salts of this invention are arginine, hi~tidine, isoleucine, leucine, lysine, methionîne, phenyl~lanine, threonine, tryptophane, and valine. Glycine, while not an essential amino cid, is also a preferred alpha amino acid in that it is readily available --and can be utilized for synthesi~ of the complex salts of this invention. The two mo~t pref-rred natural alpha amino acids are methionine and glycine.
With regard to the preferred zinc methionine complexed salts which are prepared in accordance with the improved process of this invention, they have~the general Eormula:
20 ~ ~ ++
~CH3-S-CH2-CH2-CH-~-OZn lwX ~;
wherein X is an anion and w is an integer equal to the anion-c charge of X. The cation of these complexed salts is represented by the bracketed material in the above formula and represents a 1:1 complex of zinc and methionlne.
Wi~h regard to the manganess alpha amino acid complex salts of ~he present invention, they have the formula:
I LR C ~ O Mn ++~ X
3 0 ¦ N112 W
l -5-~, .
1 3250 1 4 ~: :
1 wherein R i5 an alpha moiety of alpha amino acid, preferably methionine or glycine, X is an anion, and W is an integer equal to the anion charge of X The cat$on of these complexed salts i8 represented by the bracketed material in the above formula and represents a 1:1 complex of manganese and alpha amino acid The proces of preparing the deslr-d zlnc and methionine 1 1 complex salts of the alpha amino aclds~referred to herein, in each instance as the~ -arlier p-tent- mention, ls straightforward and direct Co _ only lt~begin- wlth the use of a water soluble zinc salt and/or o w-ter~-oluble manganese salt, respectively Sultable zlnc solt~ ~hioh c~n be ~-employed are the halides, the sulfates, and the~phosphate6 The desired weight ratio of zinc alt~to methionine is ~
within the range of 1:1 to 2sl, pref-rably 3 2. ~Suitable manganese salts which con be mployed are llkewise halides, sulfates and phosphates. The deslr-d w-ight ratlo of manganese -~
to methionine is 1 1 to 2 1, preferably~4:3 In~each ~
instance, the sulfate salts are~preferr-d from~tbe standpoint of availability and, at least currently-, oost In the general proce~s, these~salts are at least partially water dissolved, preferably at elevated temp-ratures Temperatures within the range of from~abQut 180F~ to about ~-205~ have been found desirable,;most preferably temperatures with the range of 190F to about 205F In actu~al practice, one common tec~nique is to stlr the salt into a water solution while simultaneously injecting steam to elevate the temperature within the desired range In the most preferred embodiment of the present invention ~0 . ' 1 the catalytic ferric ion is next added. It should be under-stood, however, that the catalytic amount of ferric ion can be added both before the addition of the alpha amino acid or after, with before belng modestly preferred.
As previously m~ntioned, it ha~ been di~covered that when the react$on between the water soluble metal salt and the alpha amino acid ~s conductsd in the pre~ence of R
catalytically effective amount of ferric ion, two desirable things occur. In the first in3tance, the dissolving of the salt and the amino acid in the water appears to be significantly enhanced from the standpoint of rapidity and in the second instance, there i5 an increased yield of the desirabl4 1:1 complexes formed. _ It is not known prscisely why the ferric ion catalyzes the process, but it nevertheles~ does~ The ferric ion may be added in the form of any water soluble salt such as ferric chloride, ferric sulfate, ferric phosphate, ferric acetate or any other suitable water ~oluble ferri~c salt.
~he most preferred are ferric chloride and ferric sulfate.
The amount added can be from about 2% to about 10% based upon the dry weight of alpha amino acid, preferably from about 4% to about 8~ based upon the dry weight of alpha amino acid employed. For the most preferred alpha amino acid o~ this invention, methionine, 4% by weight has been ~ound best in experimentation to date. However, it should be understood that any amount within the range from about 2~ up to about 10% by weight of the alpha amino acid will work.
¦ The lower limit expressed herein, i.e., 2~, is about the 3~ ¦ ~inimum quantity needed for any sign~ficant improvement.
_~... I
1 ~he upper level is a practical and economic level, since amounts in excess do not ~eem to add anything except expense.
After the preferred c~talyti~ amount of ferric ion i5 added to the water ~oluble salt of either zinc or manganese, and S mixed therein, the desired alpha amino acid fs then stirred into the reaction mixture ~long with increa~ed injection of steam in order to elevate the temper~ture again to within the desired temperature range.
It is noted in the rcaction proc-~3 that where the ferric ion i8 used, almost immed~ately the solution becomes clear, lumping does not occur-, and in the c~e of zinc methionine complexes, it immediately turns to a clear reddi h brown ~olution. In the c~se of manganese methionine complexes, the reaction immediately turns to a d~istinct clear ~olution of similar color. In both instances, there is no problem of "lumping~ and the re~ction becomes straightforward ;
and direct to the desired lsl complexe .
~fter the re~ction i~ completed, which i8 ordinarily a ~atter of minutes, but may be up to an hour or longer if desired, the product is ready for fini~hing.
If product concentrate is d-sired, it may be spray dried -in each instance. On the other hand, if the product is to be -mixed with a carrier, such as a cereal product, it may be mixed together at varying ratios, put into drying drums, and dry coated on the cereal product.
The following examples are of~ered to further illus-l tr~te the improved process of this invention.
~
'''~"
ll .
(Preparation of 1:1 Z~nc Meth~onine Complexes) Thi3 proces~ prepares in batch form a 1,010 pound batch _ of product. ~
Flve hundred pound~ of water are he~ted to ~ithin the range of frsm 200F. to 205F. by ln~:ecting steam into a batch holding stainle~s steel vessel. Three hundred pounds of reagent grade zlnc sulfate are added to th- ve~ el, while continually ~tirring the same. S~multan-ously lO~ounds of ferric sulfate are added and st-am i9 continuously injected in order to maintain the temperature withln the~range of 200F. to 205F. ~hereafter, 200 poundQ of methionine is ~ -added, whils continuously stirri~g.
Immediately, the reaction product turn~ clear, all 1~ lumping i8 elminated, and the product appears to be a true solution, redd~h brown in color. When lt is roadlly apparent that everything i8 d1ssolved and nothing i~ in suspension, the-product i~ then passed to a spray dryer and spray dried -~
to provide a 1:1 zinc methionine complex. ~
The formation of the 1:1 complex is confirmed by infra-red ana1ysis, titration curve analysis, and quantitative -l analysisO Such was found to be present ln excess of a 90%
i yield of the desired product.
25 ¦ EXAMPLE 2 (Formation of 1:1 Manganese Alpha Amino Acid Complexes) A substantially similar process as used in Example 1 is done with the following changes. In this instance again the ¦1 am~unt of the batch was 1,010 pounds, 500 pounds of water, _g_ , I
I , 1 and 500 pounds of ~olids. In the -olid~, the mangane~e ~alt employed was man~ane~e sulfate, and the ferric catalyst employed was again ferric ~ulfat~. ~he ount of mangane~e sulfate employed wa~ 286 pounds, and the amount of methionine employed was 214 pounds. The ratio of these *as 4:3. The amount of catalyst employed wa~ 10 pounds.
Agaln, it wa~ evident that no lumping occurred, that there was a true solution formed, and that the reaction was nearly instantaneously complete upon stirring with the reactants present. Again, the desired 1:1 manganèso methionine complex was formed in a-yield in excess of 904.
It therefore can be ~een that the invention accomplishes at least all of its ~tated objectives.
Claims
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1.
A method of making 1:1 complex salts of alpha amino acids and a metal ion selected from the group consisting of zinc and manganese, said method comprising:
reacting a water soluble metal salt selected from the group consisting of zinc salts and manganese salts which are at least partially water dissolved, with an alpha amino acid, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
2.
The method of claim 1 wherein the alpha amino acid is methionine.
3.
The method of claim 2 wherein the metal salt is a zinc salt.
4.
The method of claim 3 wherein the zinc salt is zinc sulfate.
5.
The method of claim 2 wherein the metal salt is a manganese salt.
6.
The method of claim 5 wherein the manganese salt is manganese sulfate.
7.
The method of claim 3 wherein the source of ferric ion is ferric sulfate.
8.
The method of claim 6 wherein the source of ferric ion is ferric sulfate.
9.
The method of claim 1 wherein at least the partially dissolved salt solution of a metal ion selected from the group consisting of zinc salts and manganese salts is initially heated to a temperature of from 180°F. to about 205°F.
group, 10.
The method of claim 9 wherein the initial heating is to a temperature of from 190°F. to about 205°F.
11.
The method of claim 9 wherein the reactants are continually mixed during the addition of said alpha amino acid.
12, The method of claim 4 wherein the weight ratio of zinc sulfate to methionine is within the range of from 1:1 to 2:1.
13.
The method of claim 12 wherein the weight ratio of zinc sulfate to methionine is about 3:2.
14.
The method of claim 6 wherein the weight ratio of manganese sulfate to methonine is within the range of from 1:1 to 2:1.
15.
The method of claim 14 wherein the weight ratio of manganese sulfate to methionine is about 4:3.
16.
A method of making 1:1 complexes of zinc and methionine, said method comprising:
reacting a water soluble zinc salt which is at least partially water dissolved with methionine, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
17.
The process of claim 16 wherein said ferric ion is provided by ferric sulfate.
18.
A method of making 1:1 complexes of alpha amino acids and manganese, said method comprising:
reacting water soluble manganese salt with an alpha amino acid, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
19.
The reaction of claim 18 wherein said manganese salt is manganese sulfate.
1.
A method of making 1:1 complex salts of alpha amino acids and a metal ion selected from the group consisting of zinc and manganese, said method comprising:
reacting a water soluble metal salt selected from the group consisting of zinc salts and manganese salts which are at least partially water dissolved, with an alpha amino acid, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
2.
The method of claim 1 wherein the alpha amino acid is methionine.
3.
The method of claim 2 wherein the metal salt is a zinc salt.
4.
The method of claim 3 wherein the zinc salt is zinc sulfate.
5.
The method of claim 2 wherein the metal salt is a manganese salt.
6.
The method of claim 5 wherein the manganese salt is manganese sulfate.
7.
The method of claim 3 wherein the source of ferric ion is ferric sulfate.
8.
The method of claim 6 wherein the source of ferric ion is ferric sulfate.
9.
The method of claim 1 wherein at least the partially dissolved salt solution of a metal ion selected from the group consisting of zinc salts and manganese salts is initially heated to a temperature of from 180°F. to about 205°F.
group, 10.
The method of claim 9 wherein the initial heating is to a temperature of from 190°F. to about 205°F.
11.
The method of claim 9 wherein the reactants are continually mixed during the addition of said alpha amino acid.
12, The method of claim 4 wherein the weight ratio of zinc sulfate to methionine is within the range of from 1:1 to 2:1.
13.
The method of claim 12 wherein the weight ratio of zinc sulfate to methionine is about 3:2.
14.
The method of claim 6 wherein the weight ratio of manganese sulfate to methonine is within the range of from 1:1 to 2:1.
15.
The method of claim 14 wherein the weight ratio of manganese sulfate to methionine is about 4:3.
16.
A method of making 1:1 complexes of zinc and methionine, said method comprising:
reacting a water soluble zinc salt which is at least partially water dissolved with methionine, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
17.
The process of claim 16 wherein said ferric ion is provided by ferric sulfate.
18.
A method of making 1:1 complexes of alpha amino acids and manganese, said method comprising:
reacting water soluble manganese salt with an alpha amino acid, said reaction occurring in the presence of a 1:1 complexing catalytically effective amount of ferric ion.
19.
The reaction of claim 18 wherein said manganese salt is manganese sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000616315A CA1325014C (en) | 1987-08-31 | 1992-02-19 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US091,391 | 1987-08-31 | ||
| US07/091,391 US4764633A (en) | 1987-08-31 | 1987-08-31 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
| CA000563806A CA1301772C (en) | 1987-08-31 | 1988-04-11 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
| CA000616315A CA1325014C (en) | 1987-08-31 | 1992-02-19 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000563806A Division CA1301772C (en) | 1987-08-31 | 1988-04-11 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325014C true CA1325014C (en) | 1993-12-07 |
Family
ID=25671831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000616315A Expired - Lifetime CA1325014C (en) | 1987-08-31 | 1992-02-19 | Ferric ion catalyzed complexation of zinc and/or manganese with alpha amino acids |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1325014C (en) |
-
1992
- 1992-02-19 CA CA000616315A patent/CA1325014C/en not_active Expired - Lifetime
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