This application relates to the field of sweeteners and more particularly to new carbohydrate and dipeptide sweetener compositions and their usage in foods and beverages. Sweeteners are a critical ingredient in the food supply. Development of convenience foods has lead to increased consumption of sweeteners. Demand for lower calorie food products has led to various attempts to reduce the sweetener contribution of calories. The primary means to accomplish this objective has been through the use of artificial or high intensity sweeteners (e.g. saccharin). However, the use of such sweeteners, in many food systems, results in bitter flavors or objectionable aftertastes. The use of caloric sweeteners other than sucrose (e.g. fructose) has become more common in recent years. Fructose has been reported to be from 1.0 to more than 1.8 times as sweet as sucrose when evaluated under similar conditions (Hardy et al, J. Am. Dietetic Assoc. 74(1):41-46, January, 1979). The extra sweetness of fructose has allowed the formulation of foods with sweetness equivalent to sucrose sweetened foods, but which contain less sweetener and, therefore, fewer calories. The use of nutritive, high intensity sweeteners as described in U.S. Patent 3,642,491 issued to Schlatter has gained in popularity in the last few years. L-aspartyl-L-phenylalaπine lower alkyl esters commonly known as aspartame, and the like are typical of the available dipeptide sweeteners. Such high intensity sweeteners, while improvements over saccharin and cyclamates, still have some objectionable tastes and are very expensive. Additionally, when products such as

beverages are sweetened with high intentity or artificial sweeteners,, the body or mouthfeel of the product is changed .

The blending of ^• sweeteners to develop synergism has been reported by Hyvonen et al (J . Food Sci . 43 :251 -254, 1978) . Synergism is inferred when the sweetness of a mixture is greater than the sum of its components . However, the quantitive measu rement of synergism is difficult. The Hyvonen group studied synergism between fructose and saccharin and other sweeteners . They reported the synergism between fructose and saccharin was found to be greatest when each sweetener provided approximately equal contributions to the sweetness of the mixture, i . e. one-half of the sweetness contributed by fructose and one-half contributed by saccharin .

A review of synergism between sweeteners was published as a chapter (pages 173-184) in "Carbohydrate Sweeteners in Foods and Nutrition" edited by P . Koivistoinen and L. Hyvonen published by Academic Press (1980) . Cyclamate was reported to be synergistic with fructose, sucrose, glucose, invert sugar and xylitol . Mixtures of synthetic and carbohydrate sweeteners were found to be a useful alternative for sucrose in many drinks . Such mixtu res provided 50-70% less energy and a lack of aftertaste in the case of saccharin .

U . S . Patent No . 4,497,841 (Wudel et al . ) discloses dessert mixes obtained by preparing aqueous solutions or dehydrated powders containing butterfat; nonfat dry mil k solids containing a certain portion of whey protein concentrate; a fructose-based sweetening agent and a stabilizer . It is disclosed that the

preferred sweetening agent comprises substantially pure fructose, but up to 25% of the fructose can be replaced by other sweetening agents such as corn syrup solids, maltose, glucose, sucrose, honey, invert sugar, saccharin and aspartame. Example IX discloses that a fructose-based sweetener comprised of 90% fructose and 10% aspartame (Run Q), or 95% fructose and 5% aspartame (Run U), can be used, but does not specify whether the percentages are by weight or by contribution to sweetening effect. If the percentages are by weight, the ratio of fructose to aspartame by weight is 9:1 and 19:1, respectively. There is no disclosure that fructose and aspartame are synergistic as sweeteners. It is an object of this invention to provide a sweetener composition that has sweetness equal to or greater than sucrose, but will provide significantly fewer calories in the finished food product. Another object is to provide a sweetener that has substantially reduced bitter flavor or unpleasant aftertaste and yet produces the desired body and mouthfeel in the finished food or beverage product. A still further object is to provide a reduced or low calorie beverage with improved flavor and textural properties. Throughout the specification and claims, all ratios and percentages are stated on a weight basis and temperatures are in degrees Celsius unless otherwise indicated.

SUMMARY OF THE I NVENTION This invention relates to a sweetener composition comprising a mixture of a) a carbohydrate component comprised predominantly of fructose and b) a dipeptide sweetener component, wherein the weight ratio on a dry solids basis of fructose to dipeptide sweetener is greater than about 19: 1 .

This invention also relates to foodstuffs, particularly beverages, comprised of the components of said sweetener composition and to dry beverage mixes comprised of the components of said sweetener composition .

DETAI LED DESCR I PTION

The sweetener composition of the present invention is comprised of two components, a carbohydrate component that is predominantly fructose and a dipeptide component such as aspartame. It has been found that when a predominantly fructose sweetener is blended with a dipeptide sweetener within certain ratios, a dramatic synergistic sweetening effect results .

The carbohydrate component is predominantly (i . e. , greater than 50% by weight of dry solids) fructose, preferably 90% fructose high fructose corn syrup (H FCS) , crystalline fructose or crystalline fructose that has been dissolved in water to ma ke a fructose syrup . It is preferred that the fructose component be at least about 90% fructose, and most preferably at least about 98% fructose on a dry solids basis .

The dipeptide sweetener component of this invention is selected from lower al kyl esters of

aspartylphenylalanine or aspartylhexahydrophenyialanine as represented by the following structural formula:

C h\ R'

Hj N C H C O N H C H C O O R

C H ₂ C 0 0 H

wherein R is a lower alkyl radical and R' is a phenyl or cyclohexyl radical. Each optionally substituted by one or more groups selected from hydroxy and lower alkoxy.

The lower alkyl radicals encompassed by that formula are typified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and the branched-chain isomers thereof. Other acceptable dipeptide sweetener components include L-aspartyl-D-alanine alkyl amides disclosed in European Patent Application No. 34,876 to Pfizer, published Sept. 2, 1981, L-aspartyl-L-1-hydroxymethylalkaneamide sweeteners disclosed in U.S. Patent No. 4,338,346 to Brand, issued December 21, 1982, L-aspartyl-l-hydroxyethylalkaneamide sweeteners disclosed in U.S. Patent No. 4,423,029 to Rizzi, issued December 27, 1983, and the like. The sweetener composition may be prepared by blending the components, by co-processing the components to yield a dry product or by mixing the components with added water to prepare a sweetener syrup solution. Relative Sweetness of various sweetener compounds can be evaluated by several techniques. One technique commonly used is the Relative Sweetness Test in which water-sweetener solutions containing 10% dry

solids are prepared; the temperature of the solution is adjusted to about 20°C; and the solution is evaluated by persons trained in sensory evaluation . Using such a technique, sucrose is arbitrarily defined as 100%. Other sweeteners are then ranked relative to sucrose. Fructose usually has a Relative Sweetness of about 115% ^" as determined by this particular evaluation technique. Relative sweetness is measured by determining the concentration at which a sweetener is judged to be sweeter than the control sweetener by one-half of a given taste panel and less sweet than the control by the other half of the test panel . The relative sweetness is then calculated by dividing the control's concentration by the concentration determined for the sweetener being evaluated . Such techniques are described by R . M . Pangborn , J. Food Science, Vol . 28, p . 726 (1963) .

The relative sweetness of aspartame is such that 1 part of aspartame will be equivalent to 150 to 250 parts of sucrose. Relative sweetness of fructose is reported from 1 .0 to more than 1 .8 times that of sucrose. Based on these values, it would be expected that 1 part of aspartame would be equivalent to 80 to 250 parts of fructose, with a more practical range being from about 100 to about 200 parts of fructose. The sweetener composition of this invention is comprised of 1 part of the dipeptide sweetener and from about 20 to about 1000 parts of fructose, preferably at least about 50 parts fructose. The preferred ratios are from about 150 to about 800, more preferably at least about 180, and most preferably from about 625 to about 700 parts of fructose, per part of aspartame . This ratio yields the optimum balance of synergistic sweetness , undesirable bitter taste, aftertaste, and textural

products in a food or beverage. An advantage of the increased synergism exhibited by fructose and aspartame is the ability to reduce the amounts of aspartame used and thereby reduce any risk of toxicity from aspartame e.g. the toxicity of degradation products or metabolites such as asparatate, phenylalanine, and methanol, and metabolites thereof.

The above described sweetener composition is especially effective in sweetening beverages, both carbonated and still. In general, such beverages contain from about 8 to 14% sucrose or high fructose corn syrup d.s.b. (HFCS) or combinations thereof. It has been found that the sucrose or HFCS sweetener can be replaced by from 3% to about 5% fructose and from about 0.005% to about 0.02% aspartame, preferably from 0.007% to about 0.015% aspartame. It is preferred that the fructose be crystalline and that the sweetener used is essentially dipeptide sweetener and fructose. The use of such a sweetener composition results in a beverage with reduced calories, reduced bitterness from aspartame, flavor enhancement effects from fructose, economic advantages and acceptable textural properties.

The sweetener composition hereof is sweet, soluble in water, stable in aqueous solutions and stable to most heat processing conditions encountered in the processing of foods. As such, the sweetener composition is suitable for use as the sweetening ingredient in the preparation of a wide variety of materials which are intended for consumption or at least contact with the mouth of the user, such materials being herein generically designated as edible materials or foodstuffs. Typical illustrative examples of edible foodstuffs which may be sweetened according to this invention are fruits,

vegetables, juices or other liquid preparations made from fruits or vegetables, meat products, particularly those conventionally treated with sweetened liquors , such as bacon and ham, milk products such as chocolate dairy drinks, egg products, such as eggnogs, custards, angel food mixes , salad dressings , pickles and relishes, ice creams, sherberts and ices, ice milk products, bakery products, icings, confections and confection toppings, syrups and flavors , cake and pastry mixes , beverages , such as carbonated soft drinks , fruit aids, wines, dietary-type foods , cough syrups and other medicinal preparations such as toothpastes, powders , foams and denture-retaining adhesives, mouth washes and similar oral antiseptic liquids , tobacco products, adhesives for gumming stamps, envelopes, labels and the like.

Particularly preferred embodiments of this invention relate to a dry beverage mix containing the sweetener composition of this invention . Such dry mixes typically also include a flavor concentrate and/or a coloring agent. Such concentrates and coloring agents are well known in the art.

I n using the sweetening composition of this invention , it is incorporated in the material to be sweetened in the amount required to attain the desi red level of sweetness . Moreover, the technique of sweetening materials with the compounds of the invention offers no difficulty because the sweetening agent, as a mix or as sepa rate components , is simply incorporated with the material to be sweetened . The sweeteners may be added directly to the material or they may be first incorporated with a diluent to increase their bul k and added to the material . As diluent, if needed, one may use liquid or solid carriers , such as water, starch ,

sorbitol , salt, citric acid or other non-toxic substances compatible with the material to be sweetened .

While the invention has been described as mainly concerned with foodstuffs and other non -tox ic formulations for human consumption , it is obviously within the scope of this invention that these sweetened compositions may be used for consumption by other creatu res , such as farm and domestic animals .

Having thus described the various embodiments of the present invention , the following examples are provided to more fully illustrate those embodiments; however, without limiting the invention to specific details of such examples .

EXAMPLE I

Various sweetener blends were prepared to determine the ratio of various sweetener combinations to provide sweetness equivalent to 10% sucrose (actual control was 0.067% solution of aspartame in water) . The sweetener blends were prepared by making water solutions of the sweeteners at the desired ratios and weight; adjusting the temperature to about 20°C; and

10 determining the relative sweetness by using persons trained in sensory evaluation . I n the following table, the amount of sweetener is expressed in terms of total dry solids as a percentage of the water solutions . The sweeteners , in turn , are crystalline sucrose or fructose,

¹⁵ 90% d . s . b . fructose (90 HFCS) or 55% d . s . b . fructose

(55 HFCS) .

The objective was to define the amount of aspartame required to be added to various carbohydrate sweeteners to approximate the sweetness of a 10% sucrose

^ solution . Expected aspartame usage was calculated assuming that aspartame was 150 times as sweet as sucrose. The relative sweetness factor for each carbohydrate sweetener (column 2, Table I ) was included in the calculation . For example, when 5% fructose was used as the base carbohydrate sweetener, it is necessary to include the relative sweetness factor of 127 for fructose. Therefore, 5% fructose was equivalent to .05 x 127 or 6.35% sucrose. I n order to calculate the expected

30 aspartame usage in this case, 6.35% was subtracted from 10% to yield 3.65% sucrose equivalent needed as aspartame. Since aspartame was assumed to be 150 times

as sweet as sucrose, the amount of aspa rtame expected to be needed was 3.65 ÷ 150 or 0.0243%.

10

15

20

25

30

TABLE I

Sweetness Synergy of Sucrose, Fructose, 90% HFCS , or 55% HFCS with Aspartame

Ratio of Expected Actual Fructose to Synerg

Amount of ReL Sweetness Aspartame Aspartame Aspartame Effe. Sweetener of Sweetener Usage Usage (wt) (%r

5% Sucrose 100 0.0333% 0.019% -- 43

5% Fructose 127 0.0243% 0.007% 714 71

5% 90 HFCS 114 0.0287% 0.007% 643 76

5% 55 HFCS 96 ¹ 0.0347% 0.011% 250 68

3% Sucrose 100 0.0467% 0.030% -- 36

3% Fructose 132 0.0403% 0.016% 188 60

3% 90 HFCS 117 0.0433% 0.015% 180 65

3% 55 HFCS 94 ¹ 0.0479% 0.026% 63.5 46

2% Fructose 135 0.0487% 0.027% 74. 1 45

1 - I nterpolated data .

2 - Synergy Effect - % reduction in aspartame, i . e. (Expected Usage - Actual Usage)/Expected Usage.

Some synergy between sweeteners may be expected, however, as shown by the results in Table I , the combination of fructose and aspartame exhibited significantly more synergism than would be expected . The actual amount of aspartame required was much less than that expected by calculations which accounted for the greater sweetness of fructose compared to sucrose. Sucrose at 5% and 3% required 43% and 36%, respectively, less aspartame than was calculated as necessa ry . Th is can be viewed as the "expected" degree of synergy . However, fructose and 90% H FCS at both the 3 and 5% levels consistently had a more significant synergy effect . The 55 H FCS had some increased synergy but the deg ree was not consistent at both the 3 and 5% levels . The increased synergism of fructose and aspartame as compa red with the synergism of sucrose and aspa rtame is measu rably sign ificant . The weight ratio of fructose to dipeptide sweetener necessa ry to exhibit significant synergism can be determined by routine experimentation along the lines outlined above . The preferred compositions wi ll exh ibit a synergism greater than the maximum synergism exhibited by sucrose and a given dipeptide sweetener . For example, a solution of 5% sucrose and 0. 19% aspartame exh ibited a synergy effect of 43%. This synergy effect is probably the maximum for sucrose and aspa rtame based on the theory of Weickman n et al . , German Patent 1961769 ( 1969) that synergism is at its maximum when components contribute about the same amou nt to sweetness of a mixtu re. The maximum synergy effect for f ructose with other dipeptide sweeteners ca n be determined along the lines outl ined above .

EXAMPLE 2 Carbonated beverages were prepared from the ingredients shown in Table 11 . All of the ingredients except the seltzer were blended to make a cola base syrup. The cola base syrup was refrigerated, i . e. cooled to about 40°F (4°C) . Seltzer (carbonated water) was chilled and added to the cola base syrup which was stirred just until visibly blended .

TABLE

AMOUNT (WT )

INGREDIENTS REGULAR COLA LITE COLA LOW CALORIE COLA

Kola flavor base 0.360 0.360 0.360 (Globe G4617)

High Fructose Corn 15.103 Syrup (55% fructose d.s.b. available as ISOSWEET ¹ " 5500, A. E. Staley Mfg. Co. )

Crystalline 3.488 Fructose _TM (Crystar , A.E. Staley Mfg. Co.)

Aspartame - 0.025 0.077 (NutraSweet Co)

Water - 11.590 15.026

Seltzer 84.537 84.537 84.537 (Carbonated Water) 100.000 100.000 100.000

EXAMPLE 3

Non-carbonated beverages were prepared from the ingredients shown in Table III below by simply mixing the ingredients until all solids were visibly dissolved.

TABLE III AMOUNT (WT. %)

INGREDIENTS SUCROSE CONTROL FRUCTOSE/ASPARTAM

Dry Beverage Mix 0.200 0.200 (Cherry Kool-Aid, Unsweetened, General Foods. Co.)

Sucrose 5.000

Crystalline Fructose 5.000

( (CCRRYYSSTTAARR™ A. E. STALEY

MFG. CO.)

Aspartame (Nutrasweet Co.) 0.033 0.015

Water (distilled) 94.767 94.785 100.000% 100.000%