BULKING AGENT

Abstract: A bulking agent comprised of cellobiitol is disclosed that, when combined with a high potency sweetening agent, possesses the physical structure, texture, moisture retention and density of sucrose in formulated foods without the high caloric content. The cellobiitol bulking agent is produced by a process that results in a substantially pure crystalline compound that is freely flowing, without objectionable flavors and does not require extensive purification or isolation.

Description: _ χ „ BULKING AGENT CROSS REFERENCE TO RELATED APPLICATIONS This application is a Continuation-in-Part (CIP) of co-pending Serial No. 124,691 filed 24 November 1987 incorporating the data included with the affidavit filed under 37 C.F.R. §1.132 on 12 October 1988. BACKGROUND The present invention relates generally to a bulking agent suitable for incorporation into foods. Specifically, the invention relates to a bulking agent suitable for replacing sucrose incorporated into formulated foods. Sucrose (alpha-D-glucopyranosyl-β-D- fructofuranoside) , also known as cane or beet sugar, is a widely used sweetening agent for sweetening foods and beverages. Sucrose, however, is cariogenic and highly caloric. For these reasons, strong efforts have been expended to reduce the intake of sucrose and other sweeteners so disadvantaged. As a consequence of these efforts, high-potency/low calorie sweeteners such as aspartame, saccharin and the like have become increasingly popular. While the use of small amounts of high potency sweeteners such as aspartame is particularly successful in reproducing the taste sensation of sucrose, the use of such high potency sweeteners fails to adequately reproduce other properties of sucrose that are important to its function in formulated foods. In particular, sucrose, as a consequence of its bulk properties, provides actual physical structure, texture, moisture retention, density and appearance characteristics to formulated foods. These properties are in significant part due to the volume occupied by sucrose and are therefore dependent on its bulk. In order that sucrose may be replaced by high potency sweeteners in formulated foods, it is therefore desirable to incorporate agents to reproduce the structure, texture, moisture retention, density and appearance characteristics of sucrose without adding the calories that sucrose would provide. The prior art discloses the use of various bulking agents for reproduction of such characteristics. Mitsuhashi, et al. , in U.S. Patent 3,741,776 discloses the use of maltitol (4-O-alpha-D-glucopyranosyl-D-sorbitol) as a sweet bulking agent for incorporation into low-calorie foods and beverages. Maltitol provides solid volume, body, moisture absorbance, luster and increased viscosity while also providing a sweet taste said "to be greater than that of grape sugar but less than that of sucrose." Schiβweck, et al. , in U.S. Patent 3,865,957 discloses the use of isomaltitol (6-O-alpha-D- glucopyranosyl-D-sorbitol) as a sweet bulking agent for incorporation into low-calorie foods, either alone or in combination with high potency sweeteners such as aspartame. ayton, in U.S. Patent 4,024,290 discloses a bulking agent for incorporation into formulated foods prepared according to a process wherein glucose and sorbitol are subjected to a condensation reaction at low pressures and elevated temperatures in the presence of an acid-exchange resin. The bulking agent prepared according to the disclosed method comprises a viscous syrup which contains as a major component about 70% of the isomeric β-anomers of glucosylsorbitol, i.e. 1,2,3,4,5 and 6-glucopyranosyl-D-sorbitol. The bulking agent further includes various minor components including about 1% sorbitol and 15% other carbohydrates. The reference further discloses that residual sorbitol may be removed from the mixture of β-anomers of glucosylsorbitol. The reference also discloses the combination of the bulking agent with high potency sweeteners such as aspartame to render the bulking agent as sweet as an equal weight of sucrose. The bulking agents, comprising effective amounts of high potency sweeteners, are disclosed to be thick and viscous and are preferably either warmed to increase their fluidity or diluted with about 30% water to form a syrup. Of interest to the present invention is the disclosure of Levine, et al. , Science, £5, 550 (1937), disclosing the reduction of cellobiose (4-O-β-D-glucopyranosyl-D-glucose) to cellobiitol (4-0-β-D-glucopyranosyl-D-sorbitol) . Cellobiitol is disclosed to comprise crystalline platelets, melting at 133°C and having a specific rotation in water of [al D "—8.7°. Also of interest to the present invention is the disclosure of Abdel-Akher, et al. , J. Amer. Chem. Soc. 73, 4691 (1951) disclosing a method for the reduction of sugars to their corresponding alcohols by means of treatment with sodium borohydride in an aqueous solution. The reference discloses preparation of cellobiitol from cellobiose although it is noted that cellobiitol fails to crystallize in a "reasonable" time. Of further interest to the present invention is the disclosure of Yoshien in Japanese Patent Application No. 72001820 of January 19, 1972 allegedly disclosing the use of cellobiitol as a non-caloric sweetening agent that confers about the same degree of sweetness as grape sugar (glucose) and slightly less than that of beet sugar (sucrose). The reference states that cellobiitol "does not easily crystallize" and "can be used in food or beverages without the risk of crystallization or milkiness." The material is said to provide foods and beverages with water retention and moisture absorbent qualities, which enhance viscosity and thus provide body and luster in the same way as sugar-based sweeteners. The reference discloses production of cellobiitol by catalytic conversion of cellobiose at a pressure of 60 to 80 atmospheres in hydrogen gas at temperatures of 90 to 120 β C for between 4 and 9 hours. Suitable catalysts include 9% to 10% Raney nickel and 0.1% carbonized calcium. However, a comparison of the data presented therein together with that presented in U.S. Patent No. 3,741,776 (filed at approximately the same time by an assignee common to both inventions) and the cellobiitol data of the present invention cannot help but raise the question whether Yoshien et al. ever really developed cellobiitol at all. Also of interest to the present application is a technical publication of Towa Chemical Industry Co., Ltd., entitled "Sugar Collection." Cellobiose and cellobiitol are disclosed as being development products (page 5) which the company has plans to manufacture and sell. Literature values for the melting points and specific rotation of cellobiitol are listed as 142 - 143 β C and [aj D 20 ■** -8°, respectively. SUMMARY OF THE INVENTION The present invention provides a reduced calorie bulking agent consisting essentially of cellobiitol suitable for incorporation into formulated foods. The material is crystalline and free flowing and formulated foods containing the bulking agent have approximately the texture, moisture retention capability, appearance and density of formulated foods containing the same percent by weight of sucrose. Cellobiitol has been found to be caloric which is contrary to Yoshien, supra, but it possesses less than 4 calories/gram which is the caloric content of sucrose. The invention also provides sweetened bulking agents comprising cellobiitol in combination with an amount of high potency sweeteners effective to render the bulking agent as sweet as an equal weight of sucrose. DETAILED DESCRIPTION The present invention provides bulking agents suitable for incorporation into formulated foods which are lower in calories through the absence of sucrose. These foods, through incorporation of a reduced calorie bulking agent, retain approximately the same texture, moisture retention capability, appearance and density found in formulated foods containing the same amount of sucrose. The bulking agent is crystalline and free-flowing and as a result it is not necessary to combine it with materials such as modified starch in order to obtain a freely flowing product. Sweetened bulking agent compositions are provided which comprise cellobiitol in combination with an amount of high potency sweetener(s) which may be selected so as to render the sweetener/bulking agent mixture as sweet as an equal weight of sucrose. Such sweetened bulking agents may then be added to formulated foods to provide the taste, texture, moisture retention, appearance and density characteristics normally associated with sucrose yet without the associated calories. In the present invention, cellobiitol is produced according to a method that yields a pure product. Layton ('290) for example, discloses a process that results in the formation of six iso ers of glucosylsorbitol, one of which is cellobiitol. The isomer mixture is difficult to crystallize. Moreover, the process also generates a bulking agent with other impurities such as residual sorbitol and other carbohydrates. These impurities are undesirable and further isolation and purification steps are required that are unnecessary in the present invention. The pure form of cellobiitol disclosed herein also possesses superior solubility and bulking properties. The bulking agent of the present invention is produced through the reduction of cellobiose in the presence of a catalyst and water under pressure and elevated temperatures. Suitable catalysts include Raney nickel, platinum, platinum oxide, rhodium and palladium with Raney nickel being the preferred embodiment of this invention. The reaction may be carried out at temperatures ranging from approximately 25.0° to 100.0°C under pressures of from approximately 14.7 to 3000 psi. The specific temperature and pressures utilized are variables of each other, as well as functions of time that the reaction is run. The reduced calorie bulking agents of the invention may be added directly to formulated foods as a separate ingredient and an appropriate high potency sweetener may likewise be added as a separate ingredient to accomplish the same final effect as sucrose in formulated foods. Growth trial studies in animals have shown cellobiitol to be lower in calories compared to sucrose. Therefore the use of the present bulking agent, when sweetened with a high potency sweetener such as aspartame, will contain fewer calories than sugar. High potency sweeteners useful with the present invention include saccharin, cyclamate, acesulfame-K, alitame, sucralose, thaumatin, neohesperidin dihydrochalcone, stevioside and the like. Particularly preferred is the use of aspartame (alpha-L-aspartyl-L- phenylalanine methyl ester). The bulking agents of the present invention may be combined with various high potency sweetening agents in any desired proportion. The bulking agents may be subjected to drying procedures such as spray-drying, vacuum-drum drying or other techniques known in the art. The bulking agent of the present invention can conveniently be incorporated into formulated foods such as candy, cookies, ice cream, pastries, cakes, jellies, preserves, chocolate coatings, puddings, soft drinks, syrups and the like. By combining the bulking agent with a high potency sweetener such as aspartame, a sweetened bulking agent product is possible that can replace sucrose altogether and make foods that are otherwise prohibitively high in calories less fattening and non-cariogenic. The following examples are illustrative of methods of producing the bulking agent of the present invention and of incorporating the bulking agent into formulated foods in an effort to describe and teach the manner in which the invention disclosed may best be practiced. These are for illustration only and since other minor variations of methodology or ingredients to the basic concept of the invention are possible, they are not to be construed as limiting the spirit and scope of the claims. Example 1 To a solution of cellobiose (8.50 g, 25 mmol) in 75 ml of water is added 1.3 g of Raney nickel and the mixture is shaken under a hydrogen pressure of 1460 psi at 75°C for 48 hours. The resulting solution is then concentrated to an oil. Water (96 ml), methanol (100 ml), and ethanol (120 ml) are mixed with the oily syrup, which then results in the crystallization of cellobiitol as a white solid. The crystals can be separated from the mother liquor by one of any number of methods known in the art, yielding a substantially pure product. Cellobiitol having an empirical formula c i 2 H 2 °ιι as calculated to have an elemental composition; C, 41.86; H. 7.03. The product of this reaction exhibited the elemental composition: C, 41.67; H, 7.14. Example 2 The cellobiitol useful as a low-calorie bulking agent in the practice of the present invention was produced by the standard method of hydrogenation of cellobiiose in the presence of a catalyst and water as described in Example 1. The compound, as set forth by the following formula was found to be highly pure. A quantitative purity check was done on the above compound and that data that was obtained is shown below: HPLC 100% using the PAD detector (electrochemical) Mobile Phase : 0.15 M NaOH, 100% H 2 0 Stationary Phase: Dionex AS6 Flow Rate : 1.0 mL/ in Example 3 The relative sweetness of cellobiitol was compared with that of sucrose, maltitol and dextrose and a statistical analysis was performed on the data gathered from the impressions of eight independent judges as follows: TABLE 1 TOTAL 24 14 10 The data were treated as arising from a replicated, balanced incomplete block design with rank data. A rank value of one was assigned to the sample that was evaluated as being less sweet in each pair. A rank value of two was assigned to the sweeter sample in each pair. A Friedman type statistic, appropriate for BIBD designs, was used to determine if, overall, there were any differences among the rank sums of the four samples. The value of the test statistic was T = 37, which is highly significant when compared to the critical values of a chi-squared statistic with three degrees of freedom (e.g., the alpha = 0.05 critical value of a chi-squared (3) = 7.8). The individual rank sums of the samples were: Sucr. Malt. Dext. Cello. 48 A 38 B 34 B 24 C where larger values indicate greater sweetness. The rank sums were compared using a 95% LSD multiple comparison procedure. Two rank sums were declared to /04609 -10- be significantly different at the 95% level if they differed by more than LSD(95%) = 7.8. Rank sums not followed by the same letter in the table, above, are significantly different at the 95% confidence level* The findings, based on the eight judges who have completed all six paired comparisons, are as follows: 1) Sucrose is significantly sweeter than all of the remaining compounds in the study. 2) The data would indicate there is no significant difference in sweetness between maltitol and dextrose, but both of these compounds are sweeter than cellobiitol. 3) Cellobiitol is significantly less sweet than all of the remaining compounds in the study. Cellobiitol Study Results of the Rank-Sum Analysis of the Relative Sweetness of 10% Solutions of Sucrose, Maltitol, Dextrose, and Cellobiitol (Non-overlapping LSD Intervals Indicate that Samples are Significantly Different) Sweeter 50 40 E s tn 30 Less Ctiiobntoi Dt-trose fc ititol Sucrose Sweet Example 4 The solution viscosity characteristics of cellobiitol were studied at various temperatures. The viscosity of a 70% (w/w) solution of cellobiitol in water was measured with a Brookfield Viscometer Model LVT, using a Small Sample Adapter (SSK) accessory. Measurements were made starting at 22°C and at various higher temperatures as noted in the table below. A thin layer of DC-200 silicone oil was added to the surface of the solution to prevent water loss. Temperature Viscosity (Cps) 22 Θ C 30 e C 143.8 40°C 77.8 50 β C 45.0 59°C 29.5 70°C 19.0 It was noted that the cellobiitol solution crystallized at 24°C and, as it is apparent above, no viscosity value was therefore obtainable at 22°C. Heating the solution to 70°C gave a clear solution. Example 5 The solubility of cellobiitol was determined by stirring an excess of the sample in water at 25°C. Several aliquots were removed at periodic intervals. These aliquots were filtered and analyzed by HPLC. During the last 3 hours, out of the total 6 hours of stirring, there was not much change recorded in the concentration of sample in solution. The mean concentration during the last 3 hours is reported as the solubility of the compound. The solubility at 25°C in water = 51% w/w. Example 6 The solubility of cellobiitol at 70°C was also determined by stirring a suitable quantity of water and a known quantity of the sample in a vial kept in a water bath at 70°C. Additional small portions of water and the sample were added until the last addition of the sample (ca. 1% of the total sample weight) did not dissolve completely. The solution was cooled and weighed. The difference in the weight of the solution and the total weight of the sample added is reported as the solubility of the compound expressed in percent of the total solution weight. The solubility at 70°C in water • = 71% w/w. Example 7 PRESERVES PROCEDURE: The following lists of ingredients are given for the preparation of strawberry jelly and strawberry preserves and are mixed according to their respective proportions. The cellobiitol bulking agent of Example 1 is dissolved by heating in distilled water. Micrσcrystalline cellulose and carboxymethylcellulose are added separately until mixed well. All ingredients but the aspartame sweetener are then mixed in and the temperature is maintained at 180°F. Any water lost during the heating period is replaced. The mixture is cooled and the sweetener is added at 115°F. It is then packed in a canning jar. STRAWBERRY JELLY Ingredients Parts by Weight Water Cellobiitol Strawberry Juice Microcrystalline Cellulose (Avicel RC-591) Natural Flavor Carrageenan DG Cellulose 7MF Aspartame Fumaric Acid Potassium Citrate Carrageenan GH Citric Acid Color Potassium Sorbate Sodium Benzoate Artificial Flavor 400.00 STRAWBERRY PRESERVES Ingredients Parts by Weight Water 228.55 Cellobiitol 80.00 Quick Frozen Strawberries 80.00 Microcrystalline Cellulose (Avicel RC-591) 3.20 Natural Flavor 3.00 Carrageenan DG 1.28 CMC 7MF 1.20 Aspartame 1.00 Fumaric Acid 0.48 Potassium Citrate 0.44 Carrageenan GH 0.32 Citric Acid 0. 32 Color 0, 10 Potassium Sorbate 0, 08 Sodium Benzoate 0, 08 Artificial Flavor 0, 05 400.00 Example 8 CAKE Cakes are baked according to the recipe and instruction of Practical Baking, William J. Sultan, 2nd Edition, p. 356, AVI Publishing Co., Inc., Westport, Conn., 1969 which is hereby incorporated by reference. The proportions of ingredients remain the same, except for sugar which is replaced by the cellobiitol bulking agent of Example 1. The weights of ingredients used are as follows: Ingredients Parts by Weight Cellobiitol Saccharin Salt W.F. Milk Powder Cake Flour Shortening Water Fresh Egg White Baking Powder The cake ingredients are mixed 8 minutes and then baked for 30 minutes at 350°F in a 7.5 inch square aluminum pan. This cake has essentially the texture, luster and properties of cakes baked with 90.8 parts of sugar and 52.8 parts of water. Example 9 CANDY BASE The candy base is cooked according to the recipe and instructions given in Gelatin Gum Drops, Formula 391, p. 477, Candy Production: Methods and Formulas, Walter L. Richmond, The Manufacturing Confectioner, Chicago, Illinois, 1948. The recipe is reduced but the proportion of ingredients is maintained. The weights are given below: Ingredients Parts by Weight Agar-Agar 22.8 Corn Syrup 117.5 Gelatin 9.3 Water 192.3 Cellobiitol 130.8 454.7 A high potency sweetener, color and flavor are added as desired. After cooking, the candy is poured into a 4 by 8 inch square cake pan which has been dusted with potato starch to prevent sticking. The candy is air dried for 9 to 10 days and then sealed in a plastic wrap. The candy has the texture, lustre and mouthfeel of candies prepared from sucrose but contains fewer calories. Example 10 CHOCOLATE COATING Ingredient Parts by Weight Cocoa, 11% Fat Non-Fat Dry Milk Solids Salt Aspartame Coating Fat-Durkee Lecithin Cellobiitol in 87% Solution PROCEDURE: Cocoa, milk solids, salt, aspartame and sugar are dry mixed using a Waring Blender. Melted fat and lecithin is added to the dry blend and warmed to 140°F. To this mixture is added an 87% cellobiitol bulking agent solution. This is then blended thoroughly followed by cooling to approximately 100 β F. or to a point wherein the viscosity of the batch is proper for dipping or coating. Example 11 "TOOTSIE-ROLL" TYPE CANDY A B Cocoa 10.13 9.158 Aspartame 0.42 0.677 Cellobiitol in 90% Solution 65.40 65.693 Maltrin M050, Malto Dextrin 10.97 Starch, Instant 13.08 14.57 Vanilla Flavor - 1.248 Butter Flavor - 1.166 High Protein Concentrate - 10.4 PROCEDURE : Cocoa, aspartame and salt are dry blended in a Hamilton Beach mixer. Cellobiitol prepared according to Example 1, is dissolved in a solution with the maltodextrin and starch, warmed to 120°F and added to the dry blend mixture. The flavor is added and the texture is whipped to a soft pliable consistency with all the ingredients thoroughly distributed. The candy may be shaped and cut on flat surface and the individual pieces wrapped. The type A candy had 82% of its total sweetness attributable to aspartame, while the type B candy had 88% of its total sweetness attributable to the aspartame. Numerous modifications and variations in the practice of this invention are expected to be realized by those skilled in the art upon consideration of the foregoing descriptions of the preferred embodiments. Consequently, only such limitations should be placed upon the scope of the invention as appear in the appended claims.

Claims: WHAT IS CLAIMED IS: 1. A bulking agent of such purity that it is free of objectionable flavors and is easily converted to powdered or crystalline form that is suitable for incorporation into formulated foods, wherein the formulated foods containing the bulking agent have approximately the texture, moisture retention capability, appearance, and density of formulated foods containing the same percent by weight of sucrose, and wherein said bulking agent is cellobiitol. 2. A sweetened bulking agent suitable for incorporation into formulated foods, wherein formulated foods containing the sweetened bulking agent have approximately the same percent by weight of sucrose and wherein said sweetened bulking agent consists of cellobiitol and a high potency sweetener in amounts effective to render the sweetened bulking agent as sweet as an equal weight of sucrose. 3. The sweetened bulking agent of claim 2, wherein the high potency sweetener is selected from the group comprising cyclamate, saccharin, aspartame, thaumatin, acesulfame-K, alitame, sucralose and mixtures thereof. 4. Formulated food products wherein sucrose is replaced by an equivalent weight of a low calorie bulking agent which is cellobiitol. 5. The formulated food products of claim 4 wherein sucrose is replaced by an equivalent weight of a low calorie sweetened bulking agent comprising cellobiitol and a high potency sweetener. 6. The formulated food products of claim 5 wherein the high potency sweetener is selected from the group comprising cyclamate, saccharin, aspartame, thaumatin, acesulfame-K, alitame, sucralose and mixtures thereof. 7. A low calorie bulking agent useful in the incorporation of formulated foods as a replacement for sucrose wherein the bulking agent is produced by reducing a sufficient amount of cellobiose in the presence of a catalyst and water at a suitable temperature and pressure for an appropriate time. 8. The bulking agent of claim 7 wherein said catalyst is selected from the group comprising Raney nickel, platinum, platinum oxide, rhodium and palladium. 9. The bulking agent of claim 8 wherein said temperature is approximately 25.0 - 100.0°C. 10. The bulking agent of claim 9 wherein said pressure is approximately 14.7 - 3000 psi. 11. In a food, beverage or confectionery composition which contains sucrose, the improvement which comprises: substituting the sucrose with a sweetened bulking agent composition comprising: (a) cellobiitol and (b) a high potency sweetener. 12. The composition of claim 11 wherein the high potency sweetener is selected from the group comprising aspartame, cyclamate, saccharin, alitame, thaumatin, acesulfame-K, thaumatin, sucralose or mixtures thereof. 13. The composition of claim 12 wherein the high potency sweetener is aspartame. 14. The composition of claim 11 wherein the high potency sweetener is a combination of aspartame and acesulfame-K.

Inventors: DUBOIS GRANT E, MULLER GEORGE W, SINGER NORMAN S, DUBOIS, GRANT, E., MULLER, GEORGE, W., SINGER, NORMAN, S.
Applicants: NUTRASWEET CO, THE NUTRASWEET COMPANY
Application year: 1988
Main classification: A23L1
IPC codes: A23G3, A23L1