Method for producing sugar composition

Abstract

To provide a method of easily producing a saccharide composition containing a disaccharide having excellent sugar absorption inhibitory effect.SOLUTION: The method comprises heating a mixture containing sucrose and fructose to produce a saccharide composition containing a compound represented by the structural formula in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a sugar composition. [Background technology]

[0002] α-Glucosidase is a saccharide-degrading enzyme that is involved in glycoprotein processing and glycogenolysis and is localized on the small intestinal epithelium. α-Glucosidase inhibitors that specifically inhibit α-glucosidase can directly inhibit carbohydrate absorption when taken orally (Patent Document 1).

[0003] Invertase is a digestive enzyme present in the small intestinal wall that hydrolyzes sucrose. Sucrose ingested by humans and taken into the small intestine is hydrolyzed by invertase into glucose and fructose. Glucose and fructose are absorbed from small intestinal epithelial cells into blood vessels, through which they are transported to various organs in the body. Oral administration of invertase inhibitors can directly inhibit the absorption of sucrose and other fructosyl sugars (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-51916 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-153399 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have conducted extensive research into functional substances that inhibit the absorption of sugars such as sucrose, and as a result have found that disaccharides obtained from the sap of maple trees of the genus Maple, which belong to the family Maple, have excellent sugar absorption inhibitory effects. Furthermore, they have found that the sap of maple trees also contains fructooligosaccharides. Neokestose, a type of fructooligosaccharide, can be produced using fructosyltransferase derived from microorganisms or plants. Another method involves producing neokestose using a fructan hydrolase derived from burdock.

[0006] The present invention aims to provide a method for easily producing a sugar composition containing a disaccharide having an excellent sugar absorption inhibitory effect, or a trisaccharide in which fructose is added to a disaccharide having an excellent sugar absorption inhibitory effect. [Means for solving the problem]

[0007] The present invention is a method for producing a sugar composition by heating a mixture containing sucrose and fructose to produce a sugar composition containing compound (I) or compound (II) represented by the following structural formula: [ka] [ka] [Effects of the Invention]

[0008] According to the present invention, a sugar composition containing a disaccharide having an excellent sugar absorption inhibitory effect or a trisaccharide in which fructose is added to a disaccharide having an excellent sugar absorption inhibitory effect can be easily produced. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below, but it goes without saying that the present invention is not limited to the following.

[0010] The sugar composition produced by the present invention contains at least Compound (I) or Compound (II). When the sugar composition is used as a sweetener, it contains at least sucrose and Compound (I) or Compound (II). The sugar composition may also contain fructose and glucose. Fructose may be contained in the sugar composition as a raw material or a by-product. Glucose may be contained in the sugar composition as a by-product. The ratios of sucrose, fructose, glucose, Compound (I), or Compound (II) in the sugar composition are not particularly limited. However, from the viewpoint of improving the yield of Compound (I) or Compound (II), i.e., for the purpose of isolating Compound (I) or Compound (II) from the sugar composition, it is preferable that the ratio of Compound (I) or Compound (II) be as high as possible. On the other hand, when the sugar composition is used as a sweetener and Compound (I) exerts its function on the absorption of sucrose contained in the sugar composition, it is preferable that Compound (I) be contained within a range that exerts its α-glucosidase inhibitory function on the sucrose remaining in the sugar composition. Furthermore, it is assumed that compound (I) has a β-glycosidic bond between the carbon at position 6 of glucose and the carbon at position 2 of fructose. In sucrose, the carbon at position 1 of glucose is α-bonded, and the carbon at position 2 of fructose is β-bonded. In the production method of the present invention, it is assumed that compound (I) in which the carbon at position 6 of glucose is β-bonded to the carbon at position 2 of fructose is predominantly produced.

[0011] The sugar composition produced may be in the form of a solid such as a powder or crystal, or in the form of a liquid such as a syrup. The sugar composition produced may be used as a sweetener as is, or may be used in the form of an extract or powder. The sugar composition produced may be added to foods for oral intake. Examples of foods include beverages, confectioneries, prepared foods, and seasonings. Compound (I) can function as an α-glucosidase inhibitor, an invertase inhibitor, or a sugar absorption inhibitor.

[0012] Sucrose, fructose, glucose, and the like contained in the produced sugar composition can be analyzed by, for example, gas chromatography, anion exchange chromatography, or high-performance liquid chromatography (HPLC). Compound (I) can also be confirmed by acid hydrolysis of a fraction containing compound (I) obtained by HPLC, followed by HPLC. As a result of HPLC, two major peaks corresponding to glucose and fructose are observed, and if the peak areas of glucose and fructose are approximately equal, it is assumed that the compound is compound (I), a disaccharide consisting of glucose and fructose.

[0013] Compound (II) can be confirmed by acid hydrolyzing fractions containing compound (II) obtained by HPLC over time and then performing HPLC. If the HPLC results show that a peak for compound (I) is observed shortly after the start of the hydrolysis reaction, then the peak for compound (I) eventually disappears, and finally glucose and fructose are observed as the main peaks, then it is assumed that the compound is compound (II), a trisaccharide consisting of glucose and fructose.

[0014] In the present invention, a mixture containing sucrose and fructose is heated to produce a sugar composition containing compound (I). From the viewpoint of improving the yield of compound (I), the mixing ratio of sucrose and fructose is preferably equal. To leave a large amount of sucrose in the produced sugar composition and use it as a sweetener, the mixing ratio of sucrose to fructose is preferably higher than the fructose, for example, within a range of 9:1 to 7:3 by mass, more preferably 8:2. Since the melting point of sucrose is higher than that of fructose, when a sugar composition of sucrose and fructose is heated, the fructose melts first in the sugar composition. This results in a state in which molten liquid fructose is present around unmelted powdered sucrose, which is presumably facilitating the production of compound (I).

[0015] The mixture containing sucrose and fructose is heated using, for example, an oil bath, an oven, an autoclave, or the like. The heating temperature range is preferably 120°C or higher and 160°C or lower, more preferably 120°C or higher and 140°C or lower, and particularly preferably 130°C. If the heating temperature is low, the fructose does not melt sufficiently and is difficult to contact with the sucrose, resulting in a decrease in the production rate of Compound (I). If the heating temperature is high, the produced sugar composition will be deeply colored. Alternatively, the mixture containing sucrose and fructose may be heated under pressure above atmospheric pressure using an autoclave, etc. Note that stirring may be performed during heating to bring the molten fructose into contact with the sucrose.

[0016] From the viewpoint of improving the yield of compound (I) in the sugar composition, the heating time is preferably 20 minutes or more, but within the time required for sucrose to completely melt. If the heating time is too short, sucrose and fructose will not react sufficiently, resulting in a decrease in the production rate of compound (I). On the other hand, from the viewpoint of using the resulting sugar composition as a sweetener having a sugar absorption inhibitory function, if the heating time is too long and sucrose is completely melted, the glucosidic bond of sucrose will be broken and it will be converted into monosaccharides, which is not preferable.

[0017] Furthermore, in the present invention, a mixture containing sucrose and fructose is heated to produce a sugar composition containing compound (II). The mixture containing sucrose and fructose is heated, for example, using an oil bath, an oven, an autoclave, or the like. The heating temperature range is preferably 120°C or higher and 140°C or lower, and more preferably 130°C. If the heating temperature is low, the fructose does not melt sufficiently and is less likely to come into contact with the sucrose, resulting in a decrease in the production rate of compound (II). If the heating temperature is high, the production rate of compound (II) decreases. This is thought to be due to the decomposition of the produced compound (II) and unreacted sucrose before they react with fructose.

[0018] From the viewpoint of improving the yield of compound (II) in the sugar composition, the heating time is preferably within the range of 20 minutes to 360 minutes, more preferably within the range of 20 minutes to 120 minutes. If the heating time is short, sucrose and fructose do not react sufficiently, resulting in a decrease in the yield of compound (II). If the heating time is long, the yield of compound (II) also decreases.

[0019] Alternatively, a mixture containing sucrose and fructose may be heated under pressure equal to or higher than atmospheric pressure using an autoclave or the like. Pressurization tends to shorten the preferred range of heating time. Stirring may be performed during heating to bring the molten fructose into contact with the sucrose.

[0020] When pressure is applied using an autoclave or the like, the mixing ratio of sucrose to fructose is preferably 18:2 from the viewpoint of improving the yield of compound (II).When pressure is not applied, the mixing ratio of sucrose to fructose is preferably 8:2.

[0021] Alternatively, the surface area of ​​the sucrose may be increased by freeze-drying or pulverizing it. The pulverized sucrose preferably has a maximum outer dimension of less than 300 μm, more preferably 250 μm or less, and particularly preferably 200 μm or less.

[0022] [Example] The present invention will be described in detail below using examples, but it goes without saying that the present invention is not limited to the following examples.

[0023] A total of 0.2 g of sucrose and fructose in the proportions shown in Table 1 was placed in a stoppered centrifuge tube and heated in an oil bath at the temperature and for the time shown in Table 1 to prepare Examples 1 to 11. Also, a total of 20 g of sucrose and fructose in the proportions shown in Table 1 was placed in a stoppered wide-mouthed polypropylene bottle and heated in an oil bath or an autoclave (TOMY BS-325, 168.9 kPa) at the temperature and for the time shown in Table 1 to prepare Examples 12 to 14.

[0024] A total of 0.2 g of sucrose and fructose in the proportions shown in Table 2 was placed in a stoppered centrifuge tube and heated in an oil bath at the temperature and for the time shown in Table 2 to obtain Examples 15 to 24. Also, a total of 20 g of sucrose and fructose in the proportions shown in Tables 3 and 4 was placed in a stoppered wide-mouthed polypropylene bottle and heated in an autoclave (TOMY BS-325, 168.9 kPa) at the temperature and for the time shown in Tables 3 and 4 to obtain Examples 25 to 39. Of the 20 g of sucrose and fructose in the proportions shown in Table 4, sucrose that was crushed or freeze-dried, and the crushed sucrose that was sieved to the size shown in Table 4, were placed in a stoppered wide-mouthed polypropylene bottle and heated in an autoclave (TOMY BS-325, 168.9 kPa) at the temperature and for the time shown in Table 4 to obtain Examples 40 to 45.

[0025] [Analysis of the produced sugar composition] 200 μg of the sugar compositions of Examples 1 to 45 were dissolved in 1 mL of water, and 20 μL of the solution was further diluted 50-fold to prepare a sample, which was subjected to high performance liquid chromatography (HPLC). The HPLC conditions were as follows. HPLC pump: LC-10AD (Shimadzu Corporation) Detector: Corona charged particle detector Corona Veo (Thermo Fisher Scientific) Column: Asahipak NH2P-50 4E (5 μm; 250 × 4.6 mm I.D.) (Showa Denko) Mobile phase: acetonitrile-deionized water (3:1, v / v) Flow rate: 1.0mL / min Column temperature: room temperature (up to 23°C) Injection volume: 20μL The peak area of ​​Compound (I) or Compound (II) relative to the area of ​​all peaks confirmed from the HPLC results was calculated as a relative area ratio (%). The results are shown in Tables 1 to 4.

[0026] The concentrations of Compound (I), Compound (II), and sucrose in each example were calculated by multiplying the concentration determined from the peak area of ​​the sample used in HPLC using the following calibration curve by 50. Although the sucrose concentration was higher than the upper limit of the calibration curve, it was calculated by extrapolating the calibration curve. [Creating a calibration curve] 50 μL of an aqueous solution prepared by dissolving 2 mg of sucrose in 1 mL of deionized water was diluted with 950 μL of deionized water. The diluted solution was serially diluted with deionized water to 100 μg / mL, 50 μg / mL, 10 μg / mL, 5 μg / mL, 1 μg / mL, and 0.5 μg / mL to prepare standard solutions. 20 μL of each standard solution was measured by HPLC, and the regression line obtained from the peak area versus the standard solution concentration was used as the calibration curve.

[0027] [Table 1]

[0028] [Table 2]

[0029] [Table 3]

[0030] [Table 4]

[0031] [evaluation] As shown in Table 1, the production of compound (I) was confirmed in Examples 1 to 14. Furthermore, the amount of compound (I) produced tended to be greater in Examples 2 to 12, in which the heating temperature was 130°C or higher. On the other hand, in Example 3, in which the heating temperature was 150°C, and Example 4, in which the heating temperature was 160°C, the amount of compound (I) produced tended to be smaller than in Examples 6 and 8, despite the higher temperatures. From this, it is considered that a heating temperature in the range of 130°C to 140°C is preferable from the viewpoint of improving the yield of compound (I). Furthermore, the amount of compound (I) produced tended to be greater in Example 6, in which the heating time was 360 minutes, than in Example 5, in which the heating time was 60 minutes.

[0032] In Examples 3, 4, 6, and 8, sucrose was completely melted, resulting in a large amount of compound (I). On the other hand, no sucrose remained in the produced sugar composition, suggesting that sucrose was decomposed into monosaccharides. To suppress sugar absorption from the produced sugar composition through the α-glucosidase inhibitory function of compound (I), it is preferable that sucrose remain undecomposed. It was confirmed that approximately the same amount of compound (I) was produced when the mixing ratio of sucrose to fructose was within the range of 9:1 to 1:1. Since the fructose released from sucrose during the production process of compound (I) is further involved in the production of new compound (I), it is believed that the mixing ratio of sucrose to fructose can be increased. It has been reported that compound (I) inhibits sucrose absorption by approximately 50% when present at a mass ratio of 0.11% relative to sucrose (International Journal of Molecular Sciences, 2019, 20, 5041; doi:10.3390 / ijms20205041). In Examples 2 to 14, a sufficient amount of compound (I) was produced. Furthermore, in Examples 9 to 14, in which the sucrose content was higher than the fructose content, a sufficient amount of sucrose remained in the resulting sugar composition. This suggests that a higher sucrose content than fructose content is suitable for use as a sweetener in the resulting sugar composition.

[0033] In Example 12, in which the sample was 20 g (sucrose 16 g, fructose 4 g), the amount of compound (I) produced was smaller than in Example 5. This is thought to be due to slower heat conduction in the sample. In Example 13, in which the sample was heated using an autoclave and pressurized above atmospheric pressure, the amount of compound (I) produced was greater, even though the heating temperature was the same as in Example 1 (not pressurized) but for a shorter heating time. In Example 14, the amount of compound (I) produced was greater, even though the heating temperature was the same as in Example 12 (not pressurized) but for a shorter heating time. In Examples 13 and 14, in which the sample was 20 g (sucrose 16 g, fructose 4 g), the amount of compound (I) produced tended to increase with increasing heating temperature. This suggests that pressurization can shorten the heating time relative to the amount of compound (I) produced. Furthermore, since an autoclave was used for pressurization, it is thought that compound (I) is produced even in the presence of a small amount of water in the mixture of sucrose and fructose.

[0034] As shown in Table 2, the production of Compound (II) was confirmed in Examples 15 to 24. Furthermore, in Examples 15 to 17, where the heating temperature was in the range of 120 to 140°C, the amount of Compound (II) produced tended to be large. In particular, the amount of Compound (II) produced was large at heating temperatures of 130 and 140°C. On the other hand, in Example 18, where the heating temperature was 150°C, and in Example 19, where the heating temperature was 160°C, the amount of Compound (II) produced tended to be smaller than in Example 15. From this, it is considered that a heating temperature in the range of 130 to 140°C is preferable from the viewpoint of improving the yield of Compound (II). Furthermore, in Example 20, where the heating time was 360 minutes, and in Example 21, where the heating time was 105 minutes, the amount of Compound (II) produced tended to be smaller than in Examples 16 and 17, where the heating time was the same but for 60 minutes. In Examples 22 to 24, in which the mixing ratio of sucrose to fructose was in the range of 9:1 to 7:3, the production of compound (II) was confirmed to be similar to that of Example 16, in which other conditions were equivalent. In particular, the production amount of compound (II) was large in Example 23, in which the mixing ratio was 8:2.

[0035] In Examples 25 to 29, in which the mixture was heated in an autoclave at a pressure higher than atmospheric pressure and the total weight was 20 g with a sucrose to fructose ratio ranging from 10:10 to 18:2, the amount of compound (II) produced was greater than the total amount, even though the heating temperature was the same as in Example 16 (not pressurized) and the heating time was shorter. In particular, the amount of compound (II) produced was greater in Example 28, in which the sucrose to fructose ratio was 16:4. Furthermore, in Examples 30 to 34, in which the sucrose to fructose ratio was 16:4 and the heating time was 40 to 240 minutes, the amount of compound (II) produced tended to decrease with increasing heating time. In Examples 35 to 39, in which the sucrose to fructose ratio was 18:2 and the heating time was 40 to 240 minutes, the amount of compound (II) produced also tended to decrease with increasing heating time.

[0036] In Example 40, in which sucrose was pulverized, and Example 41, in which sucrose was freeze-dried, the amount of compound (II) produced was greater than in Example 28, in which the other conditions were the same. Furthermore, in Examples 42 to 45, in which the pulverized sucrose was sieved to set the maximum outer length of the sucrose particles to >300 μm, 250 to 300 μm, 150 to 250 μm, and 100 to 150 μm, the amount of compound (II) produced tended to increase as the size of the sucrose became smaller.

Claims

1. A method for producing a sugar composition, comprising heating a mixture containing sucrose and fructose at a temperature in the range of 120°C to 160°C in the absence of an acid catalyst to produce a sugar composition containing compound (I) represented by the following structural formula: 【Chemistry 1】

2. 2. The method for producing a sugar composition according to claim 1, wherein the mixture containing sucrose and fructose is heated for 20 minutes or more, within a time range in which the sucrose in the mixture is completely melted.

3. 3. The method for producing a sugar composition according to claim 1, wherein the mixture containing sucrose and fructose is heated under a pressure higher than atmospheric pressure.

4. 4. The method for producing a sugar composition according to claim 1, wherein the mixture containing sucrose and fructose has a higher mixing ratio of sucrose than fructose.

5. A method for producing a sugar composition by heating a mixture containing sucrose and fructose at a temperature in the range of 120°C to 160°C in the absence of an acid catalyst to produce a sugar composition containing compound (II) represented by the following structural formula: 【Chemistry 2】

6. The method for producing a sugar composition according to claim 5, wherein the mixture containing sucrose and fructose is heated for a period of 20 minutes to 180 minutes.

7. 7. The method for producing a sugar composition according to claim 5 or 6, wherein the mixture containing sucrose and fructose is heated under a pressure higher than atmospheric pressure.

8. The method for producing a sugar composition according to any one of claims 5 to 7, wherein the mixture containing sucrose and fructose has a higher mixing ratio of sucrose than fructose.

9. 9. The method for producing a sugar composition according to claim 5, wherein in the mixture containing sucrose and fructose, the maximum outer shape length of the sucrose is less than 300 μm.

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