NO131443B - - Google Patents

Description

Sweetener.

The present invention relates to a sweetener containing as active substances saccharin or cyclamate and a dipeptide with the general formula:

where the stereochemical configuration is L-L, DL-DL, L-DL or

Said dipeptide is described in US Patents No. 3,92,131 and No. 3,475,403.

It has now surprisingly been found that when a dipeptide with the above formula is mixed with a known sweetener such as saccharin or cyclamate, the sweetening ability of the mixture will be enhanced. This synergistic effect is completely unexpected and could not have been predicted from previously known knowledge in the area. The known fact that the dipeptide, saccharin or cyclamate individually has a sweet taste is thus in no way an indication or a prerequisite for the synergistic effect (i.e. that the composition has a sweetening ability that is greater than the cumulative effect of the individual components, and where this synergistic effect can be said to be an enhancing effect of one agent on the other), which can be observed when the dipeptide is combined with known sweeteners, e.g. saccharin.

A preferred embodiment of the present invention is a composition containing saccharin and one of the aforementioned dipeptides of formula (I). A particularly preferred embodiment of the present invention is a sweetener containing saccharin and an aspartyl phenylalanine methyl ester.

A more particularly preferred embodiment of the present invention is a sweetener containing saccharin and L-aspartyl-L-phenylalanine methyl ester.

L-aspartyl-L-phenylalanine methyl ester is a special one

sweet dipeptide with a sweetening power in the range of 125-150 times that of sugar. The sweetening power of the various stereochemically isomeric forms of aspartyl phenylalanine methyl ester depends on the amount of L-L isomer present. The DL-DL form thus has 1/4 of the sweetening power of the L-L form, while the DL-L and L-DL forms have half the sweetening power of the L-L form.

Sweeteners containing a dipeptide of formula I and saccharin or cyclamate can be prepared in a number of different forms for further use. Typical forms that can be used include fixed forms, e.g. powders, tablets, granules, etc., in addition to liquid forms, such as solutions, suspensions, syrups and emulsions, as well as other commonly used^ forms which are particularly suitable for combination with edible substances. The term "edible substances" is understood here as all non-toxic substances that are digestible by humans or other animals in solid or liquid form. Examples of similar substances are among other foods, including foodstuffs, manufactured and processed foodstuffs, chewing gum and beverages, food additives, including flavor and color additives, as well as taste-enhancing agents, in addition to pharmaceutical preparations etc.

The present sweeteners can be processed into preparations which can consist of the present sweeteners either alone or together with other non-toxic carriers for sweeteners, e.g. of the type usually used with sweeteners. Such suitable carriers are liquids such as water, ethanol, sorbitol, glycerol, citric acid, corn oil, peanut oil, soybean oil, sesame oil, propylene glycol, corn syrup, maple syrup and liquid paraffin, solids such as lactose, cellulose, starch, dextrin and others modified starches, calcium phosphate and di- and tri-calcium phosphate. Toxic substances, such as methanol and dimethyl sulphoxide, will of course not be able to be used together with the existing sweeteners.

Examples of specifically edible substances, which can be made sweeter by adding a sweetener containing a compound of formula I as well as saccharin and cyclamate, especially saccharin, are among others fruit, vegetables, juice, meat products, such as ham, bacon and sauces, egg products, fruit concentrates , gelatin and gelatin-like products, such as jam, jelly, preservatives,

etc, dairy products such as ice cream, sour milk etc, syrup, including molasses, corn, wheat, rye, soybean, oat and rice products, such as bread, biscuits, cake mixes etc., fish and sea products in general, cheese and cheese products, nuts and nut products, beverages, such as coffee, tea, soft drinks with and without carbon dioxide, beer, wine and other alcoholic beverages, confectionery, confectionery and chocolate, vegetables, spices, vinegar and other taste-enhancing substances,

such as monosodium glutamate, besides chewing gum. Other types of commercial products where you can use a sweetener containing a sweetener of formula I as well as saccharin or cyclamate are, for example, packaged products, such as diabetic sugar, liquid sweeteners, granulated flavor mixes, which when added to water give beverages without carbon dioxide, pudding mixes, coffee and tea powder, artificial cream mixes, dry milk, foodstuffs

for livestock, tobacco, toothpaste and mouthwash, in addition to a number of pharmaceutical preparations.

Depending on which edible substance saccharin is added, it can. sweetening ability be up to 500 times stronger than that of sucrose. It has now surprisingly been found that when saccharin

mixed with one of the aforementioned dipeptides, you will get an enhanced sweetening ability. An addition of L-aspartyl-L-phenylalanine methyl ester to saccharin, will e.g. produce a bla^^lng with a sweetening ability which is approx. 1000 times stronger than sucrose.

Specific examples of the synergistic effect produced by mixing the above-mentioned dipeptides with saccharin or cyclamate are given below. The concentrations stated below are only intended as an illustration, as the desired degree of sweetness will vary greatly from individual to individual.

The above-mentioned synergistic effect has been confirmed by standardized experiments with different mixtures of L-α-aspartyl-L-phenylalanine methyl ester with sodium saccharin and -cyclamate. In the following, the term "APM" stands for L-α-aspartyl-L-phenylalanine methyl ester. Likewise, the terms "cyclamate", "Sucaryl®" and "cyclamate sodium" are used interchangeably, which is also the case for "sodium saccharin" and "SS".

The provision of the S.E.V. (sweetness equivalence value) for mixtures of L-α-aspartyl-L-phenylalanine methyl ester and sodium saccharin was made by first determining the S.E.V of APM alone, and SS alone, in coffee (compared to h% sucrose level), and in "Kool-aid " (compared to a 9% sucrose level). These values were then used in connection with a judging panel comprising 11 judges and using the two-sample difference test (Hall, Tarver and McDonald, Food Technology, page 699, December 1959) and ranking test (Kramer, Food Technology , page 576, November 1960, and Kramer, Food Technology, page 124, December 1963). The sweetness value for L-α-aspartyl-L-phenylalanine methyl ester of 150 in coffee or 125 in "Kool-aid" was assumed to be constant and the S.E.V. for sodium saccharin was determined for mixtures of L-α-aspartyl-L-phenylalanine methyl ester and sodium saccharin. Table I below illustrates the results from these experiments.

The S.E.V. contribution due to sodium saccharin represents its contribution in a beverage where half of the sweetness comes from each sweetener (L-α-aspartyl-L-phenylalanine methyl ester and sodium saccharin).

Aqueous samples of L-α-aspartyl-L-phenylalanine methyl ester, sodium saccharin and compositions consisting of a mixture of these two substances were analyzed by a taste evaluation committee. The trial solutions were compared to a 10% sucrose solution to ensure that they were iso-sweet. Solutions were defined as iso-sweet when the taste panel determined that the solutions were equal in terms of sweetness. The accuracy of the sweetness determination is limited to around 10% of the sweetness level. The concentration of L-α-aspartyl-L-phenylalanine methyl ester and sodium saccharin required to result in certain conditions at an equivalent sweetness to 10% sucrose is shown in the table below.

Potency values as a function of concentration were determined by comparing sucrose, L-α-aspartyl-L-phenylalanine methyl ester and sodium saccharin at various concentrations whereby they were iso-sweet. These data are indicated in the table below.

Taufel and Klemm (1925) in "Principles of Sensory Evaluation of

Food" of Amerin, Pangborn and Roessler, Academic Press (1965)•

The determination of synergism for L-α-aspartyl-L-phenylalanine methyl ester and cyclamate was made by first determining the individual S.E.V. values for L-α-aspartyl-L-phenylalanine methyl ester when compared to 4.0%, 2.0% and 1.0% sucrose levels in black coffee, and cyclamate when compared to 4.0% and 2.0% sucrose levels in black coffee. The S.E.V. values and corresponding concentrations are given in the table below.

The relevant synergism tests were carried out organoleptically using a mixture containing 0.1033 g L-α-aspartyl-L-phenylalanine methyl ester/liter (equivalent to 2% sucrose) and 0.5478 g cyclamate/liter (equivalent to 2% sucrose). A further mixture with the same weight ratio of cyclamate/L-α-aspartyl-L-phenylalanine methyl ester (5.3:1) containing 0.0904 g L-α-aspartyl-L-phenylalanine methyl ester/liter and 0.4792 g cyclamate/liter was also prepared . Examination of these mixtures showed that the resulting sweetness of the mixtures was 12.5% greater than would be expected if synergism were not present.

The examples below illustrate the application of the invention.

Example 1

An imitation strawberry drink without carbon dioxide was prepared using four different sweeteners: A) Sucrose alone, B) L-aspartyl-L-phenylalanine methyl ester alone, C) Saccharin alone, and D) Saccharin and L-aspartyl-L-phenylalanine methyl ester together. The composition of each individual drink with a total volume of 300 ml is indicated below:

A. Sucrose alone

Sucrose 27 g

Dextrose 2.61 g

Citric acid 0.15 g

Artificial strawberry flavor (Dragoco N1132) 0.12 g

Lactose 1.827 g

Water 268 g

B. L-aspartyl-L-phenylalanine methyl ester alone L-aspartyl-L-phenylalanine methyl ester 0.216 g Citric acid 0.15 g

Artificial strawberry flavor (Dragoco N1132) 0.12 g

Lactose 1.827 g

Water 299 g

C. Saccharin alone

Saccharin 0.054 g

Citric acid 0.15 g

Lactose 1.827 g

Artificial strawberry flavor (Dragoco N1132) 0.12 g

Water 299 g

D. Saccharin plus L-aspartyl-L-phenylalanine methyl ester L-aspartyl-L-phenylalanine methyl ester 0.108 g Citric acid 0.15 g

Lactose 1.827 g

Saccharin 0.0165 g

Artificial strawberry flavor (Dragoco N1132) 0.12 g

It was determined by a test group that each of the above compositions had an equally strong sweet taste.

Example 2

About. 3000 ml of coffee was prepared by dissolving 16.5 g of coffee powder in 3000 ml of water. 600 ml portions of this coffee were taken out and each added one of the following sweeteners:

E) 24 g sucrose, F) 0.16 g L-aspartyl-L-phenylalanine methyl ester,

G) 0.048 g saccharin and H) 0.012 g saccharin with 0.08 g L-aspartyl-L-phenylalanine methyl ester.

It was determined by a test group that all the coffee blends produced had the same strong sweetness.

Example 3

A cola drink was prepared by first preparing the following base containing:

140.8 ml Cola concentrate

2.75 g sodium benzoate

18.85 g of a mixture of 1 part by weight of L-α-aspartyl-L-phenylalanine methyl ester and 10 parts by weight of sodium cyclamate,

sufficient water for a final volume of 1300 ml.

Each bottle of beverage made was prepared by diluting 29.6 ml of this base with sufficient carbonated water to give a final volume of 178 ml with a carbonation volume of 3.6.

Example 4

A cola drink was prepared by first preparing the following base containing:

140.8 ml Cola concentrate

2.72 g of sodium benzoate

16.72 g of a mixture of' 1 part by weight of L-a-aspartyl-L-

phenylalanine methyl ester and 7 parts by weight of sodium cyclamate,

sufficient water for a final volume of 1300 ml.

Each bottle of prepared beverage was made by diluting 29.6 ml of said base with sufficient carbonated water to give a final volume of 178 ml with a carbonation volume of 3.6.

Example 5

An orange soda was prepared by first preparing the following base containing:

63.0 ml orange base

17.0 ml 50% citric acid

14.5 ml of 25% sodium benzoate

21.41 g of a mixture of 1 part by weight of L-α-aspartyl-L-phenylalanine methyl ester and 10 parts by weight of sodium cyclamate,

sufficient water for a final volume of 1250 ml.

Each bottle of prepared beverage was made by diluting 29.5 ml of said base with sufficient carbonated water to a final volume of 178 ml with a carbonation volume of 1.75.

Example 6

An orange soda was prepared by first preparing the following base containing:

63.0 ml orange base

17.0 ml 50% citric acid

14.5 ml of 25% sodium benzoate

18.99 g of a mixture of 1 part by weight of L-α-aspartyl-L-phenylalanine methyl ester and 7 parts by weight of sodium cyclamate,

sufficient water for a final volume of 1250 ml.

Each bottle of beverage produced was made by diluting 29.5 ml of said base with sufficient carbonated water to give a final volume of 178.ml and with a final carbonation volume of 1.75-

Claims (2)

1. Sweetener, characterize tr. in that it contains as active substances saccharin or cyclamate and a dipeptide with the general formula: wherein the stereochemical configuration is L-L, DL-DL, L-DL or DL-L. 2. Sweetener according to claim 1, characterized in that it contains saccharin and L-aspartyl-L-phenylalanine methyl ester.