Food products comprising a slowly digestible or digestion resistant carbohydrate composition

Background of the invention

Various carbohydrates, such as various sugars and starches, are used in food products. Many of these carbohydrates are digested in the human stomach and small intestine. Dietary fiber in food products, in contrast, is usually not digested in the stomach and small intestine and is potentially fermented by microorganisms in the large intestine.

There is interest in developing non-digestible or only somewhat digestible materials suitable for use in food products in order to increase fiber content or reduce the calorie content of foods. These changes have some health benefits.

There is a need for edible substances that have low content of easily digestible carbohydrates and are used in place of or in addition to commonly used carbohydrate products in foods.

Outline of the invention

One aspect of the present invention is a method for producing an oligosaccharide composition. This method involves saccharification of starch to produce an aqueous composition comprising at least one oligosaccharide and at least one monosaccharide, and the aqueous composition is membrane filtered to produce a monosaccharide-rich stream and oligo. It involves forming a sugar-rich stream and recovering an oligosaccharide-rich stream. In one aspect of the invention, the oligosaccharide-rich stream is slow digestible in the human digestive system. As used herein, the term "slow digestibility" refers to the substantial amount of carbohydrates present in the stream (eg, at least about 50% on a dry solid basis, in some cases at least about 75% or at least about 90%. ) Is not digested at all in the human stomach and small intestine, or is only somewhat digestible. In another aspect of the invention, the oligosaccharide-rich stream is resistant to digestion by the human digestive system.

Both in vitro and in vivo tests can be performed to assess the rate and extent of carbohydrate digestion in humans. The "Englyst Assay" is an in vitro enzyme test used to assess the amount of carbohydrate material that is fast-digesting, slow-digesting or resistant to digestion (European Journal of Clinical Nutrition (1992) Volume 46 (Suppl). .2), pages S33-S50). At this time, any reference herein to a substance that is "at least about 50 percent by weight on a dry solid basis" or "mainly slow digestible" of the substance that is slow digestible is slow digestible or resistant in the Englyst assay. Means that the sum of the percentages classified as is at least about 50%. Similarly, any reference herein to a substance that is digestive resistant, "at least about 50 percent by weight on a dry solid basis" or "mainly digestive resistant", is classified as resistant in the Englyst assay. It means that the percentage is at least about 50%.

In one aspect of the process, the aqueous composition produced by isomerization following saccharification of starch comprises a mixture of dextrose, fructose, and oligosaccharides. This aqueous composition can be nanofiltered to separate it into a monosaccharide-rich permeate stream and an oligosaccharide-rich retainer stream. The oligosaccharide-rich stream comprises at least about 50% by weight or in some cases at least about 90% oligosaccharides on a dry solid basis. In some aspects of the process, the oligosaccharide-rich stream may further contain small amounts of dextrose and fructose. "Small amount" is used here to mean less than 50% by weight on a dry solid basis.

The process also includes, in some embodiments, one or more of the following steps: (1) contacting the oligosaccharide-rich stream with the isomerizing enzyme so that at least part of the dextrose is converted to fructose. The process of producing a stream rich in isomerized oligosaccharides in this way, (2) the oligosaccharide-rich stream is membrane-filtered to form a second monosaccharide-rich stream and about 90% by weight or more on a dry solid basis. A step of producing a second oligosaccharide-rich stream containing an oligosaccharide and a small amount of monosaccharides, (3) hydrogenating the oligosaccharide-rich stream to remove at least a portion of the monosaccharides therein. The step of converting to alcohol and thus producing a stream rich in hydride oligosaccharides, (4) contacting the stream rich in oligosaccharides with glucosidase enzymes, at least part of the residual monosaccharides present in the stream is oligo The step of producing a conversion product that is covalently attached to a sugar or other monosaccharide, and (5) diluting its color by contacting an oligosaccharide-rich stream with activated charcoal.

Another aspect of the invention is the process for producing sugar oligomers. The sugar oligomer composition produced by some aspects of this process is primarily digest resistant. In other embodiments, the composition is predominantly slow digestible. The process uses an aqueous feedstock composition that comprises at least one monosaccharide or linear sugar oligomer and has a solid concentration of at least about 70% by weight. The feed composition is heated to a temperature of at least about 40 ° C and is contacted with at least one catalyst that accelerates the rate of cleavage or formation of glucosyl bonds for a time sufficient to cause the formation of non-linear sugar oligomers. To. A production composition containing a higher concentration of non-linear sugar oligomer than the linear sugar oligomer is produced.

In one aspect of the process, at least one catalyst is an enzyme that accelerates the rate of cleavage or formation of glucosyl bonds. In another aspect of the process, at least one catalyst is an acid. In some embodiments of the process, acids and enzymes are used sequentially and the feedstock composition is treated first with the enzyme, then with the acid, or vice versa.

Another aspect of the invention is an edible carbohydrate composition (sometimes referred to herein as an oligosaccharide composition) that contains large amounts of oligosaccharides on a dry solid basis and is slow or resistant to digestion in the human digestive system. Is done). This composition can be produced by any of the above processes. "Large amount" is used here to mean at least 50% by weight on a dry solid basis.

In one embodiment, the oligosaccharide-rich stream has a solid content of 70.0% mass / mass (m / m) or more and a reduced sugar content represented as D-glucose, which is 20.0% m / m or more calculated on a dry basis. An edible carbohydrate composition is produced by a process having (dextrose equivalent). This aspect of the composition is classified as corn syrup under food labeling regulations. In another embodiment, the oligosaccharide-rich stream has a solid content of greater than 70.0% mass / mass (m / m) and a reduction represented as D-glucose, less than 20.0% m / m calculated on a dry basis. Has sugar (dextrose equivalent). This aspect is classified as maltodextrin under food labeling regulations.

Another aspect of the present invention comprises a large amount of linear and non-linear sugar oligomers on a dry solid basis (ie, 50% by weight or more on a dry solid base), the concentration of the non-linear sugar oligomers being linear sugars. An edible carbohydrate composition that is greater than the concentration of oligomers. In some aspects of the invention, the concentration of non-linear sugar oligomers in the composition is at least twice as high as the concentration of linear sugar oligomers.

Another aspect of the present invention is the method of producing food products. In the method, a food composition suitable for combination with a carbohydrate substance is prepared, and the slow-digesting or digestive-resistant edible carbohydrate composition as described above is combined with the food composition.

Another aspect of the present invention is a food product comprising the edible carbohydrate composition as described above. The food products include, for example, bread, cakes, cookies, crackers, extruded snacks, soups, frozen desserts, fried foods, pasta products, potato products, rice products, corn products, wheat products, dairy products, yogurts, confectionery, hard candy, etc. Nutrition bar, breakfast cereal or beverage.

In one aspect of the invention, the food product is a baked food, breakfast cereal, anhydrous coating (eg, ice cream compound coating, chocolate), dairy products, confectionery, jams and jellies, beverages, fillings, extruded and sheeted snacks, gelatin. Desserts, snack bars, cheese and cheese sauces, edible and water-soluble films, soups, syrups, sauces, dressings, creamers, icing, frosting, glazes, pet foods, tortillas, meat and fish, dried fruits, infant foods, butter and Selected from bleeding. Edible carbohydrate compositions, sometimes referred to herein as oligosaccharide compositions, can be present in food products for one or more purposes, eg, as a complete or partial substitute for solid sweets, or as a source of dietary fiber.

Another aspect of the invention is a method of controlling blood glucose in a diabetic mammal. The method provides mammals with food products such as those described above in various embodiments.

Explanation of specific aspects

One aspect of the present invention is the process of making a slow-digesting or digestive-resistant carbohydrate composition (eg, a sugar oligomer composition) suitable for use in foods.

Both in vitro and in vivo tests can be performed to assess the rate and extent of carbohydrate digestion in humans. The "Englyst Assay" is an in vitro enzyme test used to assess the amount of carbohydrate material that is fast-digesting, slow-digesting or resistant to digestion (European Journal of Clinical Nutrition (1992) Volume 46 (Suppl). .2), pages S33-S50).

The term "food" is used broadly here, including various substances that can be ingested by humans, such as beverages and pharmaceutical capsules or tablets.

The terms "oligosaccharide" and "sugar oligomer" are used herein to refer to sugars containing at least two sugar units, such as sugars having a degree of polymerization of about 2-30 ("DP"). ing. For example, the disaccharide has a DP of 2.

In some aspects of the invention, the aqueous feedstock composition may contain at least one monosaccharide and at least one linear sugar oligomer, each containing several. In many cases, monosaccharides and oligosaccharides make up at least about 70% by weight on a dry solid basis of the feedstock composition. Having as high a concentration of monosaccharides as possible is usually useful as a starting material in order to maximize the production of the desired oligomers. High solid concentrations tend to produce high molecular weight products by directing the equilibrium from hydrolysis towards the condensation (condensation) direction. Therefore, the water content of the starting material is preferably relatively low. For example, in some embodiments, the feedstock composition comprises at least about 75% by weight dry solid ("dry solid" is sometimes abbreviated here as "ds"). In some cases, the feedstock composition will contain approximately 75-90% by weight solids and will usually exhibit the appearance of a viscous syrup or moist powder at room temperature.

Examples of suitable starting materials are syrups obtained by hydrolysis of starch, such as dextrose greens syrup (ie, a stream of mother liquor from dextrose monohydrate crystallization), other dextrose syrups, corn syrup and maltodextrin There are solutions of, but not limited to them.

If the feedstock composition contains maltodextrin, the process hydrolyzes the maltodextrin to form a hydrolyzed sugar solution and at least about 70% of the hydrolyzed sugar solution to form the feedstock composition. It may also include the step of concentrating to a dry solid. Concentration of the feedstock and contact with the catalyst may be performed simultaneously, or concentration may be carried out prior to contacting the feedstock composition with the catalyst.

The feedstock composition is contacted with at least one catalyst over various time periods. In some cases, the contact period is at least about 5 hours. In some aspects of the invention, the feedstock composition is contacted with at least one catalyst for about 15-100 hours. In other embodiments, shorter contact times are used at higher temperatures, sometimes less than an hour.

In one aspect of the invention, enzymatic conversion is used to produce non-linear oligosaccharides. Enzymes, for example, accelerate the rate of cleavage of α1-2, 1-3, 1-4 or 1-6 glucosyl bonds to form dextrose residues. One suitable example is a glucoamylase enzyme composition, eg, a commercially available enzyme composition called glucoamylase. Such compositions can also contain enzymes other than pure glucoamylase in certain amounts, and it cannot be determined that it is actually glucoamylase itself that catalyzes the desired production of non-linear oligosaccharides.

Therefore, the feedstock composition is contacted with glucoamylase or any other enzyme that acts on the dextrose polymer. The amount of enzyme is appropriately about 0.5 to 2.5% by volume of the feedstock composition. In some embodiments of the process, the feedstock composition is maintained at about 55-75 ° C, or in some cases about 60-65 ° C, upon contact with the enzyme. At this temperature, depending on the water content, the substance becomes a liquid or a mixture of liquid and solid. Optionally, the reaction mixture is mixed or stirred to disperse the enzyme. The reaction mixture is maintained at the desired temperature for the time required to achieve the desired conversion to non-linear oligomers. In some embodiments of the process, the feedstock composition is contacted with the enzyme for about 20-100 hours prior to inactivation of the enzyme, or in some cases for approximately 50-100 hours prior to deactivation. Techniques for inactivating glucoamylase are well known in the art. On the other hand, instead of inactivating the enzyme, it may be separated and recycled by membrane filtration.

The resulting composition has a high concentration of non-linear oligosaccharides, such as isomaltose. This production composition contains a higher concentration of non-linear sugar oligomers than linear sugar oligomers. In some cases, the concentration of non-linear sugar oligomers in the final composition is at least twice as high as the concentration of linear sugar oligomers.

Gastrointestinal enzymes easily recognize and digest carbohydrates in which dextrose units are α-bonded (1 4) ("linear" bonds). Replacing these bonds with other bonds (eg α (1 3), α (1 6) ("non-linear" bonds) or β bonds) significantly reduces the ability of gastrointestinal enzymes to digest carbohydrates. .. This allows carbohydrates to pass through the small intestine, largely unchanged.

In some cases, the production composition comprises a small amount (ie, less than 50 wt% on a dry solid basis, usually a fairly low concentration) of residual monosaccharides. The process includes the removal of at least a portion of the residual monosaccharides (and possibly other species) from the produced composition by membrane filtration, chromatographic fractionation or digestion by fermentation. The separated monosaccharides are combined with other process streams, for example for the production of dextrose or corn syrup. On the other hand, the separated monosaccharides may be recycled into the feedstock composition.

Another aspect of the invention is a process involving acid conversion of monosaccharides. The starting material is similar to that described above for the enzymatic version of this process. Various acids are used, such as hydrochloric acid, sulfuric acid, phosphoric acid or combinations thereof. In some aspects of the process, the pH of the feedstock composition is sufficient to bring it to about 4 or less, or in some cases the pH of the feedstock composition is about 1.0-2.5 or about 1.5-2.0. The acid is added to the feedstock composition in an amount sufficient to make up. In some embodiments, the feedstock composition has a solid concentration of about 70-90% and the amount of acid added to the feedstock is about 0.05% -0.25% (w / w) acid solids in syrup dry solids. The feedstock composition is maintained at a temperature of about 70-90 ° C upon contact with the acid. As in the enzymatic version of the process, the reaction conditions are maintained for a time sufficient to produce the desired oligomer, which in some embodiments of the process is about 4-24 hours.

In one specific embodiment, the solid concentration of the feedstock composition is at least about 80% by weight, and the acid is added to the feedstock composition in an amount sufficient to bring the pH of the composition to about 1.8. The composition is maintained at a temperature of at least about 80 ° C for about 4-24 hours after it has been contacted with the acid.

In another specific embodiment, the feedstock composition has a solid concentration of about 90-100% by weight and the feedstock composition is at a temperature of at least about 149 ° C (300 ° F) after it has been contacted with the acid. Maintained for about 0.1-15 minutes. The acid used to process the feedstock may be a combination of phosphoric acid and hydrochloric acid (at the same concentration as above). In one specific embodiment, the contact of the feedstock composition with the acid is carried out in a continuous pipe / flow-through reactor.

The most abundant glycosidic bond in starch is the α-1,4 bond, which is the most broken bond during acid hydrolysis of starch. However, given that acid-catalyzed conversion (condensation) occurs between any two hydroxyl groups and that there are various combinations and geometries available, the probabilities of forming α-1,4 bonds are comparative. Small. The human digestive system contains α-amylase, which easily digests the α-1,4 bonds of starch and corn syrup. Replacing these bonds with bonds that are not recognized by the enzyme in the digestive system allows the product to pass through the small intestine, largely unchanged.

The sugar distribution obtained from the acid treatment is considered to be slightly different from that in the case of the enzyme treatment. These acid-catalyzed condensation products are considered to be less recognizable by enzymes in the human gastrointestinal tract than enzyme products.

Acid treatment proceeds unlike enzyme treatment. Enzymes hydrolyze linear oligomers quickly to form non-linear oligomers, while acids cause a decrease in linear oligomers and an increase in non-linear oligomers at comparable rates. Dextrose is formed rapidly by enzymatic hydrolysis of oligomers and is slowly consumed when non-linear condensation products are formed, while acid slowly increases the concentration of dextrose.

In some cases, hydrogenation follows enzyme or acid conversion. The hydrogenated product should have a lower calorie content than current commercial hydrogenated starch hydrolysates. In one aspect, hydrogenation is used to decolorize the production composition without substantially altering its dextrose equivalent (DE).

In one version of this process, enzymes and acids are used sequentially in either order. For example, at least one catalyst used in the first treatment is an enzyme, then the production composition is contacted with an acid that accelerates the cleavage or formation of glucosyl bonds. On the other hand, at least one catalyst used in the first treatment may be an acid, and then the production composition may be contacted with an enzyme that accelerates the rate of cleavage or formation of glucosyl bonds.

In aspects of the process in which acid treatment is used first and then enzyme treatment, the acid is phosphoric acid, hydrochloric acid or a combination thereof. In this embodiment, after contact with the enzyme, the composition is contacted with an ion exchange resin. After contact with the ion exchange resin, the concentration of the sugar oligomer having a degree of polymerization of at least 3 in the composition is at least about 50% by weight on a dry solid basis.

The production composition produced by treatment with acid, enzyme or both has an increased concentration of non-linear sugar oligomers on a dry solid basis. In some cases, the concentration of non-linear sugar oligomers having a degree of polymerization of at least 3 (DP3 +) in the production composition is at least about 20% by weight, at least about 25%, at least about 30% or at least on a dry solid basis. It is about 50%. In some embodiments, the concentration of non-linear sugar oligomers in the production composition is at least 2-fold higher than the concentration of linear sugar oligomers.

In one specific embodiment, the concentration of non-linear sugar oligomers in the production composition is at least about 90% by weight on a dry solid basis and the concentration of isomaltose is at least about 70% by weight on a dry solid basis.

The production composition usually contains a small amount (typically less than 50% by weight on a dry solid basis, usually much less) of residual monosaccharides. Optionally, at least a portion of the residual monosaccharide (and other species) is separated from the oligomer (eg, by membrane filtration, chromatographic separation or digestion in fermentation) and the monosaccharide stream is recycled to the process feed. In this way, the simple sugar syrup is converted into a high value food additive.

Oligomer-rich syrups produced by the processes described herein are used in foods to increase dietary fiber. The syrup contains natural oligosaccharides that have both low viscosity and hypoglycemic index. Many of these oligomers contain at least one non-α-1,4 bond. They must be highly fermentable in the large intestine, which adds health benefits to them as prebiotics. In some embodiments of the invention, at least about 50% by weight of the produced composition on a dry solid basis is slow digestible.

Many of the beneficial effects of oligosaccharides as dietary fiber have been documented. Sugar oligomers, which resist digestion in the small intestine but are fermentable in the large intestine, have been shown to have several beneficial effects, such as lowering cholesterol, reducing blood glucose and maintaining gastrointestinal health.

FIG. 1 shows an aspect of a process in which the conversion technique can be utilized. The process is initiated with starch, such as vegetable starch. Common cornstarch is one good example. If the starting starch has a relatively high purity, the process usually works more efficiently. In one aspect, the high purity starch contains less than 0.5% protein on a dry solid basis. Although some of the following description focuses on corn, it should be understood that the present invention can also be applied to starches derived from other sources, such as potatoes and wheat.

As shown in FIG. 1, starch 10 has an acid 12 added to it, and then gelatinized 14 with a starch cooker, eg, a jet cooker in which starch granules are contacted with the stream. In one version of this process, the starch slurry adjusted to a pH target of 3.5 with the addition of sulfuric acid is quickly mixed with the stream in a jet cooker and 149-152 ° C (300-305 ° F) at the tailline for 4 minutes. Is kept in. The gelatinized starch 16 is hydrolyzed by exposure to an acid at a high temperature during jet cooking 18. Hydrolysis reduces the molecular weight of starch and results in an increase in the proportion of monosaccharides and oligosaccharides in the composition (as mentioned above, the term "oligosaccharide" refers to sugars comprising at least two sugar units, such as about. Used here to refer to sugars with a degree of polymerization (DP) of 2-30). A neutralizer 20, such as sodium carbonate, is added to stop acid hydrolysis, and then the composition can further depolymerize by contacting it with hydrolase 22. Suitable enzymes include α-amylase, eg Termamyl commercially available from Novozymes. This enzymatic hydrolysis further increases the proportion of monosaccharides and oligosaccharides present in the composition. The overall result of hydrolysis by acid and enzyme treatment is to saccharify starch. The saccharified composition can be isomerized to alter the monosaccharide profile, eg to increase the concentration of fructose.

The saccharified composition 26 can then be purified, for example by chromatographic fraction 28. In one embodiment using continuous pseudo-moving layer (SSMB) chromatography operation, a solution of mixed sugar is fed to a column filled with resin beads. Depending on the chemical properties of the resin, some of the sugars interact strongly with the resin, resulting in a delayed flow through the resin compared to sugars that interact weakly with the resin. This fractionation can result in one stream 30 with a high content of monosaccharides such as dextrose and fructose. High fructose corn syrup is an example of such a flow. Fractionation is a raffinate stream that has a relatively high concentration of oligosaccharides (eg, about 5-15% oligosaccharides on a dry solid base (dsb)) and also contains lower concentrations of monosaccharides such as dextrose and fructose. 32 (ie, a component that moves quickly through the resin layer) is also produced. Although the term "stream" is used herein to describe some part of the process, it should be understood that the process of the invention is not limited to continuous operation. This process can also be done in batch or semi-batch method.

Raffinate 32 can be further separated by membrane filtration 34, eg nanofiltration, and optionally by diafiltration. For example, these filtration steps can be performed using a Desal DK spiral-wound nanofiltration cartridge at a pressure of approximately 500 psi and a temperature of 40-60 ° C. The fractionation described in step 34 can also be performed by continuous pseudo-moving layer chromatography (SSMB). Membrane filtration produces a permeation substance 36 (ie, a component that passes through the membrane) primarily containing monosaccharides and a retention substance 38 (ie, a component rejected by the membrane) primarily containing oligosaccharides (ie, components rejected by the membrane). As used herein, "mainly" means that the composition is on a dry solid basis and contains more of the listed ingredients than any other ingredient). The permeate 36 may be combined with a monomer stream 30 (eg, high fructose corn syrup). The permeating material is a monosaccharide-rich stream and the retaining material is an oligosaccharide-rich stream. In other words, nanofiltration concentrates monosaccharides with oligosaccharides and permeates as retention substances compared to nanofiltration feeds.

The retainer 38, which may be described as oligosaccharide syrup 40, has a sufficiently high content of slow-digesting oligosaccharides (eg, at least about 50% by weight dsb, or in some cases at least about 90%). As such, it is dried or easily evaporated into concentrated syrups for use as a material in foods. However, in many cases it will be useful to further process and purify this composition. Such purification involves one or more of the following steps (Figure 1 shows four such purification steps 42, 44, 46 and 48 as options, but if two or more of these steps are used in this process Should be understood).

Oligomer syrup 40 may be subjected to other fractions 42, such as membrane filtration, eg second nanofiltration, to remove at least some of the residual monosaccharides such as fructose and dextrose. Suitable nanofiltration conditions and equipment are as described above. This nanofiltration produces a permeate, which is a second monosaccharide-rich stream, which may be combined with the monomer stream 30. On the other hand, further fractionation 42 can also be performed by chromatographic separation, for example pseudomixed layer chromatography.

Syrup 41 can be isomerized 44 by contacting it with an enzyme such as dextrose isomerase. It converts at least some of the residual dextrose present to fructose, which is more beneficial under certain circumstances.

As mentioned above, the syrup can be treated with an enzyme or acid to cause conversion or repolymerization 46, where at least some of the monosaccharides still present are covalently attached to other monosaccharides or oligosaccharides. Thus, the residual monomer content of the syrup can be further reduced. Enzymes suitable for use in this step include glucosidases such as amylase, glucoamylase, transglucosidase and pullulanase. Cellulase enzymes can produce beneficial conversion products for some applications.

The syrup can be hydrogenated 48 to convert at least a portion of the residual monosaccharide to the corresponding alcohol (eg, to convert dextrose to sorbitol). When hydrogenation is involved in the process, it is typically (but not always) the final purification step.

The purified oligomeric syrup 49 produced in one or more of the above purification steps may then be decolorized 50. Decolorization can be performed, for example, by microfiltration following treatment with activated carbon. In a continuous flow system, the syrup stream is sent to a column filled with granular activated carbon for decolorization. The bleached oligomeric syrup is then evaporated to, for example, greater than about 70% dry solid (ds) 52 to accommodate high content oligosaccharides (eg, greater than 90 wt% dsb, in some cases greater than 95%) and corresponding. Produces a product consisting of low monosaccharide content. The product comprises multiple sugars that are slowly or incompletely digested if not completely indigestible in humans. These sugars include isomaltose, panose and branched oligomers with a degree of polymerization of 4 or higher.

Process conditions may be modified to recover most of the maltose in the feed feed to the monomer-rich stream (30,36) or oligomer-forming logistics. For example, a slightly wider pore size nanofiltration membrane operated at a pressure of less than 500 psi, such as Desal DL, is used to increase the amount of maltose in a monomer-rich stream.

The product is suitable as a food material and is slow-digesting or resistant to digestion in the human digestive system. As mentioned above, some components of the product are virtually completely indigestible in the human stomach and small intestine. Depending on the starch source used, the products are classified in some embodiments as corn syrup or wheat syrup, as those terms are used in food labeling. When a wider pore size is used in nanofiltration, higher molecular weight oligomeric syrup products classified as maltodextrin are obtained.

The oligosaccharide-containing syrup produced in this process is added to foods as a substitute or supplement for common carbohydrates. Thus, another aspect of the invention comprises a large amount of linear and non-linear sugar oligomers on a dry solid basis, the concentration of the non-linear sugar oligomers greater than the concentration of the linear sugar oligomers. It is a food product containing. Specific examples of foods in which syrup is used include processed foods such as bread, cakes, cookies, crackers, extruded snacks, soups, frozen desserts, fried foods, pasta products, potato products, rice products, corn products, wheat products, milk. There are products, yogurt, sweets, pancakes, nutrition bars, breakfast cereals and beverages. Food products containing oligosaccharide syrup have a lower glycemic response, lower glycemic index and lower glycemic load than similar food products that use common carbohydrates such as cornstarch. In addition, at least some of the oligosaccharides are digested in the human stomach or small intestine to a very limited extent or not at all, thus reducing the caloric content of food products. The syrup is also a suitable source of dietary fiber.

The digestive resistant oligomeric syrup as described above is used as a syrup as a material in food products, or it is first concentrated to form a solid syrup. In both, it is used in several ways. As mentioned above, this syrup can be derived from various starch sources, such as corn. Although this patent uses the phrase "digestive resistant corn syrup" or "resistant corn syrup" (sometimes abbreviated as "RCS") in some cases, the present invention is a corn-derived syrup or It should be understood that it is not limited to solid syrup.

Digestive resistant oligomeric syrups are added to food products as a soluble fiber source. It can increase the fiber content of food products without having a negative effect on flavor, mouthfeel or texture.

The function of digestive resistant oligomeric syrups is similar to that of corn syrups and sugars, which makes them suitable for complete or partial substitution of various nutritional sweeteners in food products. For example, resistant syrup is used in food products as a full or partial substitute for sucrose, high fructose corn syrup (HFCS), fructose, dextrose, regular corn syrup or solid corn syrup. As one embodiment, digestive resistant syrups or digestive resistant syrup solids are used in place of other solid sweeteners from a 1: 1 base to a complete substitute for sugar solids. At high solid sweetness substitute levels, the sweetness of the food product is reduced, but the mouthfeel and flavor release remain substantially the same, while the sugar and calorie content is reduced. Moreover, digestive resistant syrups are used in food formulations as bulking agents, fat substitutes, flours or other ingredients. On the other hand, digestive resistant syrups may be used in food products in combination with sweeteners such as sucrose, HFCS or fructose and do not change the overall sweetness of the food products. As another example, digestive resistant syrups are used in food products in combination with sucralose or other high intensity sweeteners and can replace sweeteners without changing the sweetness or mouthfeel of the food product.

Digestive resistant oligomeric syrups increase fiber content in food products, increase physiological benefits from product consumption, reduce calorie content, and / or enhance the nutritional profile of products, resistant starch, polydextrose or Used in food products in combination with other fiber sources.

Digestive resistant oligomeric syrups are used in food products in combination with bulking agents such as sugar alcohols or maltodextrin to reduce calorie content and / or enhance the nutritional profile of the product. The syrup is also used as a partial substitute for fat in food products.

Digestive resistant oligomeric syrups are used in food products as softeners or texturers to increase crispness or snapping, improve appearance, and / or improve rheology of dough, butter or other food compositions. .. The syrup is also used in food products as a moisturizer to extend product shelf life and / or produce a softer, more moist texture. It is also used in food products to reduce water activity or to fix and control water. Additional uses of the syrup include: to replace egg wash and / or to increase the surface gloss of food products, change the starch gelatinization temperature, change the texture of the product, and enhance the browning of the product. ..

In at least some aspects of the invention, the digestive resistant oligomeric syrup has one or more of the following advantages: high stability that makes it relatively easy to incorporate into food compositions such as butter and dough; Stability under high temperature and / or acidic pH (some other soluble fibers, such as inulin, are not very stable), low sweetness, clean flavor and clear color. Due to the nature of the syrup, the food products in which it is used can be given a clean label. In some aspects of the invention, the digestive resistant oligomeric syrup contains about 2 calories / gram (dsb) and can reduce the total calorie content of the food product.

The digestive resistant oligomeric syrups of the present invention are used in various types of food products. One type of food product in which the syrup can be very useful is bakery products (ie, baked foods) such as cakes, brownies, cookies, cookie crisps, muffins, breads and sweet dough. Regular bakery products are relatively high in sugar and high in total carbohydrates. The use of digestive resistant syrup as an ingredient in bakery products helps reduce sugar and carbohydrate levels and total calories while increasing the fiber content of bakery products.

There are two main categories of bakery products: yeast fermentation and chemical fermentation. In fermented yeast products such as donuts, sweet dough and bread, digestive resistant oligomeric syrups are used in place of sugars, but small amounts of sugars are still desired as they are required for yeast fermentation substrates or crust browning. Digestive resistant oligomeric syrup solids (eg, digestive resistant corn syrup solids) will be added along with other dry ingredients in a manner similar to nutrient dry sweeteners and will not require special treatment. Resistant corn syrup is added along with other liquids as a direct substitute for syrup or liquid sweeteners. The dough is then subjected to processing, including mixing, fermentation, splitting, shaping or extrusion into loaf or form, proofing, and baking or frying, under conditions commonly used in the baking industry. The product is baked or fried under conditions similar to traditional products. Bread is usually baked at a temperature of 420 ° F to 520 ° F for 20 to 23 minutes, and donuts are fried at a temperature of 400 to 415 ° F, but other temperatures and times are also used. High-intensity sweeteners can also be added to the dough as needed to obtain the optimum sweetness and flavor profile.

Chemically fermented products typically have more sugar and may contain higher levels of resistant corn syrup / solids. The final cookie may contain 30% sugar, which can be completely or partially substituted with resistant corn syrup / solids. These products have a pH of, for example, 4 to 9.5. The water content is, for example, 2 to 40%.

The resistant corn syrup / solid is readily formulated and added to the fat at the beginning of the mixing in some way similar to the syrup or dry sweetener it is used instead during the creaming step. The products are mixed and then molded, for example by sheeting, rotary cutting, wire cutting, or by other molding processes. The product is then baked under typical baking conditions, for example at 200-450 ° F.

Resistant corn syrup / solids are also used to form sugar glass in an amorphous state, to attach particles to the baked product, and / or to form a film or coating that enhances the appearance of the baked product. Be done. Resistant corn syrup solids, like other amorphous sugars, form glass when heated and then cooled to temperatures below their glass transition temperature.

Another type of food product in which the syrup is used is breakfast cereal. For example, the resistant corn syrup according to the invention is used to replace all or part of sugar in extruded cereal pieces and / or coatings on the outside of those pieces. The coating is typically 30-60% of the total weight of the final serial piece. The syrup can be, for example, a spray or drizzle. It is applied by on). The formulation for coating may be as simple as a 75% solution of resistant corn syrup. Resistant corn syrup may be blended with various proportions of sugar or with other sweeteners or polyols. Excess water is then evaporated in a low heat oven. In the extrusion piece, the resistant corn syrup solid may be added directly with the drying material, or the syrup may be metered into the extruder with water or separately. A small amount of water may also be added to the extruder, which is then passed through various zones from 100 ° F to 300 ° F. Optionally, other fiber sources such as resistant starch may also be used in the extruded piece. Resistant corn syrup can be used to create a texture that is different from other fiber sources. When used alone or in combination with other fibers, the texture can be varied for product versatility.

Another type of food product in which the syrup is used is a dairy product. Examples of dairy products in which it is used include yogurt, yogurt drinks, milk drinks, flavored milk, smoothies, ice creams, shakes, cottage cheese, cottage cheese dressings and dairy desserts such as quag and whipped mousse type products. This includes dairy products intended for direct consumption (eg, packaged smoothies), as well as those intended to be blended with other ingredients (eg, blended smoothies). It is used for pasteurized dairy products, such as those that are pasteurized at temperatures between 160 ° F and 285 ° F. A complete substitute for sugar is possible in dairy products (within 24% of all formulas). Resistant corn syrup is usually stable at acid pH (milk beverages typically have a pH range of 2-8).

Another type of food product in which the syrup is used is confectionery. Examples of confectioneries in which it is used include hard candies, fondants, nougars and marshmallows, gelatin jelly candies or gummies, jellies, chocolate, licorice, chewing gum, caramel and toffee, chews, mint, tablet confectionery, and fruit snacks. For fruit snacks, resistant corn syrup can be used with fruit juice. Fruit juice exhibits most of the sweetness, and resistant corn syrup reduces total sugar and adds fiber. The syrup is added to the initial candy slurry and heated to the final solid content. The slurry is heated to 200-305 ° F to reach the final solid content. Acids are added before or after heating to a final pH of 2-7. Resistant corn syrup is used as a substitute for 0-100% of the sugar present and 1-100% of corn syrup or other sweeteners.

Other types of food products in which the syrup is used are jams and jellies. Jam and jelly are made from fruits. Jam contains fruit pieces, while jelly is made from fruit juice. Resistant corn syrup is used in place of sugar or other sweeteners as follows: Weigh fruits and juices into tanks. Premix sugar, resistant corn syrup and pectin. The drying composition is added to the liquid and cooked to a temperature of 214-220 ° F. Fill the jar with heat and retort for 5-30 minutes.

Another type of food product in which the syrup is used is a beverage. Examples of beverages in which it is used include carbonated beverages, fruit juices, concentrated juice mixes (eg, margarita mixes), clear water and beverage dry mixes. According to the use of the resistant corn syrup of the present invention, the transparency problem that arises when other types of fiber are added to the beverage can often be overcome. Complete substitution of sugar is possible (eg, up to 12% of all formulations). Due to the stability of the syrup at acid pH, it is used, for example, in beverages with pH in the range 2-7. Resistant corn syrup is used in cold processed beverages and pasteurized beverages.

Another type of food product in which the syrup is used is a high solid filling. Examples of high solid fillings in which it is used are snack bar, toaster pastries, donut and cookie fillings. High solid fillings are, for example, acid / fruit fillings or savory fillings. It is added to products that are consumed as-is or that are further processed by a food processor (additional baking) or consumer (bake stability filling). In some aspects of the invention, the high solid filling has a solid concentration of 67-90%. The solid may be completely substituted with resistant corn syrup, or it may be used as a partial substitute for other solid sweeteners present (eg, 5-100% of the current solid). Typically, fruit fillings have a pH of 2-6, while savory fillings have a pH of 4-8. The filling is prepared cold or heated within 250 ° F to evaporate to the desired final solid content.

Other types of food products in which the syrup is used are extruded and sheeted snacks. Examples of extruded and sheeted snacks in which it is used include puff snacks, crackers, tortilla chips and corn chips. In making extruded pieces, resistant corn syrup / solids are added directly with the dried product. A small amount of water is added to the extruder, which is then passed through various zones in the 100 ° F to 300 ° F range. This desiccant resistant corn syrup / solid is added at a level of 0-50% of the dry product mixture. Liquid resistant corn syrup is also added at one of the liquid outlets along the extruder. The product is either served with a low moisture content (5%) and then baked to remove excess water, or is served with a slightly higher moisture content (10%) and then fried to remove water. Cook. Baking is for 20 minutes at a temperature within 500 ° F. Baking is more typically at 350 ° F for 10 minutes. Flying is typically 350 ° F for 2-5 minutes. In sheeted snacks, resistant corn syrup solids are used as a partial substitute for other dry ingredients (eg, flour). It is 0-50% of dry weight. The product is dry mixed and then water is added to form a sticky dough. The product mix has a pH of 5-8. The dough is then sheeted and cut, then baked or fried. Baking is for 20 minutes at a temperature within 500 ° F. Flying is typically 350 ° F for 2-5 minutes. Another possible benefit from the use of resistant corn syrup is a fat reduction of as much as 15% in fried snacks when added as an internal ingredient or as an outer coating of fried foods.

Another type of food product in which the syrup is used is a gelatin dessert. Gelatin dessert ingredients are often sold as a gelling agent and as a dry mix with gelatin. The sugar solids are partially or completely substituted with resistant corn syrup solids in the dry mix. The dry mix is then mixed with water and heated to 212 ° F to dissolve the gelatin, then additional water and / or fruit is added to complete the gelatin dessert. Gelatin is then cooled and solidified. Gelatin can also be sold in storage stable packs. In that case, the stabilizer is usually carrageenan-based. As mentioned above, resistant corn syrup can be substituted within 100% of other solid sweeteners. The dry material is mixed into a liquid, then pasteurized, placed in a cup, cooled and solidified. The cup usually has a foil top.

Another type of food product in which the syrup is used is a snack bar. Examples of snack bars in which it is used include breakfast and meal substitute bars, nutrition bars, granola bars, protein bars and cereal bars. It is used in some part of the snack bar, for example in high solid fillings, bound syrups or fine granules. Complete or partial substitution of sugar in bound syrup is possible with resistant corn syrup. The bound syrup is typically 50-90% solid and is applied in a ratio of 10% bound syrup to 90% fine granules to 70% bound syrup to 30% fine granules. Binder syrup is obtained by heating a solution of a sweetener, bulking agent and other binder (eg starch) to 160-230 ° F (depending on the final solid required in the syrup). The syrup is then mixed with the granules to coat the granules and coat the entire matrix. Resistant corn syrup is also used for the granules themselves. It may be an extruded piece or it may be directly inflated or gun puffed. It may be used in combination with other cereal ingredients, cornmeal, rice flour or other similar ingredients.

Other types of food products in which the syrup is used are cheese, cheese sauce and other cheese products. Examples of cheeses, cheese sauces and other cheese products in which it is used include low milk solid cheeses, low fat cheeses and low calorie cheeses. In block cheeses, it helps to improve melting characteristics or reduce the effects of melting restrictions applied by other ingredients such as starch. It is also used in cheese sauces, for example as a bulking agent, as it replaces fats, milk solids or other typical bulking agents.

Another type of food product in which the syrup / solid is used is an edible and / or water-soluble film. Examples of films in which it is used include films used to wrap dry mixes for various foods and beverages intended to be dissolved in water, or spice films added to cooked foods that are still hot. There are films used to provide color or flavor. Other film applications include, but are not limited to, fruit and vegetable leathers and other flexible films.

Other types of food products in which the syrup is used are soups, syrups, sauces and dressings. A typical dressing is a 0-50% oil with a pH range of 2-7. It is cold or hot. It is mixed and then a stabilizer is added. Resistant corn syrup is readily added in liquid or dry form, along with other materials as needed. The dressing composition may also require heating to activate the stabilizer. Typical heating conditions are 170-200 ° F for 1-30 minutes. After cooling, oil is added to make a pre-emulsion. The product is then emulsified using a homogenizer, colloid mill or other high shear process.

The sauce has 0-10% oil and 10-50% total solids and has a pH of 2-8. The sauce is cold or hot. The ingredients are mixed and then heat processed. Resistant corn syrup is readily added in liquid or dry form, along with other materials as needed. Typical heating is 170-200 ° F for 1-30 minutes.

The soup is more typically 20-50% solid and is in the more neutral pH range (4-8). They may be dry mixes to which a dry resistant corn syrup solid is added, or liquid soups that are canned and then retort. In soups, resistant corn syrup is used within 50% solids, but a more typical use is to serve 5 g of fiber per serving.

The syrup may contain resistant corn syrup as a substitute for up to 100% sugar solids. Typically, it is 12-20% of the syrup on its raw base. Resistant corn syrup is added with water and then pasteurized and hot-filled (typically pasteurized at 185 ° F for 1 minute) to ensure safe and storage stability of the product.

Another type of food product in which the syrup is used is a coffee creamer. Examples of coffee creamers in which it is used include both liquid and dry creamers. The dry-blended coffee creamer can be blended with the following fat types: soy, coconut, palm, sunflower or canola oil, or commercially available creamer powder of butter fat. These fats may be dehydrogenated or hydrogenated. Resistant corn syrup solids are optionally added as a fiber source, along with fructo-oligosaccharides, polydextrose, inulin, maltodextrin, resistant starch, sucrose and / or conventional corn syrup solids. The composition may also contain high-intensity sweeteners such as sucralose, acesulfame potassium, aspartame or a combination thereof. These materials are dry blended to produce the desired composition.

Spray-dried creamer powder is a combination of fats, proteins and carbohydrates, emulsifiers, emulsified salts, sweeteners and anti-caking agents. The source of fat is one or more of soybeans, coconut, palm, sunflower or canola oil, or butter fat. The protein is sodium casein or potassium, milk protein, whey protein, wheat protein or soy protein. Carbohydrates may be resistant corn syrup alone or in combination with fructo-oligosaccharides, polydextrose, inulin, resistant starch, maltodextrin, sucrose or corn syrup. Emulsifiers are mono- and diglycerides, acetylated mono- and diglycerides, or propylene glycol monoesters. The salts are trisodium citrate, monosodium phosphate, disodium phosphate, trisodium phosphate, tetrasodium pyrophosphate, monopotassium phosphate and / or dipotassium phosphate. The composition may also contain high-intensity sweeteners such as sucralose, acesulfame potassium, aspartame or a combination thereof. Suitable anti-caking agents include sodium aluminosilicate or silicon dioxide. The product is mixed in a slurry, optionally homogenized and spray-dried in granular or agglomerated form.

Liquid coffee creamers are simply homogenized pasteurized emulsions of fat (milk fat or hydrogenated vegetable oil), some milk solids or casein, corn syrup and vanilla or other flavors, as well as stabilized blends. The product is usually pasteurized at 185 ° F for 30 seconds with HTST (high temperature short time) or at 285 ° F for 4 seconds with UHT (ultra high temperature), and in a two-stage homogenizer 500-3000 psi in the first stage and 200 in the second stage. It is homogenized at ~ 1000psi. Coffee creamers are usually stabilized so that they do not decompose when added to coffee.

Other types of food products in which the syrup is used are food coatings such as icing, frosting and glaze. In icing and frosting, resistant corn syrup is used as a sweetener substitute (full or partial) to reduce calories and increase fiber. Glaze is typically about 70-90% sugar, most of the rest is water, and resistant corn syrup is used as a complete or partial replacement for sugar. Frosting typically contains about 2-40% liquid / solid fat combinations, about 20-75% solid sweets, pigments, flavors and water. Resistant corn syrup is used in place of all or part of solid sweeteners or as a low-fat bulking agent.

Other types of food products in which the syrup is used are pet foods such as dry or moist dog food. Pet food is obtained by various methods such as extrusion, molding and prescribing as gravy. Resistant corn syrup is used at levels of 0-50% in each of these types.

Another type of food product in which the syrup is used is a tortilla that usually contains flour and / or cornmeal, fat, water, salt and fumaric acid. Resistant corn syrup is used in place of flour or fat. The ingredients are mixed, then sheeted or die cut and cooked. This addition is used to add fiber or extend shelf life.

Other types of food products in which the syrup is used are fish and meat. Common corn syrup is already used in some meats, so resistant corn syrup is used as a partial or complete substitute. For example, resistant corn syrup is added to salt water and then vacuum tumbled or injected into the meat. It is added with salts and phosphates, optionally with water binding materials such as starch, carrageenan or soy protein. It is used to add fiber and the typical level is 5g per serving, which is an excellent source of fiber.

Another type of food product in which the syrup is used is dry (injected) fruit. Many types of dried fruits are only stable and tasty when they are infused with sugar. Resistant corn syrup is used in place of all or part of the sugar. For example, resistant corn syrup is added to the salt water used to inject into the fruit before drying. Stabilizers such as sulfate are also used in this brine.

Other types of food products in which the syrup is used are infant and toddler foods. Resistant corn syrup is used in such foods as a substitute or supplement for one or more common ingredients. Thanks to its mild flavor and clear color, it is added to various baby foods to reduce sugar and increase fiber content.

Other types of food products in which the syrup is used are butter and bleeding, such as butter and bleeding for meat. This is done by substituting all or part of the dry ingredients of butter and / or bleeding (eg, flour-type ingredients) with resistant corn syrup, or in combination with the addition to lean meat or the fried food itself. Is done. It is used as a bulking agent for fiber additions or for reducing fat in fried foods.

The process described here utilizes a fraction of sugar syrup that is resistant to saccharification (eg, flow 26 in FIG. 1). By separating this substance as a purified product, it is used due to its own useful properties, rather than being an unwanted by-product in the syrup, which is primarily a monosaccharide, such as high fructose corn syrup. Removal of large proportions of oligosaccharides from high fructose corn syrup makes the product purer (ie, higher concentrations of dextrose and fructose) and thus more beneficial.

The food products of the present invention are also used to help control blood glucose levels in diabetic mammals, such as humans. When the food product is consumed in mammals, the slow-digesting and / or digestive-resistant components in the food product produce a milder relative glycemic response in the bloodstream that is beneficial in diabetic patients. "Control" in this relationship should be understood as a relative term, i.e. compared to what occurs when the mammal consumes a similar food product that does not contain such digestive and / or slow digestive components. Although the glycemic response is improved, the glycemic response does not necessarily correspond to what is observed in mammals not suffering from diabetes.

Certain aspects of the invention are further understood from the examples below.

<u style="single">Example 1</u> Raffinate syrup was obtained from a plant where cornstarch was processed into high fructose corn syrup. Raffinate was produced by chromatographic separation and contained predominantly fructose and dextrose. Raffinate was subjected to nanofiltration at a pressure of approximately 500 psi and a temperature of 40-60 ° C using a Desal DK1812C-31D nanofiltration cartridge. The retained material from the nanofiltration was decolorized with activated charcoal and then evaporated to about 80% dry solid. Sugar analysis of the dried product was performed by HPAE-PAD chromatography and the results are shown in Table 1.<tables num="1"><img id="000002" he="59" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

This substance, called light raffinate, was tested for digestibility in the Englyst assay. Approximately 600 mg of carbohydrate dsb was added to 20 mL of 0.1 M sodium acetate buffer in vitro. The contents were mixed, then heated to about 92 ° C for 30 minutes and then cooled to 37 ° C. 5 mL of the enzyme solution was then added to the test tube and stirred by shaking in a water bath at 37 ° C. Small samples were taken for both 20 and 120 minutes. The enzyme was inactivated, the sample was filtered and digestibility was measured using the YSI Inc. glucose test. Heavy raffinates processed by another but similar nanofiltration procedure were also tested using the same assay. Heavy raffinates contained 25-35% dry solids, unlike the 15-25% dry solids of light raffinates, but both had approximately the same proportion of low molecular weight sugars. Cooked potato starch that was not nanofiltered was also tested for comparison. The results of the digestibility assay and sugar analysis are shown in Table 2. Cooked potato starch is also included in Table 2 for comparison. All percentages in Table 2 are based on dsb.<tables num="2"><img id="000003" he="40" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

There was an excellent correlation between the proportion of oligosaccharides in the substance and the proportion of substances that are resistant to digestion.

<u style="single">Example 2</u> Approximately 1025 L of raffinate syrup was obtained in 21.4% dry solids from a plant where cornstarch was processed into high fructose corn syrup. Raffinate was produced by chromatographic separation and contained predominantly fructose and dextrose. Raffinate was subjected to nanofiltration at a pressure of approximately 500 psi and a temperature of 40-60 ° C using a Desal NF3840C-50D nanofiltration cartridge. After reducing the starting volume to about 1/20, the retained material was subjected to a constant volume diafiltration of about twice the volume using DI water. After diafiltration, 27.6 kg of retained material (33.8% ds) was collected. The material was decolorized with activated carbon (0.5 wt% solid syrup) by stirring overnight in a refrigerator. The slurry was sterilized by filtration through a 0.45 micron hollow fiber filtration cartridge, split and evaporated to an average concentration of about 73% ds.

Sugar analysis of the dried product was performed by HPAE-PAD chromatography and the results are shown in Table 3.<tables num="3"><img id="000004" he="59" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 3</u>-Enzymatic production of non-linear oligomers from dextrose Concentrated dextrose syrups with solid concentrations of 74%, 79.5% and 80% were prepared by (1) evaporating the diluted syrup or (2) adding water to the dextrose powder. Each dextrose / water mixture was placed in a suitable container and heated to 60 ° C in a water bath.

Glucoamylase enzyme (Dextrozyme or Spirizyme, Novozymes A / S) was added to the syrup-about 400 μL enzyme was added to a 30 mL syrup. The syrup container was capped and then shaken vigorously to disperse the enzyme. The syrup was returned to the 60 ° C water bath.

Changes in sugar distribution were monitored over time by transferring 2-4 mL syrup to a small glass vial and heating it with a heat block to about 85-90 ° C to inactivate the enzyme.

The concentrations of various sugar species were examined by High Performance Anion Exchange with Pulsed Amperometric Detection (HPAE-PAD). A Dionex ion chromatograph DX500 equipped with an electrochemical detector and a gradient pump was used for the analysis. Sugars were separated by Dionex Carbopac PA1 analysis and guard column by gradient delivery of sodium hydroxide and sodium acetate eluate. Sugar was detected using a gold electrode in a four-potential waveform. Samples were diluted with water and passed through an Amicon Ultra-4 centrifugal filter device prior to analysis.

Figure 2 shows dextrose, isomaltose and "non-linear highers" in syrups of three different early dextrose compositions treated with Novozymes' commercially available glucoamylase enzyme, 1.3% vol / vol Dextrazyme, at 60 ° C for 48 hours. "(In this figure, for non-linear oligomers with a degree of polymerization of 4 or higher) is shown. As the syrup concentration increases, the amount of monomeric dextrose decreases and the amount of non-linear higher oligomers increases as compared to other sugars.

<u style="single">Example 4</u>-Manufacture of oligomeric syrup from corn syrup Dextrose Greens (95% de mild conversion Staley 200 syrup Kisutorosu) (26DE, 5% dextrose), and thus a high (34%) to maltose syrup Neto 7300, to obtain a starting substrate having a degree of conversion range. The specific product used as a starting material in this example is Staley.^R 200, Staley^R 300, Staley^R 1300, Neto^R 7300 and Sweetose^R 4300 corn syrup, and Staleydex^R It was 3370 dextrose. Some of the characteristics of these substances are shown in Table 4.<tables num="4"><img id="000005" he="68" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

Most low-conversion syrups have a substantial amount of non-linear higher oligomers (NL DP4 +) with a degree of polymerization of 4 or higher, but they also have a substantial amount of linear oligomers. Some of these syrups contain measurable amounts of linear oligomers up to DP17. Figure 3 shows the initial sugar distribution.

The enzymes used were Spirizyme Plus FG and Dextrozyme DX 1.5X glucoamylase and Promozyme D2 pullulanase (Novozymes supply), CG220 cellulase and Transglucosidase L-500 (Genencor supply), Glucoamylase GA150 (Sunson Industry Group supply) and Transglucosidase L (Bio). -Cat Inc. supplied).

Various corn syrups were adjusted to about 70% ds. Approximately 3.3% (v / v) Spirizyme Plus FG enzyme was added to each in a 50 mL tube. The syrup was heated in a 60 ° C water bath for about 4 days. The enzyme was inactivated by heating the syrup at about 85 ° C for 10 minutes. Figure 4 shows the final sugar distribution. All syrups reached comparable sugar distributions at the end of the 4-day treatment. After conversion, only a very small amount of linear oligomers remained, and the amount of non-linear oligomers increased.

Some points should be noted. First, the converted Staleydex 3370 syrup has a slightly higher dextrose content and a lower non-linear oligomer content than other syrups. All syrups were adjusted to about 70% ds prior to conversion, but low conversion syrups were obtained by consuming water as a new distribution in the case of low initial dextrose content, with a final concentration of 4 ~ from the conversion 3370 syrup. It was 9 percentage points higher (hydrolysis of dextrose from a single DP6 oligomer to 6 dextrose molecules consumes, for example, 5 water molecules). As Table 5 shows, the water content of the converted syrup has the same trend as the glucose content, but the opposite trend to the higher oligomer content.<tables num="5"><img id="000006" he="50" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

The lower the water content, the more the equilibrium is toward the higher concentration of the product. We believe that if the water content was adjusted so that the final water content was the same, the sugar distribution would also be the same.

Second, the converted total syrup had a significantly higher rate of branched oligomers at each degree of polymerization (DP) than linear oligomers. Compare the relative amounts of maltose vs. isomaltose, panose vs. maltotriose and NL DP4 + vs. DP4 or higher linear oligomers (virtually nothing remains after conversion).

FIG. 5 shows the changes in maltose and isomaltose concentrations over time when the concentrated dextrose syrup was treated with Spirizyme. It seems that linear oligomers are kinetic products and non-linear oligomers are thermodynamic products. That is, the formation of linear dimer and maltose from dextrose is a fast reversible reaction with low activation energy. The formation of the non-linear dimer, isomaltose, is a slow reaction, and the reverse reaction has high activation energy.

Figures 6 and 7 show changes in maltose and isomaltose concentrations over time when 70% dextrose syrup was treated with different concentrations of Spirizyme enzyme at 60 ° C.

Treatment of Staley 1300 syrup with glucoamylase rapidly consumed linear oligomers above DP3 and converted them to dextrose. Concentrations of these linear oligomers reached an equilibrium of about 1% of total sugar within hours of the start of treatment (at 70% syrup concentration, 0.13% Spirizyme and 60 ° C) (see Figure 8). Over a longer period of time, the glucose concentration decreased slowly and the concentration of non-linear oligomers increased slowly. Changes in maltose and isomaltose concentrations over time reflect what is seen with dextrose conversion (Fig. 7).

Samples from the above experiments were heated above 85 ° C for 10-20 minutes to inactivate the enzyme before dilution for ion chromatography analysis. When the samples were diluted in the presence of active enzymes, they were also hydrolyzed back to dextrose.

A sample of converted syrup was diluted to 20% solid. Each part was kept at 60 ° C in the presence of Spirizyme enzyme and each other part was kept at 40 ° C in the presence of Spirizyme. The syrup was sampled over time and the enzyme in each sample was inactivated as described above.

Figure 9 shows the results. At 60 ° C, the concentration of non-linear higher oligomers (DP3 and above) dropped in half within 3 hours and appeared to reach a plateau at about 11.6% of total sugar in 7 hours. At lower temperatures, hydrolysis was delayed. As shown in FIG. 9, the glucose content increased as a result of hydrolysis. The rate of hydrolysis was the same when two different glucoamylases (Spirizyme and Dextrozyme) were used.

These experiments show that the non-linear oligomers formed by the conversion are not immune to hydrolysis by the glucoamylase enzyme (or impurities in it). However, some of them appear to be resistant to hydrolysis. At 20% ds, the equilibrium between the monomer and the oligomer is on the monomer side. Nevertheless, 11.3% DP4 + and 11.6% DP3 + remain at the optimum temperature for glucoamylase activity after 7 hours. Compare this with the virtually complete conversion of linear oligomers to dextrose at the same time frame, but at a fairly high solid (70% ds) and half the glucoamylase content, as shown in Figure 8. Glucoamylase enzymes can hydrolyze non-linear oligomers, but the hydrolysis is not fast and may not lead to complete conversion. We believe that digestive enzymes in the human gastrointestinal tract would have reduced activity on these compounds as well.

Table 6 shows the change in total sugar species concentration when the converted syrup was diluted to 20% ds at 60 ° C in the presence of the active Spirizyme enzyme.<tables num="6"><img id="000007" he="51" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>("L DP3 +" is for linear oligomers with a degree of polymerization of 3 or higher. "NL DP3" is for non-linear oligomers with a degree of polymerization of 3 or higher. "NL DP4 +" is for non-linear oligomers with a degree of polymerization of 4 or higher. Regarding the state oligomer.)

All corn syrups tested, regardless of starting sugar distribution or degree of conversion, were converted to comparable sugar distributions by glucoamylase if treated at comparable syrup concentrations.

From these experiments, it appears that during enzymatic conversion of corn syrup, linear oligomers are rapidly hydrolyzed to dextrose. At higher syrup concentrations over a longer period of time, dextrose is consumed to form non-linear oligomers. The formation of non-linear oligomers is at least partially reversible, as evidenced by hydrolysis with glucoamylase in low syrup solids. Thus, if the conversion syrup is diluted before inactivating glucoamylase, some, but not all, of the oligomers are apparently hydrolyzed to dextrose monomers. This proves that the formation of non-linear bonds by glucoamylase (or perhaps the impurities it contains) is not a complete irreversible "mistake" by the enzyme.

<u style="single">Example 5</u>-Glucose amylase quality affects conversion The amount of enzyme required to perform the conversion is high compared to a typical enzymatic process. Approximately 1.5% v / v of conventional glucoamylase (eg, Spirizyme Plus FG and Dextrozyme DX 1.5X, Novozymes supply) is required to reach 80% of equilibrium conversion over 24 hours at 60-75 ° C. Notably, enzyme manufacturers have made great strides in reducing the tendency of glucoamylase to form transformants-improvements imposed by consumers of these enzymes-corn syrup manufacturers-they. Convertible products are a source of trouble for consumers. We believe that enzymes from the 1950s would be significantly more efficient in forming these non-linear oligomeric syrups than current glucoamylases.

Support for the notion that the "impurities" hidden in these commercially available glucoamylases may be involved in the transformants in the experiments reported here is optimal for Novozymes at 59-61 ° C for both Spirizyme and Dextrozyme activity. The temperature is reported, but the fact is that the rate of conversion product formation increases when the temperature is increased from 60 to 65 ° C. Figures 10 and 11 show the formation rates of isomaltose and non-linear oligomers above DP3 (NL DP3 +) as a function of temperature for Spirizyme and Dextrozyme. The substrate syrup was Staley 1300 and the amount of enzyme used was 2.7% v / v.

<u style="single">Example 6</u>-Acid-catalyzed reconstruction of corn syrup to form non-linear oligomers The Staley 1300 syrup was diluted 1: 4 with deionized water to facilitate pH measurements. Acid (HCl or H) that lowers the syrup pH to the pH target₂SO₄) Was calculated. In one experiment, 10% Krystar crystalline fructose was added to the syrup prior to acid treatment.

The Staley 1300 syrup was heated to approximately 60 ° C in a 50 mL screw cap centrifuge tube in a shaking water bath. A predetermined amount of acid required to reach the target pH was added to the syrup. The syrup tube was shaken vigorously to distribute the acid evenly. Each tube was returned to the water bath and the bath temperature was adjusted as needed. Treatment was performed at 60, 70 and 80 ° C and pH 1.2, 1.8 and 2.3. To monitor the progress of the reaction, a portion of the syrup was removed from the tube and neutralized by adding a caustic solution.

The caustic solution was prepared so that the volume of the caustic solution was sufficient to neutralize an equal amount of acidified syrup. Approximately 80% of this volume was added all at once and the syrup was thus diluted for pH measurement. Additional caustic solution was added dropwise until the pH reached&gt; 5.0 (preferably 6.5 or less).

The syrup solution was analyzed using ion chromatography. In addition to the Phenomenex RSO oligosaccharide column, a Dionex CarboPac PA200 column was also used to analyze some samples.

The first acid condensation reaction with Staley 1300 syrup was at pH 2.3 with sulfuric acid at 60 ° C. The proportion of linear oligomers decreased and the proportion of non-linear oligomers increased.

Figure 12 compares the changes in sugar distribution in the Staley 1300 syrup that occur with acid and glucoamylase treatments (both at 60 ° C). The process appears to proceed differently. Spirizyme glucoamylase consumes linear oligomers very quickly to produce dextrose. In the case of Staley 1300 syrup, the concentration of linear oligomers above DP3 drops from about 42% of total sugar to about 1% of its equilibrium within hours of contact with the enzyme. Over a longer period of time, some of the dextrose is converted to non-linear oligomers. Concentrations above non-linear DP3 (DP3 +) have increased over about 30 hours (under the conditions of this enzyme treatment).

In contrast, contact with an acid consumes linear oligomers and forms non-linear oligomers at comparable rates. Dextrose concentration increases very slowly during the process.

In parallel experiments, 10% dry fructose was added to the Staley 1300 syrup so that the final syrup solid concentration was approximately 90%. It was treated with the same pH, temperature and time as Staley 1300 syrup alone. The Staley 1300 syrup developed color during the process, but the fructose-containing syrup turned coffee-colored almost immediately. IC analysis of the samples taken from it showed a rate of linear oligomeric reduction and non-linear oligomerization comparable to acid-treated syrup alone. The fructose content did not change significantly.

A second round of acid treatment was performed in which the Staley 1300 syrup was adjusted to 1.2 and 1.8 pH with HCl. Each pH treatment was run at temperatures of 70 ° C and 80 ° C. All syrups produced a noticeable color during the process. The degree of color increased with lower pH, higher temperature and over time. In extreme situations, dark insoluble components were formed.

As shown in FIG. 13, the acid-treated syrup product has a very wide distribution of sugar oligomers. It also shows significantly higher concentrations of DP3 oligomers than enzymatically converted syrups. Moreover, the acid-treated syrup contains sugars that do not appear in the enzyme-treated syrup. This is expected because acid-catalyzed condensation occurs between any two hydroxyl groups, while enzymatic condensation is typically very specific for how the two sugar units are bound together. ..

A Dionex CarboPac PA200 column was used for ion chromatographic separation of sugars. FIG. 14 shows a chromatographic trace of the acid treated syrup separated on this column. It clearly shows four components in the DP2-3 range that elute separately from maltose, isomaltose, maltotriose and panose. (All four of these are eluted before maltose.) It also shows some peaks for unidentified higher oligomers.

Table 7 below shows the changes in sugar distribution over time in these four low pH, high temperature treatments using the PA200 column (the last column in the table shows the amount of "unknown 1-4" peaks. Shown and not included in NL DP3 +).<tables num="7"><img id="000008" he="125" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 7</u>-Enzyme conversion-High sugar Approximately 35 gallons of 80% dry solid 43DE corn syrup (Staley 1300) was added slowly in a tank with 5 gallons of deionized water and heated to a temperature of 60 ° C. Approximately 1.6 gallons of Spirizyme Plus FG enzyme was slowly added to the syrup with good stirring. After 24 hours at 60 ° C, the syrup was heated to 85 ° C and kept for 20 minutes. The syrup was then diluted to a dry solid concentration of 70% to 20% by adding 100 gallons of water. The sugar solution was subjected to nanofiltration at a pressure of approximately 500 psi and a temperature of 55-60 ° C using a Desal NF3840C30D nanofiltration cartridge. Fresh diafiltration water was added to maintain permeate flow in the range of 2-10 LMH. Filtration was continued until the retained material contained less than 5% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. The nanofiltration retainer was treated with 1% activated carbon on a dry solid basis. The carbon was then removed by filtration and the filtrate was evaporated to 80.2% ds.

Sugar analysis of the final product was performed by HPAE-PAD chromatography and the results are shown in Table 8.<tables num="8"><img id="000009" he="61" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>(In the above table, "higher sugar" means an oligomer having a DP of 3 or more)

<u style="single">Example 8</u>-Enzyme conversion-Low sugar Approximately 35 gallons of 80% dry solid 43DE corn syrup (Staley 1300) was added slowly in a tank with 5 gallons of deionized water and heated to a temperature of 60 ° C. Approximately 1.6 gallons of Spirizyme Plus FG enzyme was slowly added to the syrup with good stirring. After 24 hours at 60 ° C, the syrup was heated to 85 ° C and kept for 20 minutes. The syrup was then diluted to a dry solid concentration of 70% to 20% by adding 100 gallons of water. The sugar solution was subjected to ultrafiltration at a pressure of approximately 400 psi and a temperature of 55-60 ° C using a Desal UF-1 3840C50D ultrafiltration cartridge. Fresh diafiltration water was added to maintain permeate flow in the range of 10-20 LMH. Filtration was continued until the retained material contained less than 1% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. The extrafiltration retention material was treated with 1% activated carbon on a dry solid basis. The carbon was then removed by filtration and the filtrate was evaporated to 73.4% ds.

Sugar analysis of the final product was performed by HPAE-PAD chromatography and the results are shown in Table 9.<tables num="9"><img id="000010" he="59" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 9</u>-Enzyme conversion-High isomaltose The syrup from Example 7 was subjected to ultrafiltration at a pressure of approximately 400 psi and a temperature of 55-60 ° C using a Desal UF-1 3840C50D ultrafiltration cartridge. Permeates from this operation were then subjected to nanofiltration using a Desal NF3840C 30D nanofiltration cartridge at a pressure of approximately 500 psi and a temperature of 55-60 ° C. Fresh diafiltration water was added to maintain permeate flow in the range of 2-10 LMH. Filtration was continued until the retained material contained less than 5% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. The nanofiltration retainer was treated with 1% activated carbon on a dry solid basis. The carbon was then removed by filtration and the filtrate was evaporated to 90.2% ds.

Sugar analysis of the final product was performed by HPAE-PAD chromatography and the results are shown in Table 10.<tables num="10"><img id="000011" he="59" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 10</u>-Acid conversion-Moderate resistance Approximately 35 gallons of 80% dry solid 43DE corn syrup (Staley 1300) was gently agitated in a tank and heated to a temperature of 80 ° C. Approximately 4.1 lbs of 37% hydrochloric acid was added slowly to the syrup with good stirring. The reaction was maintained at a dry solid concentration of about 80%, as measured by Karl Fisher analysis with regular addition of water. After 24 hours, heating was stopped and about 35 gallons of 0.35% sodium hydroxide solution was added slowly with good stirring. The pH was then adjusted to 5.0 and water was added to reach a final sugar concentration of 30% ds. The sugar solution was subjected to ultrafiltration at a pressure of approximately 400 psi and a temperature of 55-60 ° C using a Desal UF-1 ultrafiltration cartridge. Fresh diafiltration water was added to maintain permeate flow in the range of 10-20 LMH. Filtration was continued until the retained material contained less than 5% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. The extrafiltration retention material was treated with 2% activated carbon on a dry solid basis. The carbon was then removed by filtration and the filtrate was evaporated to 71.5% ds.

Sugar analysis of the final product was performed by HPAE-PAD chromatography and the results are shown in Table 11.<tables num="11"><img id="000012" he="59" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 11</u>-Hydrogenation following acid conversion Approximately 35 gallons of 80% dry solid 63DE corn syrup (SWEETOSE)^R 4300) was slowly stirred in the tank. 37% hydrochloric acid was then added slowly with good stirring to give 0.25% (w / w) HCl to the syrup dry solid. The mixture was then heated to a temperature of 80 ° C. The reaction was maintained at a dry solid concentration of about 80%, as measured by Karl Fisher analysis with regular addition of water. After 16 hours, heating was stopped and the pH was adjusted to 4.5 with 0.35% sodium hydroxide solution. Additional water was added to reach a final sugar concentration of 30% ds. The sugar solution was subjected to ultrafiltration at a pressure of approximately 400 psi and a temperature of 55-60 ° C using a Desal UF-1 ultrafiltration cartridge. Fresh diafiltration water was added to maintain permeate flow in the range of 10-20 LMH. Extrafiltration was continued until the retained material contained less than 10% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. Desal Ultrafiltration retention material was subjected to nanofiltration at a pressure of approximately 500 psi and a temperature of 55-60 ° C using an NF3840C30D nanofiltration cartridge. Fresh diafiltration water was added to maintain permeate flow in the range of 2-10 LMH. Filtration was continued until the retained material contained less than 1% dextrose (dsb) in the combination of Karl Fisher and YSI dextrose analysis. The nanofiltration retainer was treated with 1% activated carbon on a dry solid basis. The carbon was then removed by filtration and the filtrate was evaporated to 73.5% ds.

The dextrose equivalent (DE) of this product was measured by the AOAC method 920.51 (Lane Eynon) and found to be 21 DE. Sugar analysis of this product was performed by HPAE-PAD chromatography and the results are shown in Table 12.<tables num="12"><img id="000013" he="59" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

This product was further subjected to hydrogenation reaction conditions. Approximately 1.5 kg of a 43% ds solution of the substances listed in Table 9 was introduced into the pressure reactor and while stirring 6.45 g of 5% ruthenium carbon catalyst to make 0.05% ruthenium (w / w) in syrup dry solids. added. The reactor was closed, purged with nitrogen gas and then pressurized to a pressure of 600 psi with hydrogen gas. The reactor was then heated to 120 ° C. This temperature and hydrogen pressure of 600-650 psi were maintained for 4 hours. The reaction vessel was cooled, carefully evacuated and purged with nitrogen. The reaction product was then filtered through diatomaceous earth to give a clear colorless solution.

The dextrose equivalent (DE) of this product was measured by the AOAC method 920.51 (Lane Eynon) and found to be 5DE. Sugar analysis of this product was performed by HPAE-PAD chromatography and the results are shown in Table 13.<tables num="13"><img id="000014" he="59" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

<u style="single">Example 12</u>-Englyst digestion assay The products from Examples 7, 8 and 10 were tested for digestibility using the Englyst assay. Approximately 600 mg of carbohydrate dsb was added to 20 mL of 0.1 M sodium acetate buffer in vitro. The contents were mixed, then heated to about 92 ° C for 30 minutes and then cooled to 37 ° C. A small amount of sample was then taken for both 20 and 120 minutes, with 5 mL of the enzyme solution added to the test tube and stirred in a water bath at 37 ° C. Enzymes were inactivated; samples were filtered and digestibility was measured using the YSI Inc. dextrose test. 10DE maltodextrin (STAR-DRI 10), which is known to be highly digestible, was also tested for comparison. The results of the digestibility assay and sugar analysis are shown in Table 14. 10DE maltodextrin is also included in Table 5 for comparison. All percentages in Table 14 are based on dsb.<tables num="14"><img id="000015" he="48" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>(In Table 14, "higher grade" refers to oligomers with a degree of polymerization of 3 or higher.)

Excellent correlation (R) between the percentage of non-linear luxury substances in the substance and the percentage of substances that are resistant to digestion²There was = 0.95).

<u style="single">Example 13</u>-Hard candy, lemon flavor 980 g (dsb) of Example 7 (enzyme conversion-high sugar) was added to the pot and cooked on the stove to an initial temperature of 300 ° F. Then 15 g of citric acid and 1.2 g of sucralose were added with stirring. The yellow pigment and lemon flavor were then added and the mixture was poured into a candy mold. Hard candy was formed upon cooling to room temperature.

<u style="single">Example 14</u>-Jelly candy, grape flavor 840 g of Example 8 (enzyme conversion-low sugar) was added to the mixing bowl. Purple pigment and grape flavor were added to the taste. Then 160 g of MiraThik 468 Instant Starch was added in small portions under moderately strong mixing. Jelly candy was formed after cooling to room temperature over 20 minutes.

<u style="single">Example 15</u>-Yogurt 900 g of milk (2% fat) was added to the pot on the stove. Then 80 g (dsb) of Example 10 (acid conversion-moderate resistance) was added with stirring. The mixture was then heated to a target temperature of 150 ° F. While heating the mixture, 20 g of Rezista 682 starch was added in small portions with mixing. After the mixture reached an internal temperature of 150 ° F, it was kept for 5 minutes and then passed through a two-step homogenizer (1500/500 psi). The product was then pasteurized at 190 ° F for 5 minutes. The mixture was then cooled to 90 ° F and inoculated with active yogurt culture. Incubation was continued until the yogurt reached a pH of 4.5, then refrigerated before consumption.

<u style="single">Example 16</u> The following general procedure was used to produce a sample of digestive resistant corn syrup according to the present invention. In the preparation of some low sugar samples, nanofiltration was run to less than 1% dextrose instead of 5% as described in the general procedure below.

Oligomer syrup from sample 1-HFCS raffinate 1. Transfer the mixed raffinate from the high fructose corn syrup (HFCS) process to the filtration unit and concentrate 10 × ~ 30 × volume with Desal UF-1 membrane. Note: This step is an option depending on your final DP2 goal. 2. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Continue until the retention material contains less than 5% dextrose (dsb) in a combination of Karl Fisher and YSI dextrose analysis. 3. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 4. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Sample 2-Oligomer syrup from dextrose greens 1. Transfer diluted dextrose greens (20-30% ds) to a filtration unit and concentrate 10 × -30 × volume with Desal UF-1 membrane. Note: This step is an option depending on your final DP2 goal. 2. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Continue until the retention material contains less than 5% dextrose (dsb) in a combination of Karl Fisher and YSI dextrose analysis. 3. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 4. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Staley for forming&gt; 25% non-linear oligomers of sample 3-dextrose^REnzymatic conversion of 1300 corn syrup Send 1.35 gallons of Staley 1300 syrup and 5 gallons of water to the tank. Start the stirrer and start heating. 2. Heat the syrup to 60 ° C and check that the temperature stabilizes at 60 ° C ± 5 ° C. 3. Add 1.6 gallons (6.1 L) of Spirizyme Plus FG enzyme to the syrup. 4. Keep at 60 ° C ± 5 ° C for 24 hours. 5. At the end of 60 ° C / 24 hours holding, heat the syrup to 85-90 ° C. When the syrup temperature stabilizes above 85 ° C, hold for 20 minutes. 6. Stop heating the tank. Dilute the syrup from 70% to 20% solid by adding 7.100 gallons of water (140 gallons total). 8. Transfer to filtration unit and concentrate 10 × ~ 30 × volume with Desal UF-1 membrane. 9. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Karl Continue until the retained material contains less than 1% dextrose (dsb) in a combination of Fisher and YSI dextrose analysis. 10. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 11. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Sample 4-Tate &amp; Lyle SWEETOSE^RAcid catalyst reconstruction of 4300 corn syrup 1.35 gallon SWEETOSE^RSend 4300 syrup to the tank. Start the stirrer and start heating to 80 ° C. 2. Syrup ~ 2.8 lbs of 37% hydrochloric acid (calculated to give 0.25% HCl dry solids in the reaction solution, assuming a 4300 syrup density of 11.9 lb / gallon) Add slowly with good stirring. Keep at 3.80% ds ± 5%. Take the reaction sample every 2 hours and dilute with an equal volume of DI water. Run Karl Fisher on the diluted sample. If it is less than 40% ds, do nothing. For more than 40% ds, add 4 lb DI water for every 1% ds above 40% ds for every 100 lb of initial reaction. 4. In addition to the above samples for Karl Fisher, collect samples used to monitor the progress of the reaction. Remove these at the following intervals: 2 hr, 4 hr, 8 hr and 16 hr after acid addition. After each sampling, act quickly to adjust the pH of the sample by adding an equal volume of 0.35% NaOH solution, mix well and measure the pH. Adjust the sample pH as needed to 5.0-6.5. At the end of holding at 5.80 ° C / 16 hours, stop heating. Add the 0.35% caustic solution slowly with good stirring until the pH stabilizes in the range 4.5-5.5. 6. Add diluted water as needed to reach a final solid concentration of 30% ds. 7. Transfer to filtration unit and concentrate 10 × ~ 30 × volume with Desal UF-1 membrane. Note: This step is an option depending on your final DP2 goal. 8. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Continue until the retention material contains less than 5% dextrose (dsb) in a combination of Karl Fisher and YSI dextrose analysis. 9. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 10. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Sample 5-SWEETOSE^RPhosphorus and hydrochloric acid catalytic reconstruction of 4300 corn syrup 1.35 gallon SWEETOSE^RSend 4300 syrup to the tank. Start the stirrer and start heating to 80 ° C. 2. Then (based on the assumption that the 4300 syrup density is 11.9 lb / gallon, 0.08% H in the syrup dry solid in the reaction solution.₃PO₄And slowly add 0.10 lb of 37% hydrochloric acid (calculated to obtain a 100 ppm HCl dry solid) into the syrup with good stirring. Keep at 3.80% ds ± 5%. Take the reaction sample every 2 hours and dilute with an equal volume of DI water. Run Karl Fisher on the diluted sample. If it is less than 40% ds, do nothing. For more than 40% ds, add 4 lb DI water for every 1% ds above 40% ds for every 100 lb of initial reaction. 4. In addition to the above samples for Karl Fisher, collect samples used to monitor the progress of the reaction. Remove these at the following intervals: 2 hr, 4 hr, 8 hr and 16 hr after acid addition. After each sampling, act quickly to adjust the pH of the sample by adding an equal volume of 0.35% NaOH solution, mix well and measure the pH. Adjust the sample pH as needed to 5.0-6.5. At the end of holding at 5.80 ° C / 16 hours, stop heating. Add the 0.35% caustic solution slowly with good stirring until the pH stabilizes in the range 4.5-5.5. 6. Add diluted water as needed to reach a final sugar concentration of 30% ds. 7. Transfer to filtration unit and concentrate 10 × ~ 30 × volume with Desal UF-1 membrane. Note: This step is an option depending on your final DP2 goal. 8. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Continue until the retention material contains less than 5% dextrose (dsb) in a combination of Karl Fisher and YSI dextrose analysis. 9. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 10. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Sample 6-Tate &amp; Lyle Staley^RAcid-catalyzed reconstruction of 1300 corn syrup 1.35 gallon SWEETOSE^RSend 1300 syrup to the tank. Start the stirrer and start heating to 80 ° C. 2. Syrup ~ 2.8 lbs of 37% hydrochloric acid (calculated to give 0.25% HCl dry solids in the reaction solution, assuming a 4300 syrup density of 11.9 lb / gallon) Add slowly with good stirring. Keep at 3.80% ds ± 5%. Take the reaction sample every 2 hours and dilute with an equal volume of DI water. Run Karl Fisher on the diluted sample. If it is less than 40% ds, do nothing. For more than 40% ds, add 4 lb DI water for every 1% ds above 40% ds for every 100 lb of initial reaction. 4. In addition to the above samples for Karl Fisher, collect samples used to monitor the progress of the reaction. Remove these at the following intervals: 2 hr, 4 hr, 8 hr and 16 hr after acid addition. After each sampling, act quickly to adjust the pH of the sample by adding an equal volume of 0.35% NaOH solution, mix well and measure the pH. Adjust the sample pH as needed to 5.0-6.5. At the end of holding at 5.80 ° C / 16 hours, stop heating. Add the 0.35% caustic solution slowly with good stirring until the pH stabilizes in the range 4.5-5.5. 6. Add diluted water as needed to reach a final solid concentration of 30% ds. 7. Transfer to a filtration skid and concentrate 10 × ~ 30 × volume with Desal UF-1 membrane. Note: This step is an option depending on your final DP2 goal. 8. Switch the filtration membrane to nanofiltration (Desal NF3840C30D "DL"). Add fresh diafiltration water in the range of 2-10 LMH at a rate that maintains the permeate flow. Continue until the retention material contains less than 5% dextrose (dsb) in a combination of Karl Fisher and YSI dextrose analysis. 9. Collect the retained material and add 1% activated charcoal on a dry solid basis. Refrigerate. 10. Remove carbon by filtration and evaporate the filtrate to&gt; 70% ds.

Some of the syrups produced by these methods were used in the examples below, where they are labeled with sample numbers.

<u style="single">Example 17</u> Breakfast cereals comprising the oligosaccharide compositions according to the invention can be prepared as described below. The cereal comprises an extruded portion and a coating placed on the extruded portion. The composition of the extruded portion is as follows (by weight%): Cornmeal 54.80 Whole grain flour 25.19 Resistant corn syrup solid (Sample 5) 13.51 Whole grain auto wheat flour 5.00 Vitamin Blend 0.50 salt <u style="single">1.00</u> 100.0 in total

Produce the extruded portion using the steps below: Mix the ingredients together in a mixer / blender. Serve with a dry blend and water to reach the target extrusion moisture. Typical extrusion and drying conditions are used. Cool and package.

The coating composition is a 75% solid solution of 50% sugar, 50% resistant corn syrup. Manufacture it using the steps below: Place the spray gun in a convection oven at 250 ° F to preheat. Approximately 100 g of cereal is weighed and placed in a tumbler first coated with an oil-based stripper. Blend the dry material (75% total dry solid) in a kettle. Add water and mix. The syrup is heated to about 230 ° F (rapid boiling). Weigh the desired amount of syrup required to achieve the correct cereal: coating ratio to obtain the proper ratio (approx. 45-50% coating on final cereal weight). Pour the syrup into a preheated spray gun and connect the airline hose to the spray gun. Once the serial is tumbled, spray the syrup onto the serial until all of the syrup has been applied. After the desired amount of coating has been applied, the coated cereal is tumbled on an enrobing drum for 3 minutes to ensure a uniform coating. Pour the coated cereal onto a baking sheet sprayed with a stripper. Dry the cereal at 250 ° F in a convection oven for 6 minutes or until the cereal appears dry. Stir halfway to dry to prevent cereals from sticking to bread and clamping cereals. After drying, allow the cereal to cool for 5 minutes. After cooling, weigh the cereal to check the coating rate. Pack cereals in a plastic storage bag.

<u style="single">Example 18</u> A yogurt containing the oligosaccharide composition according to the present invention was produced. The material was: 2% milk 3614 Fat-free dry milk (NFDM) 133 Resistant corn syrup (sample 5) 200 Rezista 682 Starch 53 Total weight: 4000g The yogurt was made using the steps below: Disperse the dry material into the liquid material using a pump and a funnel or liquefier. Preheat to 150 ° F. Homogeneize at 1500/500 psi using a two-step homogenizer. Pasteurize at 190 ° F for 5 minutes. Cool to 90 ° F and add culture. Incubate to final pH 4.4. Stir the product and start cooling to stop active culture growth. Package and cool.

<u style="single">Example 19</u> A yogurt drink containing the oligosaccharide composition according to the present invention was produced. The material was: Skimmed milk 94.21 Whey Protein Concentrate 1.2 Resistant corn syrup (sample 5) 4.25 Stabilizer Blend 0.442 Sucralose solution <u style="single">0.008</u> 100.0 in total The yogurt drink was made using the following steps: Add the drying material to the liquid using a pump and a funnel or liquefier. Preheat to 150 ° F. Homogeneize at 1500/500 psi using a two-step homogenizer. Pasteurize at 190 ° F for 5 minutes. Cool to 90 ° F and add culture. Incubate to final pH 4.4. Stop, package and cool.

<u style="single">Example 20</u> A frozen novelty containing the oligosaccharide composition according to the present invention can be produced as follows. The materials are:<tables num="15"><img id="000016" he="66" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Frozen novelties can be produced using the following steps: standardize creams, milks and non-fat dry milk to the desired butter fat and milk solids, non-fat (MSNF) levels. Stabilizers are added to the liquid sugar with moderate agitation to ensure proper dispersion. Thoroughly blend the milk and liquid sugar portions in a batch tank. Mix the solid milk fat portion with the mix and use low agitation to minimize air inclusions. Pasteurize at 185 ° F for 30 seconds or for a considerable amount of time and temperature. Homogeneize with a two-stage homogenizer at 2500 psi double stages (2000 and 500 psi, first and second stages, respectively). Cool the mix to 34-38 ° F and keep for a minimum of 4 hours for aging (preferably overnight aging).

<u style="single">Example 21</u> A sugar-free ice cream containing the oligosaccharide composition according to the present invention was produced. The material was: Butter fat 7-12% Milk solids fat-free 10-12% Resistant corn syrup (sample 5) 12 ~ 15% Maltodextrin 3-5% Sucralose 0.0085 ~ 0.012% Vitamin A Palmitate 0.009% Stabilizer blend 0.40 ~ 0.50% The following steps were used to make sugar-free ice cream: Stabilizer blend, sucralose, vitamin A and maltodextrin mixed with skim milk under shear. Resistant corn syrup is added to the mixture under shear. Then add cream (butter fat) slowly to avoid churning and aeration. The ice cream is then pasteurized and homogenized at 175 ° F for 30 seconds at 2500 psi in two steps. The mix is refrigerated overnight (35-40 ° F) and then frozen using a continuous freezing system.

<u style="single">Example 22</u> A marshmallow comprising the oligosaccharide composition according to the present invention was produced. The material was prepared in three separate parts: Part A Gelatin 250 Bloom 22.5 Cold water 44.5 Part B Resistant corn syrup (sample 5,71%) 337.5 Part C Hystar maltitol syrup <u style="single">585.5</u> Total 990g Marshmallows were made using the steps below: Mix the ingredients of Part A (gelatin into water). Preheat the resistant corn syrup to 135 ° F. Heat the maltitol syrup to 200 ° F. Combine parts B and C and cool to 145 ° F. Melt Part A in the microwave for 30 seconds to melt the gelatin. Add Part A to the other parts and whip the mixture with a whisk with a Hobart mixer until 0.5 density is reached. Pack the marshmallows in a pastry bag and place in a starch mold.

<u style="single">Example 23</u> A hard candy containing the oligosaccharide composition according to the present invention was produced. The material was: Sugar 42.0 Resistant corn syrup (Sample 4) 43.7 water <u style="single">14.3</u> 100.0 in total Hard candy was made using the steps below: Mix sugar and resistant corn syrup with water. Heat to approximately 138 ° C with a Bosch cooker and vacuum to 129 ° C for 2 minutes. Add citric acid (18g for 3kg product) and flavor. Mold or form a suite.

<u style="single">Example 24</u> A gelatin jelly candy containing the oligosaccharide composition according to the present invention was produced. The material was: Sugar 35.2 Resistant corn syrup (sample 5,71%) 36.6 Water 12.3 Gelatin 6.6 water <u style="single">9.3</u> 100.0 in total Gelatin jelly candy was made using the steps below: Mix gelatin and water and keep at 70 ° C. Mix sugar, resistant corn syrup and water. Heat until solids reach 89% (about 120 ° C). Cool to 90 ° C. Add gelatin solution. Add 50% (18g / 1000g) of citric acid solution and matching flavors and pigments. Place in molding starch and dry under environmental conditions to 81-82% by weight of dry solids (ds).

<u style="single">Example 25</u> A jam comprising the oligosaccharide composition according to the present invention was produced. The material was: Water 36.5 Apricot 32.8 Resistant corn syrup (sample 5,71%) 15.5 Maltodextrin 10.2 Pectin (low methoxy) 4.58 Xanthan gum 0.10 Citric acid 0.15 Sucralose 0.06 Potassium sorbate 0.10 Calcium chloride 0.01 100.0 in total Jam was made using the steps below: Mix the dry ingredients. Add dry ingredients to liquid ingredients and fruits. Heat to 220 ° F. Place in a container and cool.

<u style="single">Example 26</u> A sweet children's beverage containing the oligosaccharide composition according to the present invention was produced. The material was: Water 86.35 Citric acid 0.15 Strawberry flavor 0.10 Resistant corn syrup (sample 5,73.4%) 13.3 Dye (# 40,10%) 0.10 Sucralose 0.004 The drink was made using the steps below: Slowly add the ingredients to the water using a mixer. Heat the drink to 180 ° F. Immediately fill the bottle with heat. Place the bottle in a water bath for cooling.

<u style="single">Example 27</u> An orange-flavored juice soda beverage containing the oligosaccharide composition according to the present invention was produced. The material was: Material% Potassium citrate 0.0200 Acid (citric acid, apple) 0.2000 RCS (Sample 5,71% ds) 1.8750 High-strength sweetener (sucralose, Ace-K) 0.015 5% Clarification Val OJ Conc., 60.56 Brix 1.0177 Red # 40 0.0009 Yellow # 5 0.0044 Orange flavor 0.1218 Filtered water 96.7452 100 The following steps were used to make orange juice soda: dry blend potassium citrate, acid, resistant corn syrup and high-intensity sweetener. Blend the orange juice concentrate, red # 40, yellow # 5, orange flavor and blend from the previous step into the water. Desired capacity of CO₂Carbonate to (2-4 times).

<u style="single">Example 28</u> A savory high solid filling comprising the oligosaccharide composition according to the present invention was produced. The material was:<tables num="16"><img id="000017" he="60" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>¹Blend of food starch modifiers, wheat protein and maltodextrin The ingredients were added to the product mixture in the following order: (1) canola oil, (2) flavors, citric acid, lactic acid and salts, (3) resistant corn syrup and (4) Tate &amp; Lyle texture rising blends.

<u style="single">Example 29</u> A high solid fruit filling comprising the oligosaccharide composition according to the present invention was produced. The material was: Part A% Isosweet 5500 H FCS 21 Mirathik 603 (Food Modified Starch) 6 Part B Resistant corn syrup (sample 6) 70.88 Water 1.55 Nat.and art.rasp.flavor 256639 (Taste Maker) 0.3 Part C Malic acid 0.1 Citric acid 0.1 Red 09310 (WJ) 0.06 Blue 09918 (WJ) <u style="single">0.01</u> 100 Jam was made using the steps below: To Hobart Mixer Part A ISO SWEET^RPut 5500. Gently add Mirathik 603 with mixing for 1.5 minutes. Part B Add resistant corn syrup, flavor and water. Blend until uniform (1 minute). Let it sit for about 3 minutes until the mixture thickens. The ingredients of Part C are preblended and added to the mixture. Blend until uniform. Allow the filling to solidify for 24 hours until full viscosity is reached.

<u style="single">Example 30</u> A sheet-shaped cracker containing the oligosaccharide composition according to the present invention was produced. The material was: Flour 70.949 Resistant corn syrup solid (Sample 5) 17.00 Shortening 10.0 Sucralose 0.001 Sodium bicarbonate 0.70 Salt 0.50 Dicalcium phosphate <u style="single">0.85</u> 100.00 in total Amount of water 30 Made a sheet cracker using the steps below: Mix the dough until all ingredients are moist and supple. Sheet the dough to 1.1 mm. Cut into pieces. Bake in a convection oven (low fan) at 350 ° F for 5 minutes.

<u style="single">Example 31</u> An expanded extruded snack comprising the oligosaccharide composition according to the present invention was produced. The material was: Corn flour 75.00 Resistant corn syrup solid (Sample 5) 23.50 Salt 1.50 100.00 in total Expanded extruded snacks were made using the steps below: Mix the dry ingredients. Supply the dry material to the extruder. Extrude into the proper shape. Dry for 10 minutes to 1% final moisture content.

<u style="single">Example 32</u> A tortilla chip comprising the oligosaccharide composition according to the present invention was produced. The material was: Corn chips # 8 powder 23.5 Tortilla chips # 1 flour 24.0 Resistant corn syrup (sample 5) 2.50 Water 40.0 100.0 in total The following steps were used to make tortilla chips: Make a 1: 1 mixture of tortilla chip # 1 flour and corn chip # 8 flour. Mix at low speed for 1 minute with a Hobart mixer. Add resistant corn syrup and mix on low for 1 minute. Slowly add room temperature water to the dry mixture in a stream, still running the mixer at low speed. When all the water has been added, increase the mixer speed and mix for 3 minutes. Cover the dough and let it sit in a plastic beaker for 30 minutes. Sheet the dough using a Rondo sheeter and gradually roll the dough to a thickness of about 1.3 mm (check the thickness using a micrometer). Using a Rondo sheeter, cut the dough with a cutter by placing the dough horizontally. Fry in a fryer preheated to 375 ° F (until the chips look golden brown and the bubbling almost stops) for about 1:45 to 2 minutes. A metal spatula is used to stir the chips (in helping uniform fat absorption) so that they are constantly immersed on both sides while the chips are being fried. Remove from the fryer and hang the basket to drain the chips for 4 minutes. Pour the chips into a cloth towel and let it sit for 6 minutes. Pack in a plastic bag, seal and label with tortilla chips.

<u style="single">Example 33</u> A gelatin dessert dry mix comprising the oligosaccharide composition according to the present invention was produced. The material was: Resistant corn syrup solid (Sample 5) 88.66 Gelatin 250 bloom 9.00 Adipic acid 0.90 Fumaric acid 0.60 Strawberry flavor 0.50 Disodium phosphate 0.20 Dye (red # 40) 0.14 Sucralose 0.03 A gelatin dessert dry mix was made using the steps below: Mix the dry ingredients. Weigh 85.1 g of dry mix and add to 226.8 g of water at 212 ° F. Melt completely. Add 226.8 g of cold water and mix well. Refrigerate for at least 4 hours.

<u style="single">Example 34</u> A snack bar comprising the oligosaccharide composition according to the invention and comprising a high solid filling, bound syrup and extruded pieces was produced. The materials for high solid fillings were: Part A Resistant corn syrup (sample 6) 21.00 Mirathik 603 Starch 6.00 Part B Resistant corn syrup (Sample 6) 80.88 Water 1.55 Raspberry flavor 0.30 Part C Malic acid 0.10 Citric acid 0.10 Red pigment 0.06 Blue pigment <u style="single">0.01</u>100.00 in total A high solid filling was made using the following steps: Put Part A, which contains resistant corn syrup, into a mixer. Gently add Mirathik 603 while mixing at low speed for 1.5 minutes. Add Part B (resistant corn syrup, flavor, water) and blend until uniform (1 minute at low speed). Let it sit for about 3 minutes until the mixture thickens. The ingredients of Part C are preblended and added to the mixture. Blend until uniform (solidify the filling for 24 hours until full viscosity is reached).

The materials for the combined syrup were: Resistant corn syrup (Sample 2) 67.7 Glycerin 10.7 StaSlim 150 Starch 13.3 Shortening 7.5 salt <u style="single">0.8</u> 100.0 in total The combined syrup was made using the steps below: Mix and heat to 172 ° F. Add to cereal / granola pieces and mix to cover each piece evenly. Mix in a ratio of 54% syrup and 46% cereal.

The materials for the extruded pieces were: Cornmeal 55.30 Whole grain flour 25.19 Resistant corn syrup (Sample 2) 13.51 Whole grain auto wheat flour 5.00 salt <u style="single">1.00</u> 100.0 in total Extruded pieces were made using the steps below: Mix the ingredients together in a mixer / blender. Supply dry blend and water to reach target extrusion moisture. Typical extrusion and drying conditions are used. Cool and package.

Mix the bonded syrup to coat the extruded pieces or other fine particles, sheet or mold the mixture and cut into appropriate sizes. The high solid filling is typically added between the two sheets of the binder / fine particle mixture.

<u style="single">Example 35</u> A spice cake containing the oligosaccharide composition according to the present invention was produced. The material was: Material% Water 40.67 Purasnow cake flour 21.56 Sorbitol 17.70 RCS solid (sample 5) 8.85 Mira-Thik 603 Food Starch Modified 1.00 Core M90 (maltodextrin, sucralose) 0.25 EC-25 emulsifier 2.65 Provon 190 Whey Protein Isolate 1.25 HiJel S Food Starch-Modified 0.99 Dried egg white 0.99 Salt 0.79 GMS 90 emulsifier 0.59 Baking soda 0.56 Pan O Lite 0.45 Driver Nila 1011320 0.40 Dicalcium Phosphate Dihydrate 0.34 Cinnamon 0.29 Sodium propionate 0.21 Nutmeg 0.17 Xanthan gum 0.12 Durafax 60 emulsifier 0.10 Crushed cloves <u style="single">0.07</u> 100

A spice cake was made using the steps below: Dry mix procedure: Place RCS, Mira-Thik 603, Core M90 and sorbitol in a mixer bowl. Melt EC-25 in the microwave, being careful not to overheat (do not melt GMS 90 or Durfax 60). Add EC-25, mix at speed 1 for 5 minutes and scrape bowl if necessary. Add Durfax 60 while mixing at speed 1 for 1 minute and scrape the bowl if necessary. Add GMS90 while mixing at speed 1 for 1 minute and scrape the bowl if necessary. Run the dry mix in a food processor for 2 minutes and scrape after every minute. Return the dry mix to the mixing bowl. Sift the remaining dry ingredients and slowly add (1 tablespoon at a time) to the sorbitol mixture while running the mixer. Mix at speed 1 for a total of 5 minutes.

Water mixing procedure: Put the dry mix in a bowl. Add water slowly while mixing at speed 1 for 30 seconds. Scrape the bowl. Mix at speed 2 for 3 1/2 minutes and scrape the bowl if necessary. Spray the edges of the 8-inch layer cake pan with non-stick spray cooking oil and use circular parchment paper to draw on each pan. Pour 450g of butter into each cake pan. Bake at 350 ° F for 37 minutes or until finished.

<u style="single">Example 36</u> A cheese sauce containing the oligosaccharide composition according to the present invention was produced. The material was: Cheddar 23.41 Butter 5.88 Water 50.50 Sweet whey 5.44 Disodium Phosphate (DSP) 0.73 Trisodium Phosphate (TSP) 0.16 Sodium citrate 0.36 Salt 0.78 MaxiGel 420 Starch 2.73 RCS (Sample 5) <u style="single">9.09</u> 100.0 in total Made cheese sauce using the steps below: Mix all ingredients. Heat to 200 ° F with constant stirring. Heat-fill the jar or container with cheese sauce and seal with a lid or closure. Cool to 40 ° F.

<u style="single">Example 37</u> A block of imitation mozzarella cheese comprising the oligosaccharide composition according to the present invention was produced. The material was:<tables num="17"><img id="000018" he="75" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Cheese was made using the steps below: add water, sodium citrate, casein and soybean oil (120 g). Blend for 5 minutes. Add the remaining soybean oil. Add sorbic acid, salt, starch and resistant corn syrup. Then whey and lactic acid are added. Blend for 5 minutes. Add the remaining ingredients. Cook at 185 ° F.

<u style="single">Example 38</u> An edible film comprising the oligosaccharide composition according to the present invention was produced. Without being bound by theory, oligosaccharide compositions are believed to act as plasticizers in edible films. The material was:<tables num="18"><img id="000019" he="84" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Edible film was made using the following steps: Dispersion of various materials Mix pullulan and maltodextrin with a whisk in a beaker. Mix water, polysorbate 80, sodium benzoate and resistant corn syrup (RCS) in a separate beaker. A Servodyne Mixer Head model 50003-30 is used to further mix the wetting material. Start with an RPM of 700. Add the dry flavor mix slowly. When all the lumps disappear, add the pullulan mixture slowly. Once the mixture has thickened, adjust the RPM (within 1000 RPM) as needed. When all the drying material is present, stop the mixer and scrape the sides of the beaker. Increase the mixer to 1000 RPM and mix for another 2 minutes. Pour 50 g into the centrifuge tube. Centrifuge for 10 minutes to remove air.

Filming procedure: Film was picked up using a Gardco adjustable drawdown set at 0.045 in. These drawdowns were adjusted to the proper thickness using a feeler gauge blade. The film was picked up on Mylar using a vacuum plate. The film was dried in an environmental chamber at 65 ° C and 25% RH for 2 hours. They were cured overnight at 25 ° C and 28% RH in an environmental chamber. The dried film was packed in a plastic bag.

<u style="single">Example 39</u> A low-fat pound cake containing the oligosaccharide composition according to the present invention was produced. The material was: Material% Part A Cake flour 28.81 RCS solids (sample 5) 26 Water 16.27 GMS-90 emulsifier 5.92 Dextrose 4.17 Fat-free dry milk, high fever 1.6 STA-SLIM 150 Starch 1.29 STA-SLIM 142 Starch 0.64 salt 0.63 Fermentation acid, Pan-O-Lite 0.5 Baking soda 0.5 Vanilla flavor # 464174 0.45 Anato dye 0.1 Xanthan 0.09 Part B Liquid egg white 8.4 Water 4.63 100 The pound cake was made using the steps below: Blend the drying ingredients from Part A at speed 1 in a Hobart mixer. Add GMS-90 emulsifier and blend for 2 minutes (speed 1). Add water and anatto pigment and blend for 4 minutes (speed 2). Scrape the bowl and paddle after 2 minutes of mixing and at the end of mixing. Part B Mix the ingredients together. Add 1/3 of the Part B egg white / water mixture to Part A and blend for 1 minute (speed 2). Scrape the bowl and paddle after mixing. Repeat the first step of Part B twice to mix the remaining 2/3 of the egg white / water mixture. Pour 200 g of butter into a non-stick spray pre-coated loaf pan. Bake at 350 ° F for 30 minutes.

<u style="single">Example 40</u> An oatmeal chocolate chip raisin cookie having a polyol level and containing an oligosaccharide composition according to the present invention was produced. The material was:<tables num="19"><img id="000020" he="137" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Oatmeal raisin cookies were made using the steps below: shortening and flavors are mixed in an N-50 Hobart mixer at speed 1 for 30 seconds. Add the remaining step 1 material. Mix at speed 1 for 1 minute. Scrape the sides of the bowl. Mix at speed 2 for 1 minute. Step 2 Add material. Mix at speed 1 for 1 minute. Scrape the sides of the bowl. Mix at speed 2 for 1 minute. Step 3 Add material. Mix at speed 1 for 1 minute and 30 seconds. Scrape the sides of the bowl. Mix repeatedly for 1 minute and 30 seconds at speed 1. Step 4 Add material. Mix at speed 1 for 15 seconds. Weigh a 30g dopeace and place it on the parchment of a double-lined baking pan. Bake 12 cookies for 11 minutes at 375 ° F in a convection oven.

<u style="single">Example 41</u> A soft chocolate cookie containing the oligosaccharide composition according to the present invention was produced. The material was: Material% Powder, pastry 28.70 Resistant corn syrup solid (Sample 5) 22.20 Butter 20.40 RCS (Sample 5,71% ds) 10.90 Egg, hall 9.10 Natural cocoa N-11-N 3.60 Weakly alkalized cocoa D-11-A 2.00 Instant TENDER-JEL C Food Starch Modified 1.90 Vanilla flavor 0.46 Salt 0.44 Baking soda 0.30 100.00 Cookies were made using the steps below: Blend sugar / RCS solids, butter and RCS (71% ds) at speed 1 in a Hobart mixing bowl. Add eggs. The remaining ingredients are dry blended and added to this mixture. Bake at 350 ° F for 15 minutes.

<u style="single">Example 42</u> A maple syrup containing the oligosaccharide composition according to the present invention was produced. The material was: Water 80.132 Resistant corn syrup solid (Sample 5) 17.00 Cellulose rubber 1.00 Maple flavor 0.45 Salt 0.45 SPLENDA sucralose 0.35 Guar rubber 0.28 Phosphoric acid (85%) 0.15 Caramel color 0.13 Sodium hexametaphosphate 0.05 Butter flavor 0.008 100.00 in total Maple syrup was made using the following steps: Add sucralose, preservatives, salts, flavors and pigments to the water using a standard mixer at low speed. The rubber is slowly added to the mixture and hydrated for 20-25 minutes. Blend the resistant corn syrup solids while heating to 185 ° F. Hold for 1 minute. Remove heat and add acid. Fill the container at 180-185 ° F and invert for 1 minute. Cool to 75 ° F.

<u style="single">Example 43</u> A barbecue sauce containing the oligosaccharide composition according to the present invention was produced. The material was: Part A Tomato paste 27.23 Water 14.7 Apple cider vinegar 15.13 Resistant corn syrup (sample 5,71%) 33.73 Molasses 5.04 Liquid hickory smoke 0.30 Caramel color 0.21 Part B Salt 2.02 Spice Blend 1.65 Sucralose 0.014 The barbecue sauce was made using the steps below: Heat the Part A material to 190 ° F. Add the dry material to Part A and heat at 200 ° F for 15 minutes. Fill the container with heat and cool.

<u style="single">Example 44</u> A French dressing comprising the oligosaccharide composition according to the present invention was produced. The material was: Soybean oil 9.00 Resistant corn syrup (sample 5,71%) 47.57 Vinegar, 120 grain 12.00 Wed 18.59 Tomato paste 7.00 Salt 2.00 MiraThik 603 Food Starch Modified 2.00 Polysorbitol 60 0.20 Onion powder 0.18 Garlic powder 0.15 Xanthan gum 0.10 Sorbic acid 0.10 Oleoresin paprika 0.10 EDTA 0.01 100.0 in total French dressing was made using the steps below: Place water and resistant corn syrup in a container. Dry mix onion, salt, garlic, sorbic acid and EDTA and add to the water mixture. Slurry the starch and xanthan gum with a small amount of oil, add to the water mixture and mix for 5 minutes to hydrate the starch. Add tomato paste and paprika. Add vinegar. Melt polysorbitol 60 and add slowly to the mixture. Add the remaining oil and mix for 5 minutes. Process with a colloid mill at 0.26 (2 turns).

<u style="single">Example 45</u> A cream of chicken soup concentrate containing the oligosaccharide composition according to the present invention was produced. The material was: Water 65.65 Chicken Bouillon 11.30 Resistant corn syrup solid (Sample 5) 11.00 Half &amp; half 5.60 Rezista Starch 3.10 Titanium dioxide 1.00 Salt 0.50 Sugar 0.16 spices 0.69 Xanthan gum 0.10 100.00 in total The following steps were used to make a cream of chicken broth concentrate: mix the dry ingredients. Mix the liquid material for 3-5 minutes. Add the drying material slowly using a lightning mixer at medium speed. Mix for 3-5 minutes to ensure uniform dispersion. Heat to 190 ° F without stirring. Hold for 5 minutes. Fill the can with heat and seal immediately. Retort at 250 ° F for 40 minutes. Cool the can to room temperature. To serve, add 1 can of soup to an equal volume of 2% milk. mix well. Heat to stew (about 10 minutes). Serve when hot.

<u style="single">Example 46</u> A ketchup containing the oligosaccharide composition according to the present invention was produced. The material was: Tomato paste 37.54 Resistant corn syrup solid (Sample 5) 12.01 Water 41.37 Vinegar 120 grain 7.01 Garlic powder 0.02 Onion powder 0.03 Smoke flavor 0.001 Salt 2.00 Sucralose (dried) 0.02 Ketchup was made using the steps below: dry mix spices, RCS, sucralose and salt. Mix water, vinegar and dry mix using a lightning mixer. Add smoked flavor to the moist mix. Blend 1/4 of the tomato paste and wet mix (water, vinegar and dry mix) at speed 1 for 2 minutes in a Hobart mixer with paddle attachment. Blend the remaining moist mix at speed 1 for 1 minute. Stop and scrape the bowl well. Continue blending for 1 minute at speed 1. Heat the ketchup to 105 ° C and hold for 15 seconds. Cool to 80 ° C. Homogeneize at 150/50 bar using a Panda homogenizer. Immediately pack in a glass jar.

<u style="single">Example 47</u> A beef-flavored gravy mix comprising the oligosaccharide composition according to the present invention was produced. The material was: Water 90.17 Perma-Flo Starch 3.58 Beef flavor 3.25 Resistant corn syrup solid (Sample 5) 10.00 Sugar 0.43 Sweet milk whey 0.42 Caramel color 0.09 spices <u style="single">0.03</u>100.0 in total The following steps were used to make a beef-flavored gravy mix: blend the dry ingredients and the TALO TF-55 flavor (all ingredients except water) until uniformly blended. Disperse this dry mix in cold water using a whisk. Cook to 190 ° F with stirring. Keep the mixture at 190 ° F for 10 minutes with stirring.

<u style="single">Example 48</u> A dry blend coffee creamer comprising the oligosaccharide composition according to the present invention was produced. The material was: Commercial creamer powder (Jerzee blend 220077) 21.8 Resistant corn syrup solids (Sample 5) 78.2 The following steps were used to make a dry blend coffee creamer: the ingredients were blended, weighed and screened from a 10 mesh screen into a tumble blender container, ribbon blender or paddle blender. Blend and package the formulation for 10-25 minutes. If necessary, silicon dioxide or sodium aluminosilicate is added as an anti-caking agent.

<u style="single">Example 49</u> A soybean-based dry coffee creamer powder slurry containing the oligosaccharide composition according to the present invention was produced. The material was:<tables num="20"><img id="000021" he="58" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Add water to the batch tank and heat to 120-140 ° F. Sodium casein is added to water and hydrated for 10-30 minutes. The mono and diglyceride are melted in hydrogenated soybean oil or melted separately. Once the casein sodium has been hydrated, add soybean oil and mono and diglycerides to the batch tank. Blend the mixture well. The remaining resistant corn syrup is added to the batch tank, the mixture is heated to 170 ° F, homogenized by two-step homogenization (if necessary) and kept for 30 minutes. The product is thus ready to be spray-dried at an inlet temperature of 350-500 ° F and an discharge temperature of 150-200 ° F. An optional fluidized bed dryer is also used. Sodium aluminosilicate or silicon dioxide may also be included for anti-caking purposes. Phosphates and / or anticoagulants may also be included.

<u style="single">Example 50</u> A coconut-based coffee creamer powder slurry for spray drying containing the oligosaccharide composition according to the present invention was produced. The material was:<tables num="21"><img id="000022" he="58" wi="159" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> The following steps were used to make coconut-based coffee creamer powder: add water to a batch tank and heat to 120-140 ° F. Sodium casein is added to water and hydrated for 10-30 minutes. Mono and diglyceride are melted in hydrogenated coconut oil or melted separately. Once the casein sodium has been hydrated, add coconut oil and mono and diglycerides to the batch tank. Blend the mixture well. Remaining Ingredients Add resistant corn syrup and dipotassium phosphate to the batch tank, heat the mixture to 170 ° F, homogenize by two-step homogenization (if necessary) and hold for 30 minutes. The product is thus ready to be spray-dried at an inlet temperature of 350-500 ° F and an discharge temperature of 150-200 ° F. An optional fluidized bed dryer is also used. Sodium aluminosilicate or silicon dioxide may also be included for anti-caking purposes.

<u style="single">Example 51</u> Ice cream coatings and / or compound coatings can be made using resistant corn syrup solids to reduce total calories by reducing and reducing sugar content. The fiber content is significantly increased compared to a typical coating (eg, in this example we have 33g / 100g for a comparative control of a 5g / 100g coating).<tables num="22"><img id="000023" he="43" wi="158" file="JP6000504B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Ice cream coatings and / or compound coatings can be made using the steps below: Grind solid corn syrup to a particle size of 5 to 125 microns and an average of about 30 to 40 microns. Sift the solids to obtain the desired particles. Combine cocoa powder and sucralose with solid corn syrup. Melt the shortening and combine with lecithin. Add the molten shortening / lecithin mixture while mixing the blended dry ingredients and scrape the bowl regularly. Apply to frozen novelties, baked products, etc. as desired.

<u style="single">Example 52</u> Two samples of resistant corn syrup (RCS) were prepared as in sample 5 of Example 16 above, one of which had a low monosaccharide content ("LS" is "low sugar" in the description below). Regarding). The wt% dsb of monosaccharides, disaccharides, trisaccharides and 4- and higher sugars were: Where to go DP1 DP2 DP3 DP4 + RCS 12.5 4.7 4.1 78.7 RCS LS 1.6 4.6 4.6 89.2 Samples of 2-resistant corn syrup and maltodextrin were provided to dogs. Blood samples were occasionally taken from dogs after feeding to examine the glycemic response. Changes in blood glucose concentration over time are shown in FIG. 15 and summarized in the table below.<u style="single"> Item Maltodextrin RCS RCS LS SEM </u>N 5 5 5 Time to glucose peak, min 30 18 18 4.9 Increased area under the glucose curve 155.1^d 37.7^{b b} 73.9^c 12.9<u style="single">Relative glycemic response 100.0</u>^{<u style="single">d</u>}<u style="single"> 24.5</u>^{<u style="single">b b</u>}<u style="single"> 50.1</u>^{<u style="single">c</u>}<u style="single"> 7.8</u>^abThe average of different tops in the same row is different (P &lt;0.05) SEM = mean standard error

<u style="single">Example 53</u> Six samples of resistant corn syrup were prepared as in sample 5 of Example 16 above. Each sample was 72% ds syrup and the rest was water. The sample was essentially free of fat, protein or ash. 6 samples were: RCS GR1 (RCS, 72% ds syrup 70% fiber, 15% sugar) (the "sugar" in these samples is related to the sum of simple and disaccharides) RCS GR2 (RCS LS, 72% ds syrup 80% fiber, 5% sugar) RCS GR3 (RCS, 50% fructose, 72% ds syrup) RCS GR4 (RCS, 50% sorbitol, 72% ds syrup) RCS GR5 (RCS LS, 25% fructose, 72% ds syrup) RCS GR6 (RCS LS, 25% sorbitol, 72% ds syrup) A sample containing 25 g (dsb) of syrup was prepared as follows: 2.838 kg of filtered water was added to a jug containing a known weight of RCS. The lid was attached to the jug and then mixed well by shaking and stirring until all the syrup had melted. This 12 oz (350 g) solution contained 25 g of test carbohydrates on a dry solid basis. A control solution was prepared by mixing 25 g anhydrous glucose with 300 mL of water. The sample was administered to 10 healthy human subjects. Subject characteristics: 5 males, 5 females; age 35 ± 10y; body volume index 24.0 ± 3.8kg / m²Met. Each subject underwent 9 tests on separate days, including 6 test meals and 3 standard glucose drinks containing 25 g of commercial carbohydrates. Blood glucose was measured at fasting and at 15, 30, 45, 60, 90 and 120 minutes after eating. The increased area (iAUC) under the blood glucose response curve was calculated. Each subject's iAUC after consumption of each test meal was presented as a percentage of the mean iAUC of the three-time glucose control ingested by that subject. The area of increase under the curve of the product and the relative glycemic response (RGR) were: iAUC RGR Glucose (25g) 124.4 ± 13.5^a 100^a RCS GR1 38.5 ± 4.6^{b b} 32.6±3.8^{b b} RCS GR2 25.6 ± 3.7^{b b} 23.2±4.6^{b b} RCS GR3 30.1 ± 4.4^{b b} 26.2±4.2^{b b} RCS GR4 17.4 ± 4.1^{b b} 15.3±3.6^{b b} RCS GR5 27.6 ± 4.0^{b b} 25.4±4.3^{b b} RCS GR6 20.9 ± 4.0^{b b} 18.2±3.5^{b b} Different superscript values are significantly different (P &lt;0.001). There was no statistical significance in the taste between any foods.

<u style="single">Example 54</u> Sweetose^R4300 corn syrup (81% ds) was passed through a paddle mixer with a hot oil jacket at a rate of 77 kg / h to evaporate to a moisture content of less than 6%. The paddle mixer rotor speed was typically set to 300-600 rpm and the oil jacket temperature was changed from 150 ° C to 205 ° C. In some of the tests, phosphoric acid was added at a rate that resulted in 0.1% to 0.4% phosphoric acid solids in solid corn syrup. In some of the tests, hydrochloric acid was added at 25 ppm instead of or in addition to phosphoric acid. The products (25 mg) collected from these studies were dissolved in 4 mL pH 4.0 buffer and incubated with 10 μL of 10 mg / mL Amyloglucoxidase Sigma Catalog # A-7255 solution at 45 ° C for 2 hours. .. Part of this incubation was treated with a small amount of ion exchange resin and filtered (0.45 micron) prior to sugar distribution analysis by liquid chromatography. From this analysis,% by weight of carbohydrates found to be present as trisaccharides or higher are quantified as digestive resistant carbohydrates and are listed as% fiber in the table below: Sample name Temperature ° C% H₃PO₄ HClppm% fiber Run 1 194 0.2% 43 Run 2 195 0.2% 25 52 Run 3 193 0.4% 25 62 Run 4 203 0.4% 25 68 Run 5 180 0.2% 27 Run 6 181 0.4% 37 Run 7 181 0.4% 25 33 Polydextrose control 82 An experimental sample of polydextrose was used as a control in this test, showing a level of about 82% fiber.

<u style="single">Example 55</u> Sweetose^R4300 corn syrup (81% ds) was passed through a paddle mixer with a hot oil jacket at a rate of 77 kg / h to evaporate to a moisture content of less than 3%. The paddle mixer rotor speed was typically set to 800 rpm and the oil jacket temperature was set to 210 ° C. In some of the tests, phosphoric acid was added at a rate that resulted in 0.1% to 0.4% phosphoric acid solids in solid corn syrup. In some of the tests, hydrochloric acid was added at 25 or 50 ppm instead of or in addition to phosphoric acid. The products (25 mg) collected from these studies were dissolved in 4 mL pH 4.0 buffer and incubated with 10 μL of 10 mg / mL Amyloglucoxidase Sigma Catalog # A-7255 solution at 45 ° C for 2 hours. .. Part of this incubation was treated with a small amount of ion exchange resin and filtered (0.45 micron) prior to sugar distribution analysis by liquid chromatography. From this analysis,% by weight of carbohydrates found to be present as trisaccharides or higher are quantified as digestive resistant carbohydrates and are listed as% fiber in the table below: Sample name Temperature ° C% H₃PO₄ HClppm% fiber Run 2-1 210 0.0% 11 Run 2-2 210 0.2% 79 Run 2-3 210 0.0% 12 Run 2-4 210 0.1% 43 Run 2-5 210 0.1% 51 Run 2-6 210 0.2% 61 Run 2-7 210 0.3% 84 Run 2-8 210 0.2% 25 79 Run 2-9 210 0.0% 11 Run 2-10 210 0.1% 43 Run 2-11 210 0.1% 25 57 Run 2-12 210 0.2% 53 Run 2-13 210 0.2% 25 62 Run 2-14 210 0.4% 56 Run 2-15 210 0.4% 25 55 Run 2-16 210 0.4% 50 62 Run 2-17 210 0.0% 50 65 Run 2-18 210 0.0% 50 59 Polydextrose control 82 An experimental sample of polydextrose was used as a control in this test, showing a level of about 82% fiber.

The above description of specific aspects of the invention is not a list of all possible aspects of the invention. Those skilled in the art will recognize that other aspects also fall within the scope of the claims below. For example, certain slow-digesting or digestive-resistant compositions are used as ingredients in food products in some of the above examples. Other slow-digesting or resistant compositions of the present invention are also used in their alternatives, but the exact characteristics of the food product may vary to some extent depending on the exact nature of the material used. Should be recognized. Many other changes can be added to the examples here.

<figref num="1">It is a process flow diagram of one aspect of this invention.</figref><figref num="2">It is a graph of the distribution of a certain sugar in the three kinds of dextrose compositions used in Example 3.</figref><figref num="3">It is a graph of the distribution of a certain sugar in the starting material used in Example 4.</figref><figref num="4">It is a graph of the distribution of a certain sugar in the product produced by the enzyme treatment in Example 4.</figref><figref num="5">FIG. 5 is a graph of changes over time with respect to maltose and isomaltose concentrations when the composition was treated with an enzyme in Example 4.</figref><figref num="6">FIG. 5 is a graph of changes in maltose concentration when dextrose syrup was treated with enzymes of different concentrations in Example 4.</figref><figref num="7">FIG. 5 is a graph of changes in isomaltose concentration when dextrose syrup was treated with enzymes of different concentrations in Example 4.</figref><figref num="8">FIG. 5 is a graph of changes over time with respect to the concentration of a sugar when the composition was treated with an enzyme in Example 4.</figref><figref num="9">FIG. 5 is a graph of changes over time with respect to the concentration of a sugar when the diluted composition was treated with an enzyme in Example 4.</figref><figref num="10">It is a graph of the effect of temperature on the formation of certain sugars as a result of enzyme treatment in Example 5.</figref><figref num="11">It is a graph of the effect of temperature on the formation of certain sugars as a result of other enzyme treatments in Example 5.</figref><figref num="12">6 is a graph comparing changes in sugar distribution when the composition is treated with an acid or an enzyme in Example 6.</figref><figref num="13">The analysis of the acid-treated syrup is shown in Example 6.</figref><figref num="14">Chromatographic analysis of acid-treated syrup is shown in Example 6.</figref><figref num="15">It shows the change in blood glucose concentration of dogs after feeding the composition of the present invention or maltodextrin.</figref>