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Patented Sept. 2, 1947 ‘
2,426,634 ~
UNITED ‘STATES’ PATENT ‘
2,426,634
_
COMPOSITION AND METHOD-
I
OFFICE.‘
‘
Daniel Melnlck, New York, N. Y., assignor to 0011- ;
tinental Foods, Inc., Hoboken, N. J., a corpora- _
.
~
tion of Illinois '
No Drawing; - Application May 29, 1943', ‘ ~
.
v Serial naesaose
A»
9 Claims. '(CL' 99-424)
_ This invention relates to treatment of concen
trated food preparations and the like to inhibit
changes therein producing unsightly discolora-g
tion and decomposition thereof, and is more spe
2
light yellow in color while the latter was brown
in color with numerous “islands" of brown-black
pigment. It was de?nitely established that the
coloring did notl-resultu'from bacterial action or
any other organicgrowth, and that the dark
ci?cally concerned witl1_.food concentrates and
the like containing carbohydrates, particularly
ened mix was ‘still’ suitable for use as a food; but
the sugars, and amino acids, particularlydicar-j
the pigmentation, nevertheless, was such as to
boxylic amino acids- and salts thereof typi?ed by _' render the mix less appetizing, and may have
monosodium
glutamate.
'
»
__
.
,
' reduced vitamin value.
'
In the compounding of ,many ‘concentrated 10
It is accordingly a primary object of the pres
foods, constituents of' various‘ kinds are blended
ent invention to remove or correct the causes of
together to achieve a ?nished product having a
the said pigmentation and especially to provide
desired ?avor. Some of these constituents may
means for the inhibition and control of the
be relatively pure compounds or, at least sub
concomitant chemical reactions.
stances of 'simple nature as compared with the 15
It is a further object oi.’ the invention to im
corresponding components of foods prepared for
prove the keeping qualities of concentrated food
consumption directly from natural raw food ma
mixes containing amino acid material and car
terials. As exemplary of such concentrated food
bohydrate material without impairment of ?avor,
compositions, commonly referred to as “mixes,"
reference is made to a soup mix consisting of a
plastic mass adapted to form the stock of a
?nished soup, the mix being usually associated
in packaging with a suitable proportion of
noodles, dehydrated vegetables, or the like. In
vitamin potency or capacity for simple and rapid
dehydration.
Although darkening of food products has been
observed and known for a very long time, its
causes have not been generally recognized. In
some cases, it has been shown to be due to en
a typical soup mix this plastic composition was 25 zymic action; in some cases, it has been attrib
made up of the following ingredients in the pro
portions speci?ed:
Per cent
Dextrose _______________________________ __
Monosodium glutamate _________________ __
15
uted to oxidation or caramelization occurring
during drying operations; in other cases, it has
been reported that darkening is due to reactions
of substances in the food with metal salts in the
water with which the food is mixed or treated;
and in still other cases, it appears that darken
Vegetable protein hydrolysate ____________ __
2
Fats ___________________________________ __
20
ing is due to a reaction between a sugar and an
31
amino acid. The product of the latter reaction
has been produced experimentally, and com
Salt, spices, and other minor ?avoring ingre
dients ________________________________ .._
The above soup mix is selected for the purpose 35 parative studies indicate that this experimentally
produced pigment corresponds to that normally
of exempli?cation of the invention and with a
formed in the soup mix and like dehydrated food
view tov instructing others skilled in the art so
products during storage.
that they may more readily and fully understand
In all cases where a pigment was produced in
the principles of this invention and the practical
application thereof and thus may be enabled to 40 the experimental samples, said samples contained
both an amino acid material and a carbohydrate
use the inventionin numerous different kinds of
material with at least traces of water and the
food and with numerous modi?cations, each as
reaction occurred in the presence of oxygen.
may be best suited to the requirements of a
particular use.
These I have determined to be the constituents
It‘ has been found that the soup mix described 45 necessary to the reaction. The designations
above in common with other compositions con
“amino acid material" and “carbohydrate mate
taining ingredients of the same general nature
\rial” are used advisedly. The former term in
as the amino acid materials and carbohydrates
cludes salts and other compositions which may be
included in the soup mix, tend to change color
derived from amino acids wherein the amino
and especially to form isolated black spots or 50 acid structure is present. Similarly, “carbohy
“islands” or a general dark brown pigmentation
drate material” is employed to designate compo
of the entire mass. Comparison was made be
sitions having the general basic structure and
tween a relatively ‘fresh soup mix (about one
showing the general properties of sugars or such
month old) of the above type and a similar mix
as to be converted to sugars in some degree dur
about ten months old. The former was a paste, 55 ing processing or storage. The manner in which
3
of adjusting the pH to not substantially higher
these terms are used will also be apparent from
than 4.5. Where the medium, 8. g. in the ‘soup
the further discussion of the invention herein.
The darkening noted above is clearly non-en
zymic in nature, although insome instances it
mix, is more acid than pH 4.5, substantial'pig
mentation of the type with‘. which we are here
concerned does not occur even though- composi
may-involvef‘enzymic conversion offstarch to
more highlv reactive sugars.
tions including highly reactive amino acid mate
rials and highly reactive carbohydrate materials
The pigment is
clearly different from that produced in foods by
are stored for long periods of time.
active enzymes.
In many food compositions, pH below 4.5 is
distastefully sour. Soups prepared from concen
Referring back to the samples which were
stored under controlled conditions designed to
hasten the development of the undesirable pig- > -
mentation, certain additional generalizations can
trated mixes of this acidity were found to be so
' 1 souras to mask‘the agreeable ?avor intended in
the mix described above. In instances where the
sour taste is undesirable, means are provided by
be made on the basis of studies conducted. In
the speci?c compositions noted, monosodium
glutamate and dextrose are among the most- ac
tive amino acid materials and carbohydrate ma
15' '
terials respectively which have been studied. 'In
general, alkaline derivatives of the dicarboxylic
the present invention to neutralize the acid to
a suitable pH (for example about 6.6 for soups).
Sodium bicarbonate: or other suitable base may
advantageously be included in a potentially active
form
as by inclusion physically while? isolated
7 mono amino acids and the sugars seem to be es
chemically
in accordance with the above descrip
pecially reactive. Further, it appears that the 20 tion for chemically
isolating the potentially’re
more alkaline the amino acid derivatives are, the
active sugars and amino acid material. 'In'gen
more reactive they are; e. g. the disodium salts
eral, the acid used should‘ be a solid and both acid
are more reactive than the monosodium salts and
and base must be non-toxic where'the composi
the latter more than the monoacid amides. Sim
- ilarly the simpler carbohydrates, especially the 25 tion is intended for consumption as food.’ _Inor
ganic acids may be used,‘for example, metaphos
mono-and di-saccharides, react more readily with
phoric
acid and sodium bisulfate are suitable but
amino acid materials to‘ form pigmented bodies.
in preparing foods the organic acids’ are found
Referring again to the speci?c studies con
to be better suited to the purpose.
ducted on the soup mix speci?ed above; pigment
Thus, to the soup mix described above may be
is formed more slowly and seemingly to a less 30 added suf?cient dry citric acid to provide 1 to 2%
extent in the absence of monosodium glutamate
of that agent in the ?nished mix. An amount of
by reaction of the vegetable protein hydrolysate.
sodium bicarbonate to give the desired taste is
Likewise, simple polysaccharides yield substan
added as granules coated with a suitable isolat
tial pigmentation with amino acid materials but
ing medium such as ethyl cellulose. Incorpora
at a slower rate than the simple sugars, while the 35 tion or mixing of the base in or with the dry
more complex starches react so slowly with most
noodles is also satisfactory. and in- such case the
amino acids and the like as to render the pig
plastic mix of other ingredients may be isolated
mentation negligible over normal storage periods.
by coating with fat or other inert food material.
The invention contemplates inhibition of pig
With citric acid, I have found that 1.08 grams of
mentation in compositions of the type described 40 anhydrous sodium bicarbonate is suitable for
above by inhibiting the reaction between amino
overcoming the objectionable acid taste of 1
acid materials and carbohydrate materials. In
gram of added citric acid, used as the crystal
preferred embodiments of the invention, the re
line monohydrate. Similarly, 0.9% citric acid
actants of one type are isolated from the react
with 12.5% monosodium glutamate and 2.5% di
ants of the other type and/or the mass is ren 45 sodium glutamate in isolated form makes a suit
dered sufiiciently acid to inhibit the undesired
able stable soup mix. Good results are also ob-.
pigmentation reaction.
tained from use of gutamic acid and disodium
For example, in the soup mix’described above, '
glutamate, each in quantity equivalent to 7.5%
either the dextrose or the two amino acid mate
monosodium glutamate, the disodium glutamate
rials may be isolated from the remainder of the 50 being isolated in accordance with this invention.
mass. The material to be isolated may be en
Good results have also been obtained by using
closed in sheaths of a suitable substance such
‘glutamic acid instead of the monosodium salt in
as methyl or ethyl cellulose, or fat or various
any desired proportions, with a suitable neutral
combinations of these, or other materials which
izing agent, e. g. sodium carbonate or bicarbonate
will readily dissolve or disperse when the mass is 55
in isolated form.
mixed with hot water or heated after dilution
Both ethyl cellulose and methyl cellulose have
with water. Aconvenient expedient is to enclose
been used with satisfactory results in preparing
isolated neutralizing agents to impart a palat
able pH to stabilized soup mix having a pH be
mainder of the ingredients described as making 60 low 4.5. Ordinary ‘sodium bicarbonate of com
up the typical soup mix. In general the choice
merce was mixed with a solution of 50 grams of
of isolating media and isolated reactants should
ethyl cellulose in 500 cc. of 95% ethyl alcohol,
be based on consideration of relative reactivities
total of 100 grams of sodium bicarbonate being
and anticipated maximum storage period.
or mix one type of" reactant in or with the dry
‘ noodles packed with the mixcontaining the re
used.
The alcohol was then removed by heating ‘
By utilization of the invention herein disclosed, 05 on a steam bath and the coated base ground to a
powder (approximately 80 mesh). It was deter
centrated soup mixes, and a wide variety of other
it is possible to prepare compositions such as con
dehydrated » food preparations containing pig
ment-forming ingredients, which are very stable
over normal or abnormal storage periods. As an 70
mined that v1.4 grams of the coated salt are equiv
alent to 1 gram of the salt before coating. Titra
tion with hydrochloric acid indicates that the
sodium bicarbonate is released slowly when the
coated material is suspended in water at room
temperature, or at refrigeration temperatures in
the neighborhood of 5° C. for example, at 5° (7.,
su?icient to effect ionization it will have the-e?‘ect 75 about one hour is required for complete extrac
alternative, or more advantageously in combina
tion with such isolation, control of darkening
over long storage periods is achieved by addition
of an acid such that, in the presence of water
8,490,884
8
tion of the salt in acid solution. On the other
hand, at 100' 0., the temperature at which a soup
is prepared from the soup mix, release of sodium
bicarbonate is almost instantaneous.
,
The soup mixes, embodying my invention as
described above, keep well under all expected
conditions'of storage and shipment. Even under
arti?cially servere tests they retain well their
color and quality. Thus, storing at an elevated
6
invention liberate the isolated hsredient only
very slowly in water at room temperatures or
under refrigeration, whereas at 100' C. this liber
ation of the base occurs imtantaneously. when
the monosodium glutamate is used as the base
to be segregated, a simple coating with the hy
drogenated fat suinces, since the pH of this salt
is such that it does not ail'ect other fat-soluble
reactants, such as spices.
,
temperature a commercial soup mix of the type 10
Many other types of concentrated foods than
described above and a similar soup mix to which‘
the soup mixes chosen above as examples are
had been added 1% citric acid and coated sodi
subject to darkening or decomposition and can
um bicarbonate equivalent to 1.08% NaHCOa.
be protected against such deterioration by my
after 16 hours storage at 55° (3., showed general
invention. Dehydrated vegetables have been ob
discoloration and dark brown "islands” in the 15 served to show the sugar amino acid reaction.
unstabilized soup mix, whereas the soup mix con
As an example of this, dehydrated tomatoes
taining cirtric acid suifered only very slight gen
which have been observed by chemical and physi
eralized browning not noticeable upon casual
cal studies to show this sugar amino acid reaction,
inspection. Upon preparing a soup from the sta
have been effectively protected against brown
bilized soup mix, it was found to be of good taste, 20 ing by addition of citric acid in an uncoated form
comparable in every respect'to the soup from
and a base, for example, sodium bicarbonate in
freshly prepared soup mix.
the form of coated pellicles.
Under similar rigorous conditions of test, using
In some cases, it may be desirable for the pres
glutamic acid as the acid Preserving agent and
ervation of unstable nutrients to maintain a sub
disodium glutamate as the neutralizing agent, 25 stantial part of the dehydrated composition at a
in amounts such that together they are equiv
particular pH which isgmore alkaline than that
alent to the monosodium glutamate of the stand
in which the food is customarily consumed. It is
ard mix described above (equivalent to 5% mono
then necessary to add an acid material to such in
sodium glutamate), the mix was found to with‘
gredients just before consumption. This acid
stand successfully the high temperature storage. 30 ingredient may be isolated according to my pres
In another case, the monosodium glutamate was
ent invention, e. g., as pellicles coated by any of
reduced by 5.0 and equivalent amounts of di
the procedures described above, and thus isolated,
sodium glutamate and glutamic acid were added,
may be mixed with other ingredients in the same
2.5% of each were used. In each instance, the
packages during storage, so that it is readily
disodium salt was previously coated with ethyl 35 available for decreasing the pH to one compatible
cellulose in . the manner described in connection
with good taste when the mix is reconstituted for
consumption,
with sodium bicarbonate. Both these modi?ed
mixes.and a sample of the standard mix were
Although in the foregoing speci?cation I have
stored in a humid atmosphere 18 hours at 55° 0.,
given various examples of my invention and have
followed by 24 hours at 37° C. The control mix 40 suggested certain modifications and alternatives,
showed general discoloration of considerable ex
these are not intended to be exhaustive nor lim
tent and dark brown “islands”. Both stabilized
iting of my invention, but on the contrary are
mixes suii'ered only negligible discoloration.
selected and presented with a view to illustrating
It has also been found advantageous to coat
.and explaining the invention, the principles
the alkaline ingredient, e. g., individual granules 45 thereof and the best manner of applying it in
of disodium glutamate, with a highly hydro
practical use in order that others skilled in the
genated edible fat which remains solid under
art may be enabled to practice the invention and
all conditions of practical storage. If the mix
apply it under various circumstances and in var
contains fat-soluble reactants, e. g. spices, which
ious ways, and with modi?cations, each as may
are incompatible with the base, it is desirable 50 be best suited to the conditions of a particular
to add another coating of a water soluble ma
terial such as sugar or gelatin over the fat,
and to assure protection of this layer against
the darkening reaction it may contain citric or
. glutamic or other suitable acid.
use.
I claim:
~
1. A food concentrate composition comprising
a carbohydrate and an amino acid material which
Soup mixes of 55 can react therewith to form dark pigment, with
the type described above are effectively protected
su?lcient acid to maintain said composition at a
against development of dark pigment when the
pH less than 4.5, and an alkaline edible substance
glutamate content of the mix is one-half in the
in proportion su?lcient to react with said acid to
form of glutamic acid distributed, without any
give a palatable product of a pH substantially
coating, in the mix and one-half in the form of 60 above 4.5, and an edible coating which segregates
disodium glutamate isolated by a coating of hy
said alkaline substance from the other compo
drogenated fat, or the latter with an additional
nents under storage conditions and which dis
coating of sugar or gelatin. The addition of some
integrates in boiling water, whereby such forma
of the free glutamic acid in the ?nal coating
tion
of dark pigment is inhibited without destroy
65
insures absolute segregation of the enclosed al
ing
the
palatable quality of the edible product
kaline material from the other materials in the
thus prepared from said ‘composition.
mix. It is important to point out that by my in
2. A packaged food concentrate composition
vention I am able to achieve the desired results
comprising a carbohydrate and an amino acid
by physical form and only minor chemical modi
ilcation of the normal constituents of the mix 70 material which can react therewith to form dark
pigment, with sufficient acid to maintain said
and without adding any essentially foreign in
carbohydrate amino acid material at a pH less
gredients in the mix, and without a?'ecting the
relationship of one ingredient to another in the
than 4.5, and an alkaline edible substance in
re-constituted soup. It is important also that,
proportion sufficient to react with said acid to
in all these examples, the material embodying my 75 give a palatable product of a pH substantially
2,420,034
‘above 4.5, and an edible coating segregating said
alkaline substance from the carbohydrate amino
acid mixture under storage conditions, but
adapted to release the alkaline substance into said ‘
mixture by a treatment incident to the prepara- 5
tion vof the composition for serving, whereby such
formation of dark pigment is inhibited without
destroying the palatable character of the edible
product thus prepared from said composition.
edible product thus prepared from said composi
tionf
'
" ‘
6. A food composition as de?ned in ‘claim 5
wherein the_coating consists essentially of methyl
cellulose.‘
-
.
'
.
‘
7. A food composition as de?ned in claim 5
wherein the coating consists essentially of ethyl
cellulose.
'
> 8. A food composition as de?ned in claim 4
3. A food composition comprising a sugar and . 10 wherein the coating consists essentially of a
normally solid fat.
9. A food composition comprising monosodium
glutamate and a vcarbohydrate which can react
therewith to form dark pigment, and su?lcient
cient to react with said acid to give a palatable 15 acid to maintain said composition at a pH less
than 4.5, and an alkaline substance in proportion
product of a pH substantially above 4.5, and an
an amino acid material which can react there
with to form dark pigment, with suf?cient acid
to maintain 'said composition at a pH less than
4.5, and an alkaline substance in proportion su?l
sufficient to react with said acid to give a palatable
product of a pH substantially above 4.5, and an
edible coating on said alkaline substance which,
substance from the other components, but which
- disintegrates in boiling water, whereby such éo under storage conditions, segregates said alkaline
substance from the other components but which
' formation of dark pigment is inhibited without
disintegrates in boiling water, whereby the forma
destroying the palatable character of the edible .
tion of dark pigment is inhibited without destroy
productthus formed from said composition.
'
edible coating on said alkaline substance which‘
under storage conditions segregates said alkaline
ing the palatable character of the edible product
4. A food composition comprising free glutamic
acid, a carbohydrate which can react therewith 25' thus prepared from said composition.
to form dark pigments, disodium glutamate and
DANIEL MELNICK.
a coating on said disodium glutamate of an edible
material which under storage conditions segre
gates said glutamate from the other components,
but which disintegrates in boiling water, whereby 30
such formation of dark pigment is inhibited with
out destroying the palatable character of the
REFERENCES CITED
The following references are of record in the
?le of this patent:
'
' 5. A food composition‘ comprising free glutamic‘ 35
Number
Name
2,278,466
acid, a carbohydrate which can react therewith to
1,829,431
form dark pigment and disodium glutamate, and
1,286,904
1,680,865
a coating on said disodium glutamate of a cellulose
'
UNITED STATES PATENTS '
edible product thus prepared from said composi
tion.
,
ether, which under storage conditions segregates
the disodium glutamate from the glutamic acid 40
Number
and which disintegrates in boiling water, whereby
13,723
such formation of dark pigment is inhibited with
out destroying the palatable character of the
Date
'
Musher __________ __ Apr. 7, 1942
‘
Allen ____________ __' Oct. 27, 1931 -
Atkinson ________ __ ‘Dec. 10, 1918'
Fujii ____________ .._ Aug. 14, 1928
FOREIGN PATENTS
Country
Date
Great Britain _____ Sept. 26, 1907