U.S. patent number RE29,682 [Application Number 05/498,298] was granted by the patent office on 1978-06-27 for low calorie dry sweetener composition.
This patent grant is currently assigned to Alberto-Culver Company. Invention is credited to John A. Cella, William H. Schmitt.
United States Patent |
RE29,682 |
Cella , et al. |
June 27, 1978 |
Low calorie dry sweetener composition
Abstract
Pulverulent free-flowing water-soluble low calorie sweetener
compositions having the general appearance of sucrose are produced
by preparing a strong aqueous solution or slurry of an
aspartyl-phenylalanine methyl ester sweetener at a relatively low
temperature, admixing therewith a heated aqueous starch hydrolysate
having a D.E. of zero to 20, and promptly thereafter, feeding the
mixture to the preheater of a spray drier and thereupon spray
drying said mixture to provide an expanded dry pulverulent
composition containing a low moisture content.
Inventors: |
Cella; John A. (Carmel, IN),
Schmitt; William H. (Brandford, CT) |
Assignee: |
Alberto-Culver Company (Melrose
Park, IL)
|
Family
ID: |
22204368 |
Appl.
No.: |
05/498,298 |
Filed: |
August 19, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
087303 |
Nov 5, 1970 |
03753739 |
Aug 21, 1973 |
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Current U.S.
Class: |
426/548;
426/804 |
Current CPC
Class: |
A23L
27/32 (20160801) |
Current International
Class: |
A23L
1/236 (20060101); A23L 001/26 () |
Field of
Search: |
;426/215,417,380,548,804 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Jones; Raymond N.
Attorney, Agent or Firm: Wallenstein, Spangenberg, Hattis
& Strampel
Claims
We claim:
1. A method of preparing a dry pulverulent low calorie sweetener
composition containing an aspartyl dipeptide lower alkyl ester of
the formula ##STR3## wherein X is selected from the group of
radicals consisting of ##STR4## and
R being a member of the group consisting of hydrogen and a lower
alkyl radical, m an integer selected from the group consisting of 0
and 2 and n a positive integer less that three, which comprises
a. preparing an aqueous starch hydrolysate solution having a D.E.
up to 20 and having a temperature of about 30.degree. to about
80.degree. C,
b. preparing a substantially concentrated aqueous solution or
slurry of said ester having a temperature in the range up to about
40.degree. C,
c. admixing a minor proportion of the b. solution or slurry with a
major proportion of the a. solution, and
d. promptly drying the c. mixture to provide a dry pulverulent
composition containing from 0.5 to 10 percent, by weight, of said
ester, and not more than about 4 percent moisture.
2. A method of preparing a dry pulverulent low calorie sweetener
composition containing an aspartyl dipeptide lower alkyl ester of
the formula ##STR5## wherein X is selected from the group of
radicals consisting of ##STR6## and
R being a member of the group consisting of hydrogen and a lower
alkyl radical, m an integer selected from the group consisting of 0
and 2 and n a positive integer less than three, which comprises
a. preparing an aqueous starch hydrolysate having a D.E. up to 20
and having a temperature of about 30.degree. to about 80.degree.
C,
b. preparing a substantially concentrated aqueous solution or
slurry of said ester having a temperature not exceeding about
40.degree. C,
c. admixing a minor proportion of the b. solution or slurry with a
major proportion of the a. solution, said minor proportion being in
an amount sufficient to provide in the final product from 0.5 to 10
percent, by weight,
d. promptly feeding the c. mixture to a preheater of a spray dryer
and thereupon spray drying said c. mixture to provide a dry
pulverulent composition containing not more than about 4 percent
moisture.
3. The method of claim 2 in which the starch hydrolysate is a
sorghum starch hydrolysate having a D.E. in the range up to about
12.
4. The method of claim 2 in which the ester comprises from about 2
to 5 percent by weight of the dry sweetener composition. .[.5. The
method of claim 2 in which the ester is aspartyl-phenylalanine
methyl ester..]. .[.6. The method of claim 5 in which the starch
hydrolysate is a sorghum starch hydrolysate having a D.E. in the
range up to about 12..]. .[.7. The method of claim 5 in which the
dry pulverulent composition is dried to a
moisture content up to about 1 percent..]. 8. A sweetener
composition made by the method of claim 1. .Iadd. 9. A method of
preparing a dry pulverulent low calorie sweetener composition
containing aspartyl-phenylalanine methyl ester as the sweetener,
which comprises
a. preparing an aqueous starch hydrolysate having a D.E. up to 20
and having a temperature of about 30.degree. to about 80.degree.
C,
b. preparing a substantially concentrated aqueous solution or
slurry of said ester having a temperature not exceeding about
40.degree. C,
c. admixing a minor proportion of the b. solution or slurry with a
major proportion of the a. solution, said minor proportion being in
an amount sufficient to provide in the final production from 0.5 to
10 percent, by weight,
d. promptly feeding the c. mixture to a preheater of a spray dryer
and thereupon spray drying said c. mixture to provide a dry
pulverulent composition containing not more than about 4 percent
moisture. .Iaddend..Iadd. 10. The method of claim 9 in which the
starch hydrolysate is a sorghum starch hydrolysate having a D.E. in
the range up to about 12. .Iaddend..Iadd. 11. The method of claim 9
in which the dry pulverulent composition is dried to a moisture
content up to about 1 percent. .Iaddend.
Description
This invention relates to dry, low calorie sweetener compositions
which contain dipeptide sweeteners exemplified particularly by
aspartyl-phenylalanine methyl ester. This latter compound is a
white, crystalline powder which possesses a sweet taste, being
capable of replacing 100 to 200 times its weight of sucrose.
.[.Such dipeptide.]. .Iadd.Dipeptide .Iaddend.sweeteners are
disclosed in U.S. Pat. No. 3,475,403, being shown to be represented
by the formula ##STR1## WHEREIN X is selected from the group of
radicals consisting of ##STR2## and
R being a member of the group consisting of hydrogen and a lower
alkyl radical, m an integer selected from the group consisting of 0
and 2 and n a positive integer less than three.
While such dipeptide sweeteners can, of course, be utilized as such
as sweeteners for beverages such as coffee, tea and allied
purposes, it has been suggested, as is set forth, for instance, in
the aforesaid U.S. Patent, that they can be employed in the form of
powders, tablets, syrups, etc. and in conjunction with liquid or
solid carriers such as water, glycerol, starch, sorbitol, salt,
citric acid and, generally, other non-toxic substances.
The aforesaid dipeptide sweeteners have been found to be relatively
unstable compounds. Thus, for example, aspartylphenylalanine methyl
ester undergoes decomposition or change relatively readily under
certain conditions to form a diketopiperazine, causing a
significant diminution in sweetening power. When
aspartylphenylalanine methyl ester is admixed with water, it does
not dissolve readily but tends to lump, said lumps dissolving with
some difficulty. When said ester is tableted in conventional
manners, the resulting tablets do not dissolve readily in water.
Even when said ester is admixed with a major proportion of a
pulverulent carrier, such as powdered lactose, it does not go into
solution in water or aqueous media very readily. The foregoing
considerations have presented substantial problems in preparing the
said dipeptide sweeteners in a form such that advantage can be
effectively taken of their high sweetening properties while, at the
same time, avoiding as much as is reasonable possible the problems
inherent in the solubility and instability characteristics of said
dipeptides.
The present invention is based, in part, upon incorporating said
dipeptide sweeteners into certain starch hydrolysate carriers,
namely, hose having a dextrose equivalent (D.E.) of zero to 20,
preferably zero to 12, coupled, however, with certain other
critical conditions of operation, hereafter described, whereby the
aforesaid problems are, to a substantial extent, overcome.
It may be pointed out that it is recognized that it has heretofore
been known, as shown in U.S. Pat. Nos. 3,320,074 and 3,325,296, to
employ certain starch hydrolysates in the production of sweetener
compositions in which the sweetener is saccharin or cyclamates or
mixtures thereof. In the first of these two patents, an aqueous
solution of a water-soluble dextrin, having a D.E. of about zero,
is subjected to pressure, aerated and then spray dried, the final
product having a bulk density not exceeding about 0.15 g/cc and
having a caloric content in the range of about 2.7 to less than 5.5
calories per level teaspoon. In the second of said patents, an
aqueous solution of a water-soluble starch hydrolysate, having a
D.E. in excess of 13 but not more than 28, and a noncalorie
artificial sweetener such as saccharin and/or cyclamates is
subjected to vacuum drying as, for instance, on a vacuum drum
dryer. The resulting products, after milling and classification,
have caloric contents as low as about 3 calories per level
teaspoon. The procedures described in the said patents are
ineffective to produce satisfactory low calorie products simply by
substituting the dipeptide sweeteners for saccharin and/or
cyclamates. This is because the dipeptide sweeteners have certain
instability characteristics which are not possessed by saccharin or
the cyclamates, and, under the manufacturing procedures taught by
said patents, and dipeptide sweeteners break down to a very
substantial extent and their sweetening efficacy is markedly
impaired.
As has been stated above, only those starch hydrolysates which have
a D.E. of zero to 20 are satisfactory for use in the practice of
our present invention. In this connection, it has been found that
the D.E. of the startch hydrolysates is essentially directly
proportional to the instability of the starch hydrolysate dipeptide
composition in dry form as well as in solution. If starch
hydrolysates having a D.E. in excess of about 20 are sought to be
used, the rate of destruction of the dipeptide sweetener is unduly
rapid, in the process of preparing a dry pulverulent sweetener
composition, as well as in the said dry pulverulent compositions on
standing under normal storage or shelf conditions, and on
incorporation of said compositions into hot aqueous drinks such as
coffee and tea.
In the practice of our invention, an aqueous solution or slurry is
made containing, advantageously, only a dipeptide sweetener of the
type disclosed in the aforesaid U.S. Pat. No. 3,475,403,
.[.particularly.]. .Iadd.or .Iaddend.aspartylphenylalanine methyl
ester. Where a solution is made up, it is desirably concentrated
but it may be of somewhat lesser concentration, preferably,
however, not substantially less than 75 percent of the amount which
can be held in solution at the temperature involved. However, since
aspartyl-phenylalanine methyl ester is not overly soluble in water,
being about 0.5 percent at 25.degree. C, about 1.7 percent at
50.degree. C and about 5 percent at 75.degree. C, it is desirable
to make a slurry of said ester in water wherein the slurry contains
from about 8 to 20 percent of said ester. This solution or slurry
is made in the cold and, in general, the temperature thereof should
not exceed 40.degree. C, better still should not exceed 30.degree.
C, and, more advantageously, should be about room temperature or
15.degree. C or below. It is especially desirable that such
solution or slurry should be made up as shortly as possible before
it is admixed with the starch hydrolysate solution, as described
below.
A separate aqueous solution is made up of the aforesaid starch
hydrolysate having a D.E. of zero to 20. While various starches can
be used to make the starting starch hydrolysate, as a practical
proposition corn and sorghum starches are most desirable,
particularly waxy maize and waxy milo starches. The starch
hydrolysate solids content of said aqueous solution is somewhat
variable but, in general, it is desirably in the range of about 40
to about 60 percent, particularly advantageously about 55 to 58
percent, by weight of said solution. The lower solids
concentration, in the aforesaid range, produce finished dried
sweetener compositions having lower bulk densities than those
obtained with the higher solids concentrations. With solids
concentrations of about 55 to 60 percent and using a corn starch
hydrolysate having a D.E. of 10 to 12, there are commonly obtained
finished dried dipeptide sweetener compositions with a bulk density
of the order of 0.05 to 0.1 g/cc, and with caloric contents of the
order of 1 to 2 calories per level teaspoon. This starch
hydrolysate solution is preferably made up at a temperature of
about 50.degree. C, with a range of about 30.degree. C to
80.degree. C, but this temperature may be somewhat higher,
depending on the temperature of the solution or slurry of the
aforesaid ester sweetener. At any rate, the mixture of the starch
hydrolysate solution and the solution or slurry of the ester
sweetener, which mixture is prepared just before entering it or its
being fed into the preheater or preheaters of the spray dryer,
should have a temperature that is between about 50.degree. to
70.degree. C, advantageously about 60.degree. to 65.degree. C.
Between the time of preparing said mixture and the time that it is
introduced or fed into the preheater or preheaters of the spray
dryer, where drying is effected by means of a spray drier, only as
short a period of time as is reasonably possible or practicable
should be permitted to elapse. At most, only a few minutes, of the
order of 3 to 5 minutes, should be permitted to elapse and, more
desirably, such elapsed time should not exceed about 1 minute. The
spray drying operation is initiated promptly and the spray drier is
operated under conditions such that the moisture content of the
finished, spray dried sweetener composition does not exceed about 4
percent and, more desirably, does not exceed about 1 percent, by
weight of said finished composition. The exact manner of operating
or controlling the spray dryer so as to obtain a finished spray
dried product having the aforesaid moisture contents is variable,
depending upon the exact construction of the dryer, temperature
controls of inlet and outlet air and other factors which are, per
se, well known to the art. In the preheater of the spray drier, the
temperature of the mixture to be spray dried is rapidly raised, in
a matter of several seconds, commonly about 5 to 15 seconds, to a
temperature in the range of about 60.degree. to 90.degree. C or
above, prior to the spraying into the drying chamber. By reducing
the total solids content of the mixture of the starch hydrolysate
and the dipeptide sweetener, preheating may be avoided but, as a
practical proposition in general, it is especially advantageous to
effect preheating and to effect drying in a spray drier in the
manner and under the conditions described above.
While it is especially advantageous that the mixture of
ingredients, made as described above and under the temperature and
time conditions, be spray dried, in the broader aspects of the
invention other drying equipment can be used such as vacuum drum
driers, thin film driers and the like, rapid transfer to and rapid
drying being an important desideratum. In the drying operation, an
expanded dry pulverulent composition is obtained.
The starch hydrolysate constitutes a distinctly major proportion
and the dipeptide sweetener constitutes a distinctly minor
proportion of the aqueous slurry or solution, as the case may be,
and, of course, of the total solids and of the final sweetener
composition. The proportions of dipeptide sweetener utilized,
although always distinctly minor, are variable, depending upon the
sweetness characteristics of the particular dipeptide sweetener
utilized and on the degree of sweetness desired in the final
sweetening composition. In general, the dipeptide sweetener will
usually fall within the range of 0.5 to 10 percent, particularly 2
to 5 percent, of the finished spray dried sweetener composition.
The viscosities of the aforesaid aqueous compositions, as fed into
the preheater or preheaters of the spray dryer, are variable,
falling into the range of 50 to 1,000 cps as measured by a
Brookfield Viscosimeter. The viscosities depend, of course, not
only on the concentration of solids in the aqueous composition, for
a particular starch hydrolysate and dipeptide sweetener, but also
on the temperature of such aqueous composition or solution. Thus,
in an illustrative case of an aqueous composition or solution
containing 55 percent total solids, in which, on the total solids
basis, the starch hydrolysate constitutes 95 percent and the
dipeptide sweetener constitutes 5 percent the viscosity is about
300 cps at 37.degree. C, about 100 cps at 50.degree. C, and about
80 cps at 55.degree. C.
While the nature of the dry, low calorie sweetener compositions
with which our invention deals is believed apparent from the
disclosures set forth above, the following are examples of
illustrative aqueous compositions prior to drying the same in the
manner and under the conditions hereinabove described. The
percentages stated are by weight.
Example 1
______________________________________ Milo starch hydrolysate
(D.E. zero) 38 Aspartyl-phenylalanine methyl ester 2 Water 60
______________________________________
Example 2
______________________________________ Corn starch hydrolysate
(D.E. 5) 47.5 Aspartyl-phenylalanine methyl ester 2.5 Water 50
______________________________________
Example 3
______________________________________ Corn starch hydrolysate
(D.E. 12) 57 Aspartyl-phenylalanine methyl ester 3 Water 40
______________________________________
Example 4
______________________________________ Corn starch hydrolysate
(D.E. 10) 52.25 Aspartyl-phenylalanine methyl ester 1.65 Sodium
saccharin 1.1 Water 45 ______________________________________
Example 5
______________________________________ Milo starch hydrolysate
(D.E. 11.5) 52.195 Aspartyl-phenylalanine methyl ester 1.65 Calcium
saccharin 1.1 Potassium sorbate 0.055 Water 45
______________________________________
As indicated above, our sweetening compositions advantageously
contain only the water-soluble starch hydrolysate and the aforesaid
dipeptide sweetener. Supplemental ingredients can be added in small
proportions, if desired, to the aqueous compositions prior to
drying the same, to obtain special effects as, for example, sodium
or calcium saccharins, cyclamates, edible gums, thickeners,
stabilizers, surfactants, preservatives, flow conditioners, and the
like. When reference is made in the claims to the compositions
consisting essentially of the specified ingredients, it will be
understood that this does not exclude the inclusion of small
proportions of supplemental ingredients which do not fundamentally
change the character of the low calorie sweetener compositions of
our invention.
It has also been found that the dipeptide sweeteners tend to react
with the starch hydrolysate to cause a slight discoloration of the
finished dry pulverulent dipeptide sweetener composition, the
extent of which varies with the temperatures to which the mixtures
of the dipeptide sweetener and the starch hydrolysate are subjected
and the length of time of contact therebetween. Generally, if
optimum conditions under which the sweetener compositions of the
present invention are prepared are observed, the discoloration is
quite minimal. The discoloration can be substantially reduced by
adding small proportions of hydrogen peroxide to the mixture of the
starch hydrolysate and the dipeptide sweetener, or by adding
glucose oxidase to said mixture, prior to the step of drying the
mixture. This should be done under conditions such as not to
substantially affect the D.E. of the starch hydrolysate.
The pulverulent free-flowing water-soluble low calorie sweetening
compositions of our invention can be used, as are intended for use,
in the same general way as sucrose for sweetening beverages and for
various other food purposes for which sucrose is utilized.
* * * * *