Composition for inhibiting hmf production comprising allulose disaccharide

Abstract

The present application relates to a novel use of an allulose disaccharide.

Description

Composition for inhibiting HMF production comprising allulose disaccharide

[0001] The present application relates to a novel use of allulose disaccharide.

[0002]

[0003] HMF is an organic compound formed by the dehydration of compounds containing aldehyde and hydroxyl groups. It is a white, low-melting compound that is highly soluble in both water and organic solvents. The high production of HMF suggests that it is highly likely to induce a decrease in freshness during the processing and distribution of the product, quality deterioration due to accumulated heat damage, and even persistent non-enzymatic browning. Furthermore, HMF has been confirmed to have negative concerns about human health, such as the still-lingering issue of carcinogenicity (Abraham K (2011) Toxicology and risk assessment of 5-Hydroxymethylfurfural in food, Molecular Nutrition & Food Research. 55 (5): 667-678).

[0004] Heat sterilization is the most commonly used method in the food processing process, but as mentioned above, foods containing sugar generate HMF when heated, so reducing the amount of HMF produced is an important task.

[0005] To solve these problems, research is being conducted on methods for stabilizing product quality by suppressing HMF production, and these have been studied in Food Browning and Its Prevention: An Overview. J. Agric. Food Chem., Vol. 44, No. 3, etc. However, research on methods with better effects is needed, and furthermore, a method of adding carbohydrates has not yet been reported.

[0006]

[0007] Against this backdrop, the inventors of the present invention isolated a novel substance, confirmed that the substance is allulose disaccharide, and confirmed that the production of HMF is suppressed when allulose disaccharide is added to a composition containing sugars, thereby completing the present invention.

[0008]

[0009] The present application provides a composition for inhibiting HMF (Hydroxymethylfurfural) production and / or preventing browning, comprising allulose disaccharide.

[0010] The present application provides a method for inhibiting HMF production and / or preventing browning, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0011] The present application provides a method for producing a composition comprising a saccharide, comprising: preparing a mixed composition comprising a saccharide and an allulose disaccharide; and heating the mixed composition.

[0012]

[0013] The composition comprising the allulose disaccharide of the present application can be usefully used to inhibit sugar dehydration, inhibit HMF production, and / or prevent browning, since it inhibits the production of harmful substances generated during processing, sterilization, and long-term storage.

[0014]

[0015] Figure 1 is an HPLC chromatogram analyzed using a column (Biorad Aminex HPX-87C) of disaccharides produced during the allulose manufacturing process.

[0016] Figure 2 is an HPLC chromatogram of D1 and D2, which were analyzed using a column (YMC Pack Polyamine II) as a mixture of substances fractionated by a column of disaccharides produced during the allulose manufacturing process.

[0017] Figure 3 shows the three-dimensional structure of D1, an allulose disaccharide.

[0018] Figure 4 shows the structure and carbon numbering of allulose.

[0019]

[0020] This is explained in detail as follows. Meanwhile, each description and embodiment disclosed in this application can also be applied to each other description and embodiment. In other words, all combinations of the various elements disclosed in this application fall within the scope of this application. Furthermore, the scope of this application is not limited by the specific descriptions described below.

[0021] Furthermore, those skilled in the art will recognize or be able to ascertain, using only routine experimentation, numerous equivalents to the specific embodiments of the present application described herein. Furthermore, such equivalents are intended to be encompassed by this application.

[0022] One aspect of the present application provides a composition for inhibiting HMF (Hydroxymethylfurfural) production comprising allulose disaccharide.

[0023]

[0024] The term "allulose disaccharide" in the present application may be used interchangeably with terms such as "allulose dimer", "allulose diploid", and "disaccharide allulose", and means "a compound in which two allulose molecules are linked by a glycosidic bond."

[0025] Specifically, the above allulose disaccharide is a glycosidic bond in which two allulose molecules are connected by a glycosidic bond, and the glycosidic bond may be a glycosidic bond in which the hydroxyl group of the second carbon (C2) of one allulose molecule among the two allulose molecules is glycosidic bonded to the hydroxyl group of any one of the carbons of the first to sixth carbons (C1 to C6) of one allulose molecule.

[0026] Specifically, it may be a compound in which at least one of two allulose molecules is a cyclic allulose, and the hydroxyl group at the 2nd carbon of the cyclic allulose is connected by a glycosidic bond to the hydroxyl group at any one of the 1st to 6th carbons of another allulose molecule. The number of glycosidic bonds may be 1 to 2, and specifically, it may be 1.

[0027] In one embodiment, the bond may be a glycosidic bond between the hydroxyl group at the 2nd carbon of the cyclic allulose and the hydroxyl group at the 6th carbon of another allulose.

[0028] In one embodiment, one of the two allulose molecules may be in the form of psicofuranose, and the other molecule may be in the form of psicopyranose. In one embodiment, the allulose may be represented by the following chemical formula 1, but is not limited thereto.

[0029] [Chemical Formula 1]

[0030]

[0031] In one embodiment, the allulose disaccharide of the present application may be a compound named 2-(hydroxymethyl)-2-((3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol, and more specifically A compound named as (2S,3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol may be, but is not limited to.

[0032] In one embodiment, the allulose disaccharide of the present application may be a compound named 2-(hydroxymethyl)-2-((3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol, and more specifically A compound named (2S, 3R, 4R, 5R)-2-(hydroxymethyl)-2-(((2R, 3S, 4R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol may be, but is not limited to, a compound named (2S, 3R, 4R, 5R)-2-(hydroxymethyl)-2-(((2R, 3S, 4R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol).

[0033] The above (2S,3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol may collectively refer to compounds named 6-O-β-D-psicopyranosyl-α-D-psico furanose or 6-O-β-D-psicopyranosyl-β-D-psico furanose depending on the form of psicofuranose.

[0034] The above (2S,3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol is (2S,3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R,5S)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol((2S, It may be a compound named as (3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R,5S)-3,4,5-trihydroxy-5-(hydroxymethyl) tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol), or (2S,3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R,5R)-3,4,5-trihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol((2S, 3R,4R,5R)-2-(hydroxymethyl)-2-(((2R,3S,4R,5R)-3,4,5-trihydroxy-5-(hydroxymethyl) It may be a compound named as (tetrahydrofuran-2-yl)methoxy)tetrahydro-2H-pyran-3,4,5-triol), but is not limited thereto.

[0035] Specifically, the compound of the above chemical formula 1 can exist in two forms of the following chemical formulas 2 and / or 3.

[0036] [Chemical Formula 2]

[0037]

[0038] [Chemical Formula 3]

[0039]

[0040] The compound of the above chemical formula 2 may be referred to as 6-O-β-D-Psicopyranosyl-α-D-psico furanose, and the compound of the above chemical formula 3 may be referred to as 6-O-β-D-Psicopyranosyl-β-D-psico furanose.

[0041]

[0042] The “HMF” of the present application is a substance also called 5'-HMF (5-hydroxymethyl-furfural), and may have a structure represented by the chemical formula 4 below.

[0043] [Chemical Formula 4]

[0044]

[0045] The above HMF may be generated from a compound containing an aldehyde group and a hydroxyl group.

[0046] In this application, “HMF generating material” means a compound capable of generating HMF.

[0047] The above HMF generating material includes, without limitation, substances containing an aldehyde group and / or a hydroxyl group, and may also include, for example, substances such as carbohydrates, glycolipids, and glycoproteins.

[0048] Specifically, the HMF production may be due to sugar (expressed as sugar or saccharide). The HMF production may be due to sugar decomposition. The sugar decomposition includes sugar decomposition by dehydration.

[0049] Specifically, the sugar may be a monosaccharide. The monosaccharide may include, without limitation, aldotriose (glyceraldehyde), ketotriose (dihydroxyacetone), aldotetrose (erythrose, threose), ketotetrose (erythrulose), aldopentose (arabinose, lyxose, ribose, xylose), ketopentoses (ribulose, xylulose), deoxysugars (deoxyribose), aldohexoses (allose, altrose, galactose, glucose (glucose), gulose, idose, mannose, talose), ketohexoses (fructose (fructose), allulose, sorbose, tagatose), deoxysugars (fucose, fuculose, rhamnose), ketoheptoses (mannoheptulose, sedoheptulose), and the like, as long as they have the potential to produce HMF. Specifically, it may be hexose, and more specifically, it may be allulose, but is not limited thereto.

[0050] Meanwhile, a mixture containing one or more of the aforementioned substances may also be included in the HMF generating substance.

[0051] The above HMF is also an example of a glycation intermediate. The term "glycation endproduct" in the present application refers to a product produced by a reaction between an amino acid group such as a lysine residue of a protein and a reducing sugar without the action of an enzyme, and includes both glycation intermediates and glycation endproducts, and is produced from glycation intermediates to glycation endproducts (AGEs). The glycation endproducts may be brown and produce volatile odor components, or may refer to various substances produced by a reaction between blood glucose or glucose breakdown products and various protein components such as hemoglobin, LDL, and collagen in the body. Glycation endproducts are representative examples of byproducts produced during the processing, storage, and sterilization of compositions containing sugars.

[0052] Once formed, advanced glycation end products (AGEs) remain intact even after blood sugar levels return to normal, accumulating in the blood and tissues throughout the protein's lifespan. Accumulated AGEs form cross-links with proteins and interact with the receptor for advanced glycation end products (AGEs), leading to the accumulation of inflammatory cells.

[0053] Therefore, since the production of glycation end products that may have a harmful effect on the human body and the amount of HMF are closely related, the allulose disaccharide of the present application may also suppress the production of glycation end products by suppressing the production of HMF.

[0054] That is, another aspect of the present application provides a composition for inhibiting the production of glycation products comprising allulose disaccharide.

[0055]

[0056] Another aspect of the present application provides a composition for inhibiting sugar dehydration, comprising allulose disaccharide.

[0057]

[0058] The term "hydration" in this application refers to the entire process in which water is separated within or between molecules. In this application, the molecule causing the dehydration reaction may be a sugar molecule.

[0059] In this application, the term "sugar dehydration reaction" refers to a reaction in which H2O is generated within or between sugar molecules. Specifically, the sugar dehydration reaction may be a reaction in which H2O is generated within a sugar molecule.

[0060] The above sugar molecule may be specifically a monosaccharide, which is a unit of sugar (glucide). The monosaccharide is as described above.

[0061] When a dehydration reaction occurs in a sugar molecule, other substances derived from the sugar molecule may be produced in addition to H2O molecules. For example, the dehydration reaction in a hexose may be a reaction that produces hydroxymethylfurfural, or HMF, in addition to H2O molecules, as shown in the following reaction scheme 1.

[0062]

[0063] [Reaction Formula 1]

[0064]

[0065] Inhibition of sugar dehydration refers to preventing the aforementioned sugar dehydration reaction from occurring, or reducing the occurrence of sugar dehydration compared to an environment where allulose disaccharides are absent or present in relatively small amounts. This inhibition of sugar dehydration can be confirmed by measuring the amount of sugar dehydration product. For example, the presence or absence of sugar dehydration can be confirmed by measuring the amount of HMF produced.

[0066]

[0067] The above dehydration reaction may occur under heating, sterilization and / or processing conditions of the known composition, but is not limited thereto, and also includes reactions that occur naturally at room temperature, and thus also includes reactions that occur during storage of the composition.

[0068]

[0069] Another aspect of the present application provides an anti-browning composition comprising allulose disaccharide.

[0070] In this application, "preventing browning" may be used to mean preventing browning, delaying browning, suppressing browning, etc., and may be used interchangeably in this application. For example, browning reactions in foods such as cereals and cereal bars, potato chips, bakery products, carbonated beverages, fruit juices, fruit juices, fruit wines, sauces, candies, jellies, jams, ice cream, and beer cause a deterioration in quality, leading to a loss of aroma, taste, and nutritional value.

[0071] Browning reactions such as the Maillard reaction and caramelization can occur. For example, the Maillard reaction can produce brown substances (melanoidins) when the carbonyl groups of sugars and the amino acids of proteins react with heat or other factors. This reaction is also called the melanoidin reaction after the reactant, or the amino carbonyl reaction due to the reactant.

[0072] In the intermediate stage of the Maillard reaction, HMF, a highly reactive substance, is created, and the products in the final stage of the reaction are also highly reactive substances. These substances form a polymer to form a brown fluorescent melanoidin pigment, and browning occurs during this process.

[0073] As described above, since the production of HMF is closely related to the browning reaction of the composition, the allulose disaccharide of the present application can be used for anti-browning purposes by inhibiting HMF production. In other words, the anti-browning may be due to the inhibition of HMF production.

[0074]

[0075] In the above composition, the content of allulose disaccharide may be included in an amount of more than 0 and less than 15 parts by weight relative to 100 parts by weight of the HMF generating material included in the composition.

[0076] Specifically, it may include allulose disaccharide in an amount greater than 0.0001 parts by weight, greater than 0.001 parts by weight, greater than 0.01 parts by weight, greater than 0.1 parts by weight, or greater than 0.15 parts by weight but less than or equal to 15 parts by weight relative to 100 parts by weight of the total HMF producing material, and / or it may include allulose disaccharide in an amount less than or equal to 15 parts by weight, less than or equal to 13 parts by weight, less than or equal to 11 parts by weight, less than or equal to 10 parts by weight, less than or equal to 9 parts by weight, less than or equal to 8 parts by weight, less than or equal to 7 parts by weight, less than or equal to 6 parts by weight, less than or equal to 5 parts by weight, less than or equal to 4 parts by weight, less than or equal to 3 parts by weight, less than or equal to 2 parts by weight, or less than or equal to 1 part by weight but more than 0 parts by weight relative to 100 parts by weight of the HMF producing material, but is not limited thereto.

[0077] In the above composition, the content of allulose disaccharide may be included in an amount of more than 0 and less than 15 parts by weight based on 100 parts by weight of the total sugar included in the composition. Specifically, it may contain allulose disaccharides in an amount greater than 0.0001 parts by weight, greater than 0.001 parts by weight, greater than 0.01 parts by weight, greater than 0.1 parts by weight, or greater than 0.15 parts by weight but less than or equal to 15 parts by weight, relative to 100 parts by weight of total sugars, and / or it may contain allulose disaccharides in an amount less than or equal to 15 parts by weight, less than or equal to 13 parts by weight, less than or equal to 11 parts by weight, less than or equal to 10 parts by weight, less than or equal to 9 parts by weight, less than or equal to 8 parts by weight, less than or equal to 7 parts by weight, less than or equal to 6 parts by weight, less than or equal to 5 parts by weight, less than or equal to 4 parts by weight, less than or equal to 3 parts by weight, or less than or equal to 2 parts by weight but more than 0 parts by weight, relative to 100 parts by weight of total sugars, but is not limited thereto.

[0078] Alternatively, the content of allulose disaccharide in the composition may be such that the content of allulose disaccharide is greater than 0 and less than or equal to 15 parts by weight based on 100 parts by weight of the total solid content included in the composition. Specifically, it may contain allulose disaccharide in an amount greater than 0.0001 parts by weight, greater than 0.001 parts by weight, greater than 0.01 parts by weight, greater than 0.1 parts by weight, or greater than 0.15 parts by weight but less than or equal to 15 parts by weight, relative to 100 parts by weight of the total solids, or it may contain allulose disaccharide in an amount less than or equal to 15 parts by weight, less than or equal to 13 parts by weight, less than or equal to 11 parts by weight, less than or equal to 10 parts by weight, less than or equal to 9 parts by weight, less than or equal to 8 parts by weight, less than or equal to 7 parts by weight, less than or equal to 6 parts by weight, less than or equal to 5 parts by weight, less than or equal to 4 parts by weight, less than or equal to 3 parts by weight, or less than or equal to 2 parts by weight but more than 0 parts by weight, relative to 100 parts by weight of the total solids, but is not limited thereto.

[0079]

[0080] The above composition may be a food composition. The food composition of the present application includes, but is not limited to, general foods, health foods, and medical (or patient) food compositions. Specifically, the food composition of the present application may be a beverage (e.g., carbonated beverage, fruit juice beverage, fruit and vegetable beverage, dietary fiber beverage, carbonated water, millet powder, tea, coffee, etc.), an alcoholic beverage, a bakery, a sauce (e.g., ketchup, tonkatsu sauce, etc.), a dairy product (e.g., fermented milk, processed milk, etc.), a meat product (e.g., ham, sausage, jerky, etc.), a chocolate product, gum, candy, jelly, ice cream, syrup, dressing, a snack (e.g., cookies, crackers, biscuits, etc.), pickled vegetables (e.g., cheong, sugar-coated fruit, red ginseng extract, or red ginseng slices, etc.), a meal replacement (e.g., frozen foods, retort foods, and HMR (home meal replacement), etc.), or a processed food. However, this is just one example and is not limited to this.

[0081] The food composition of the present invention may contain various flavoring agents or natural carbohydrates as additional ingredients. The natural carbohydrates mentioned above include monosaccharides such as glucose and fructose, disaccharides such as maltose and sucrose, polysaccharides such as dextrin and cyclodextrin, and sugar alcohols such as xylitol, sorbitol, and erythritol. As sweeteners, natural sweeteners such as thaumatin and stevia extracts, or synthetic sweeteners such as sucralose, saccharin, and aspartame, may be used.

[0082] In addition to the above, the food composition of the present application may contain various nutrients, vitamins, electrolytes, flavoring agents, coloring agents, pectin and its salts, alginic acid and its salts, organic acids, protective colloid thickeners, pH adjusters, stabilizers, preservatives, glycerin, alcohol, acidulants and salting agents used in carbonated beverages, etc. In addition, the food composition of the present application may contain fruit pulp for the production of natural fruit juice, fruit juice drinks, and vegetable drinks. These ingredients may be used independently or in combination. In addition, a person skilled in the art may appropriately select and add substances that may be commonly included in a food composition, and the ratio of such additives may be selected in the range of 0.001 to 1 part by weight, or 0.01 to 0.20 part by weight per 100 parts by weight of the food composition of the present application, but is not limited thereto.

[0083]

[0084] Another aspect of the present application provides a method for inhibiting HMF production, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0085] The term "prepare" in the present application includes, without limitation, any method for providing a composition comprising a saccharide and an allulose disaccharide. That is, any method that results in the composition comprising a saccharide and an allulose disaccharide. For example, preparing a composition comprising a saccharide and an allulose disaccharide may include adding an allulose disaccharide to a composition comprising a saccharide, adding a saccharide to a composition comprising an allulose disaccharide, or producing an allulose disaccharide during the preparation of a saccharide / saccharide composition.

[0086] The above composition may contain other ingredients without limitation as long as it contains only sugars and allulose disaccharides.

[0087] Meanwhile, a composition comprising a saccharide and an allulose disaccharide may also be referred to as a "mixture." In the mixture composition, the "saccharide" other than the allulose disaccharide may include, but is not limited to, allulose, for example.

[0088] The above method for inhibiting HMF production may further include heating the composition after preparing the composition including saccharides and allulose disaccharides. However, the present invention is not limited thereto, and the heating may be performed before, after, or simultaneously with the preparation of the mixed composition.

[0089] The above heating may be performed at an appropriate temperature range depending on the type of composition, and the temperature range, heating time, sterilization method, etc. may be appropriately performed by a person skilled in the art based on information known in the art. Specifically, it may be performed at a temperature of 60°C or higher and 100°C or lower, and more specifically, it may be performed at a temperature of 60°C or higher and 95°C or lower, 65°C or higher and 95°C or lower, or 70°C or higher and 95°C or lower, but is not limited thereto.

[0090] The above heating may be performed for a time exceeding 0 hours and less than or equal to 108 hours, and specifically, may be performed for 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or more, but is not limited thereto.

[0091] Another aspect of the present application provides a method for producing a composition comprising a saccharide, comprising: preparing a mixed composition comprising a saccharide and an allulose disaccharide; and heating the mixed composition.

[0092] Heating the above mixture composition may, but is not limited to, inhibiting HMF production.

[0093] The above heating may be performed before, after, or simultaneously with the preparation of the mixed composition.

[0094] A composition comprising a saccharide manufactured by the above manufacturing method may have a low impurity content, a low amount of HMF production, an increase in the allulose content, a change in its physical properties, a low occurrence of by-products, or a low occurrence of crystallization, browning, oxidation / reduction, or a reaction in which a saccharide other than allulose disaccharide is converted into another substance. Specifically, the above-described reaction may occur less than when a composition containing no allulose disaccharide or having a relatively low allulose disaccharide content compared to the above-described mixed composition is heated under the same conditions. However, the present invention is not limited thereto.

[0095]

[0096] Another aspect of the present application provides a method for inhibiting sugar dehydration, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0097] Another aspect of the present application provides a method for preventing browning, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0098] Another aspect of the present application provides a method of sterilizing a composition, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0099] The method may further include heating the composition after preparing the composition comprising saccharides and allulose disaccharides. However, the method is not limited thereto, and the heating may be performed before, after, or simultaneously with the preparation of the mixed composition.

[0100]

[0101] HMF production, sugar dehydration, anti-browning, sugars, and heating are as described above.

[0102] The above composition may be, for example, a food composition, but is not limited thereto.

[0103] As for food, it is as mentioned above.

[0104]

[0105] Another aspect of the present application provides a composition for inhibiting saccharide modification comprising allulose disaccharide.

[0106] Another aspect of the present application provides a method for inhibiting denaturation of a composition, comprising preparing a composition comprising a saccharide and an allulose disaccharide.

[0107] The method may further comprise heating the composition after preparing the composition comprising the saccharide and allulose disaccharide. However, the method is not limited thereto, and the heating may be performed before, after, or simultaneously with the preparation of the mixed composition.

[0108] Allulose disaccharides, sugars, and heating are as described above.

[0109] The above-mentioned denaturation includes, but is not limited to, the conversion of sugars into other substances, changes in their physical properties, or the generation of by-products, such as crystallization, browning, and oxidation / reduction reactions.

[0110]

[0111] Another aspect of the present application provides a use of allulose disaccharide for inhibiting HMF production.

[0112] As described above, inhibition of allulose disaccharide and HMF production is the same.

[0113]

[0114] Hereinafter, this application will be described in more detail through examples and experimental examples. However, these examples and experimental examples are intended to exemplify this application and the scope of this application is not limited to these examples and experimental examples.

[0115]

[0116] Example 1: Isolation of a novel allulose disaccharide

[0117] In the allulose manufacturing process disclosed in US 2018-0327796 A1, disaccharides were separated via HPLC. Specifically, by performing the HPLC chromatogram analysis conditions shown in Table 1 below, it was confirmed that, in addition to allulose, a previously unknown novel substance (unknown) was produced from the raw solution, as shown in Figure 1.

[0118] The new substance separated as above had some differences in content depending on the manufacturing process, but it was confirmed that it existed at less than 2% in the initial raw solution and increased to 5% depending on the storage time.

[0119]

[0120] EquipmentAgilent technologies 1200 seriesColumnBiorad Aminex HPX-87C (7.8

[0121]

[0122] As a result, allulose was identified at 21.1 minutes and the novel substance at 31.7 minutes.

[0123] Accordingly, in order to separate the newly produced substance, the new substance was purified to a purity of 95% or higher using preparative HPLC, and then separated again precisely using a normal phase column.

[0124] Specifically, HPLC chromatograms were performed.

[0125] The chromatogram separation conditions are as shown in Table 2 below.

[0126]

[0127] EquipmentShimadzu LC 10AColumnYMC Pack Polyamine II (4.6

[0128]

[0129] As a result, the substance that appeared as one peak under the HPLC conditions of Table 1 was separated by confirming that it appeared as two peaks under the separation conditions of Table 2 (Fig. 2). The substance of the peak confirmed at 22.5 minutes was named D1, and the substance of the peak confirmed at 17.7 minutes was named D2.

[0130]

[0131] Example 2: Confirmation of the inhibitory effect of allulose disaccharide on HMF production.

[0132] Example 2-1: Comparison of HMF production rates of allulose disaccharides

[0133] Allulose was selected as a representative example of a monosaccharide that denatures upon heating and produces high levels of HMF. To determine whether the disaccharide (dimer) isolated in Example 1 can be applied to various food products with varying sugar content, the differences were compared by varying sugar concentrations. Furthermore, considering a more harsh environment, the HMF production rate was compared under the highest temperature among food sterilization conditions, retort (121°C, 15 minutes).

[0134] Specifically, using crystalline allulose (CJ CheilJedang, purity 99% or higher) with the highest composition ratio as a monosaccharide, ultrapure water without impurities was added, and the disaccharide with purity 95% or higher separated in Example 1 was quantitatively measured and mixed at different mixing ratios to prepare Experimental Example 1. In addition, samples (A) to (F) were prepared by varying the amount of water added to Experimental Example 1 to have concentrations of 1, 5, 10, 20, 30, and 50% (w / w), respectively (Table 3).

[0135] Meanwhile, in order to compare the effects of other disaccharides, sugar, a representative disaccharide, was added instead of allulose disaccharide and used as Comparative Example 1. Specifically, in the same manner as Experimental Example 1, sugar, a disaccharide, was added to allulose crystals, a monosaccharide, in the same ratio as Experimental Example 1, and the ratio of its components was confirmed using HPLC under the conditions of Table 1. Comparative Example 1 and Experimental Example 1, for which the ratio of components was confirmed, were dissolved in ultrapure water without impurities to prepare 1 to 50% (w / w).

[0136]

[0137] Sample composition Sugar (based on 100% solid weight) Mixing ratio Concentration (%, w / w) Monomer (Allulose) Dimer M:D (A) (B) (C) (D) (E) (F) Comparative example 195.2 14 1.90 450:115 10 20 30 50 Experimental example 194.8 5 1.90 150:115 10 20 30 50

[0138]

[0139] All prepared samples were placed in a high-pressure sterilizer (Jeotech, ST-105G) and heated at 121°C for 15 minutes. The time required for the equipment to heat up was not considered, and the heating time was measured after reaching the target temperature. After heat treatment, the samples were removed and left at room temperature for 10 minutes. They were then analyzed using HPLC under the conditions listed in Table 1 of Example 1.

[0140] All experiments were repeated three times, and the results are shown in Table 4 below.

[0141]

[0142] Sample nameConcentration (%, w / w)Composition Sugar (based on 100% solid weight)HMF Increase rateMonomer (Allulose)Dimer %Comparative example 1 (A) 193.3101.855182.8% (B) 589.4061.847458.7% (C) 1094.1671.897291.5% (D) 2092.0721.866337.8% (E) 3092.1671.897378.7% (F) 5090.4 531.872577.5%Experimental Example 1 (A) 197.5160.765114.1% (B) 598.5650.431128.8% (C) 1098.5600.449144.7% (D) 2098.1850.576156.6% (E) 3097.5240.797219.9% ​​(F) 5095.6951.533285.4%

[0143] As a result of the experiment, it was confirmed that in Experimental Example 1, which contained a certain amount of allulose disaccharide, the increase rate of HMF was significantly low. Although the heating temperature was very high and could not completely block the production of HMF, it was confirmed that the stability was significantly improved compared to Comparative Example 1, where sugar was added in the same ratio instead of allulose disaccharide as the disaccharide, in which monosaccharides directly absorbed heat damage and rapidly decomposed. In other words, it can be confirmed that allulose disaccharide has a significantly higher effect of delaying and protecting monosaccharides from deterioration due to heating compared to other disaccharides.

[0144] In addition, from the perspective of concentration, it was confirmed that the higher the absolute amount of monosaccharides, which are HMF-generating substances, the more HMF was generated in high-concentration samples under the same heating conditions. However, compared to Comparative Example 1, which added sugar, it was confirmed that in Experimental Example 1, which added allulose disaccharide, the generation of HMF was significantly lower and the denaturation of monosaccharides was delayed.

[0145] Through this, it was confirmed that allulose disaccharide suppresses dehydration, decomposition, and denaturation of monosaccharides even in harsh environments with very high temperatures, and thus allulose disaccharide can be usefully used to suppress the production of HMF and the dehydration reaction of sugars.

[0146]

[0147] Example 2-2: Comparison of HMF production rates by allulose disaccharide content

[0148] The disaccharides (dimers) separated in Example 1 were mixed as shown in Table 5 below to prepare samples with different disaccharide ratios.

[0149] Specifically, using crystalline allulose (CJ CheilJedang, purity 99% or higher) with the highest composition ratio as a monosaccharide, ultrapure water without impurities was added to prepare a 10% (w / w) similar to the average concentration of a typical beverage, and used in Experimental Example 2. In addition, allulose disaccharide with a purity of 95% or higher isolated in Example 1 was quantitatively measured and added to crystalline allulose, and then similarly dissolved in ultrapure water to prepare a 10% concentration, and used in Experimental Examples 3 and 4. The composition of each prepared sample was analyzed once again using HPLC under the conditions of Table 1 of Example 1, and it was confirmed that the amount of included disaccharide was different, as shown in Table 5 below.

[0150]

[0151] Sample composition Sugar (based on 100% solids weight) Mixing ratio Concentration Monomer Dimer Others Monomer: Dimer (%, w / w) Experimental example 299.8230.1580.019632:110 Experimental example 397.5321.1541.31485:110 Experimental example 495.2412.1452.61444:110

[0152]

[0153] Each prepared sample was heated at 95°C, the typical processing temperature for beverages, and samples were taken at 20-minute intervals to determine changes in composition and the amount of HMF produced. The amount of HMF was analyzed using HPLC under the conditions listed in Table 1 of Example 1.

[0154]

[0155] All experiments were repeated three times, and the results are shown in Table 6 below.

[0156]

[0157] Sample nameHeating time (min, 95℃)Composition Sugar (based on 100% solid weight)HMF increase rateMonomerDimer%Experimental example 2099.8a0.2a100.0%d2099.8b0.2b110.3%c4099.7c0.1c120.5%b6099.7d0.1d128.2%ap0.0000.0000.000Experimental example 3097.5d1.2a100.0%d2098.1c0.9b103.5%c4098.5b0.6c108.8%b6099.1a0.3d112.3%ap0.0000.0000.000Experimental example 4095.2d2.1a100.0%a2096.3c1.6b100.0%a4097.4b1.0c101.3%a6098.5a0.4d101.3%ap0.0000.0000.110

[0158] ※ Different strings a, b, c, d in the vertical direction indicate a significant difference (p<0.05) over the heating time in the same sample.

[0159]

[0160] In Experimental Examples 2 to 4 containing a certain amount of disaccharide, it was confirmed that monosaccharides actually increased during the decomposition process by first absorbing heat damage in a sufficient amount of disaccharide. Accordingly, it was confirmed that the increase rate of HMF generated from monosaccharides was also significantly low. In particular, in the case of Experimental Example 4 containing the largest amount of disaccharide (containing 2.1% (w / w) of the constituent sugars, approximately 0.21% (w / w) based on the total amount of the sample), it was confirmed that there was no statistically significant difference in the increase rate of HMF even after 60 minutes of heating, confirming that the effect of inhibiting HMF generation was very large.

[0161] Through this, it was confirmed that allulose disaccharide inhibits dehydration, decomposition, and denaturation of monosaccharides and inhibits the production of HMF, and thus it can be seen that allulose disaccharide can extremely delay the quality deterioration phenomenon in which HMF is produced by heat-induced deterioration during the processing and distribution process of typical food products.

[0162]

[0163] Through this experimental process, it was confirmed that when a certain amount of disaccharide including allulose is contained, the decomposition and denaturation of sugar (allulose) by heat, thereby producing HMF, can be significantly delayed.

[0164] This has the advantage of using disaccharides based on sugars, which have an extremely small impact on the taste and characteristics of the product, compared to using additives composed of completely different ingredients (e.g., antioxidants, etc.) to suppress conventional HMF production.

[0165]

[0166] Example 3: Structural identification of allulose disaccharide

[0167] In order to confirm the structure of allulose disaccharide having HMF production inhibition function, the structure of D1 and D2 separated in Example 1 was identified through ESI-MS, 1H NMR, and 13C NMR.

[0168] Specifically, the structure was identified through the following method.

[0169]

[0170] Major 6-O-β-D-Psicopyranosyl-α-D-psicofuranose은, 백색무정형가루, ESI-MS m / z 365 [M+Na]+; 1H NMR (850 MHz, D2O) δH 3.44 (1H, d, J = 12.0 Hz), 3.47 (1H, d, J = 12.0 Hz), 3.56 (1H, dd, J = 11.0, 5.0 Hz), 3.60 (1H, d, J = 12.0 Hz), 3.62 (1H, dd, J = 11.0, 2.5 Hz), 3.70 (1H, br d, J = 12.5 Hz), 3.75 (1H, d, J = 12.0 Hz), 3.75 (1H, br ma), 3.82 (1H, br d, J = 12.5 Hz), 3.84 (1H, br s), 3.92 (1H, t, J = 3.0 Hz), 3.97 (1H, d, J = 5.5 Hz), 4.09 (1H, t, J = 5.5 Hz), 4.13 (1H, br m) [D2O signal δH 4.70]; 13C NMR signalsb δC 57.6, 60.4, 62.9, 64.7, 64.9, 69.1, 68.9, 70.2, 70.3, 81.2, 101.8, 103.4.

[0171] Minor 6-O-β-D-Psicopyranosyl-β-D-psicofuranose is a white amorphous powder, ESI-MS m / z 365 [M+Na]+; 1H NMR (850 MHz, DO) δH 3.49 (1H, d, J = 13.0 Hz), 3.73 (1H, d, J = 13.0 Hz), 3.58 (1H, ma), 3.68 (1H, dd, J = 11.0, 2.5 Hz), 3.62 (1H, ma), 3.71 (1H, br d, J = 12.0 Hz), 3.82 (1H, br d, J = 12.0 Hz), 3.76 (1H, br ma), 3.78 (1H, ma), 3.87 (1H, br s), 3.98 (1H, t, J = 3.0 Hz), 3.95 (1H, d, J = 4.5 Hz), 4.00 (1H, br m), 4.34 (1H, dd, J = 8.0, 4.5 Hz) [D2O signal δH 4.70]; 13C NMR signalsb δC 57.7, 61.4, 62.2, 64.7, 64.8, 69.0, 69.2, 70.8, 74.4, 80.8, 101.8, 105.9.

[0172]

[0173]

[0174] As a result, it was confirmed that D1 is a novel allulose disaccharide and has a structure represented by the following chemical formula 1.

[0175] [Chemical Formula 1]

[0176]

[0177]

[0178] In addition, it was confirmed that D1 has two forms, a major and a minor form (Fig. 3), and the major form, 6-O-β-D-Psicopyranosyl-α-D-psicofuranose, has a structure of the following chemical formula 2, and the minor form, 6-O-β-D-Psicopyranosyl-β-D-psicofuranose, has a structure of the following chemical formula 3.

[0179]

[0180] [Chemical Formula 2]

[0181]

[0182]

[0183] [Chemical Formula 3]

[0184]

[0185] The compound of chemical formula 2 (6-O-β-D-Psicopyranosyl-α-D-psicofuranose) was named compound A, and the compound of chemical formula 3 (6-O-β-D-Psicopyranosyl-β-D-psicofuranose) was named compound B.

[0186] Meanwhile, it was confirmed that D2 is a novel allulose disaccharide having a glycosidic bond between the hydroxyl group of the second carbon (C2; according to the carbon numbering of FIG. 4) of allulose and the hydroxyl group of any one of the carbons 1 to 6 (C1 to C6) of one allulose molecule in a structural isomer relationship with the above chemical formula 1.

[0187]

[0188] From the above description, those skilled in the art will understand that the present application can be implemented in other specific forms without altering its technical concept or essential characteristics. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of this application should be interpreted to include all changes or modifications derived from the meaning and scope of the following claims and their equivalents, rather than the detailed description above.

Claims

1. A composition for inhibiting HMF (Hydroxymethylfurfural) production, comprising allulose disaccharide.

2. A composition according to claim 1, wherein the HMF is produced by sugar.

3. A composition according to claim 2, wherein the sugar is a monosaccharide.

4. A composition in claim 3, wherein the monosaccharide is allulose.

5. In the first paragraph, the allulose disaccharide is a composition in which two allulose molecules are connected by a glycosidic bond, and the glycosidic bond is a glycosidic bond in which a hydroxyl group at carbon number 2 (C2) of one allulose molecule among the two allulose molecules is glycosidic bonded to a hydroxyl group at carbon number 1 to carbon number 6 (C1 to C6) of one other allulose molecule.

6. An anti-browning composition comprising allulose disaccharide.

7. A composition according to claim 6, wherein the browning is caused by sugar.

8. A composition according to claim 7, wherein the sugar is a monosaccharide.

9. A composition in claim 8, wherein the monosaccharide is allulose.

10. In the 6th paragraph, the allulose disaccharide is a composition in which two allulose molecules are connected by a glycosidic bond, and the glycosidic bond is a glycosidic bond in which a hydroxyl group at carbon number 2 (C2) of one allulose molecule among the two allulose molecules is glycosidic bonded to a hydroxyl group at carbon number 1 to carbon number 6 (C1 to C6) of one other allulose molecule.

11. A method for inhibiting HMF production, comprising preparing a mixed composition containing a saccharide and allulose disaccharide.

12. A method for preventing browning, comprising preparing a mixed composition comprising a saccharide and an allulose disaccharide.

13. Preparing a mixed composition containing sugars and allulose disaccharides; and Comprising heating the above mixed composition, A method for producing a composition containing sugar.

14. In the 13th paragraph, heating the mixed composition suppresses HMF production. A method for producing a composition containing sugar.

15. Use of allulose disaccharide to inhibit HMF production.

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