Flavor regulator

Abstract

To provide a flavor regulator capable of regulating flavors in a composition for food and drink including an ester compound, such as alcohols.SOLUTION: A flavor regulator includes an oligosaccharide with a degree of polymerization of 3 or more which is obtained by saccharization of a starch raw material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aroma modifier, and more specifically to an aroma modifier containing an oligosaccharide having a degree of polymerization of 3 or more purified from sake. [Background technology]

[0002] In general, aroma components and flavorings are contained and used in all kinds of foods, feeds, pet foods, cosmetics, pharmaceuticals, quasi-drugs, etc.

[0003] The main aroma components of sake are known to be ester compounds such as ethyl acetate and isoamyl acetate, aldehyde compounds such as hexanal and octanal, alcohol compounds such as 1-propanol and isobutyl alcohol, ketone compounds such as β-decalonone, and terpenes such as limonene. These aroma components vary depending on the ingredients such as rice and koji, the type of yeast, and the brewing method, and the aroma of sake is determined by the combination and balance of these components.

[0004] Various methods have been studied to adjust the combination and balance of aroma components in order to achieve a desirable aroma in sake. For example, Patent Document 1 discloses a method for brewing aromatic alcoholic beverages, which is characterized by adding lipase or an enzyme preparation containing lipase to mash and increasing the content of ethyl caproate in the alcoholic beverage during fermentation. However, there have been no reports on methods for suppressing the aroma caused by ester compounds in sake. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-045166 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an aroma modifier capable of adjusting the aroma of food and beverages containing ester compounds, such as alcoholic beverages. [Means for solving the problem]

[0007] The present inventors have been studying sake oligosaccharides because they have a characteristic structure (Reference 1: Tokuoka, M., Honda, C., Totsuka, A., Shindo, H., and Hosaka, M.: J. Biosci. Bioeng., 124, 171-177 (2017)). Through further research on these sake oligosaccharides, they discovered that they have the effect of suppressing the aroma of sake. Furthermore, the present inventors confirmed that the suppression of aroma is due to the effect of suppressing the volatilization of ester compounds. The present invention has been completed based on the above findings and includes the following aspects:

[0008] In one aspect, the present invention comprises: [1] The present invention relates to an aroma modifier comprising an oligosaccharide having a degree of polymerization of 3 or more obtained by saccharification of a starch raw material. In one embodiment, the aroma adjusting agent of the present invention comprises: [2] The aroma adjusting agent according to [1] above, It is characterized by containing an extract or purified product of alcoholic beverages or fermentation products or by-products obtained in the production of alcoholic beverages. In one embodiment, the aroma adjusting agent of the present invention comprises: [3] The aroma adjusting agent according to [1] or [2] above, It is characterized by having the effect of suppressing the volatilization of ester compounds. In one embodiment, the aroma adjusting agent of the present invention comprises: [4] The aroma adjusting agent according to any one of [1] to [3] above, The ester compound is characterized in that it is at least one compound selected from the group consisting of ethyl acetate, isobutyl acetate, ethyl butyrate, isoamyl acetate, ethyl caproate, ethyl caprylate, ethyl caprate, ethyl pelargonate, ethyl laurate, phenylethyl acetate, ethyl myristate, ethyl lactate, phenylethyl alcohol, ethyl succinate, ethyl malate, diethyl succinate, and diethyl malate.

[0009] In one embodiment, the aroma adjusting agent of the present invention comprises: [5] The aroma adjusting agent according to any one of [1] to [4] above, The oligosaccharides having a degree of polymerization of 3 or more are characterized in that they are oligosaccharides having a degree of polymerization of 3 to 8. In one embodiment, the aroma adjusting agent of the present invention comprises: [6] The aroma adjusting agent according to any one of [1] to [5] above, The oligosaccharide having a degree of polymerization of 3 or more is at least one oligosaccharide selected from the group consisting of oligosaccharides represented by the following formulae (i) to (viii).

[0010] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0011] In one embodiment, the aroma adjusting agent of the present invention comprises: [7] The aroma adjusting agent according to any one of [1] to [6] above, The oligosaccharide is characterized in that it is an oligosaccharide having at least one adjacent branch selected from the group consisting of oligosaccharides represented by formulas (i), (ii), and (iv). In one embodiment, the aroma adjusting agent of the present invention comprises: [8] The aroma adjusting agent according to any one of [1] to [7] above, The oligosaccharide is characterized in that it is an oligosaccharide represented by formula (i). In one embodiment, the aroma adjusting agent of the present invention comprises: [9] The aroma adjusting agent according to any one of [1] to [8] above, The oligosaccharides having a degree of polymerization of 3 or more a step of saccharifying the starch raw material to obtain a saccharified solution; a step of adsorbing oligosaccharides contained in the saccharified solution onto activated carbon; recovering the oligosaccharides adsorbed on the activated carbon; a step of isolating oligosaccharides having a degree of polymerization of 3 or more from the recovered oligosaccharides; The oligosaccharide is characterized in that it is an oligosaccharide obtained by a method comprising the steps of: In one embodiment, the aroma adjusting agent of the present invention comprises:

[10] The aroma adjusting agent according to any one of [1] to [9] above, The oligosaccharides having a degree of polymerization of 3 or more removing ethanol from the alcoholic beverage or a fermentation product or by-product obtained by the production of the alcoholic beverage; a step of adsorbing oligosaccharides contained in the alcoholic beverage or a fermentation product or by-product obtained by the production of the alcoholic beverage onto activated carbon; recovering the oligosaccharides adsorbed on the activated carbon; a step of isolating oligosaccharides having a degree of polymerization of 3 or more from the recovered oligosaccharides; The oligosaccharide is characterized in that it is an oligosaccharide obtained by a method comprising the steps of: In another aspect, the present invention provides

[11] A composition for food or drink, comprising the aroma modifier according to any one of [1] to

[10] above.

[0012] Another aspect of the present invention is

[12] An ester compound capture agent comprising a purified alcoholic beverage containing an oligosaccharide with a degree of polymerization of 3 or more. Another aspect of the present invention is

[13] The present invention relates to an ester compound capture agent, which comprises at least one oligosaccharide selected from the group consisting of oligosaccharides represented by the following formulas (i) to (viii): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0013] Another aspect of the present invention is

[14] An aroma modifier or an ester compound scavenger, comprising an oligosaccharide having adjacent branches each consisting of four monosaccharide residues. Another aspect of the present invention is

[15] An aroma modifier or ester compound scavenger, comprising an oligosaccharide containing four monosaccharide residues, each having two adjacent α-1,6-bonded branches on an α-1,4-bonded main chain. Another aspect of the present invention is

[16] An aroma modifier or ester compound scavenger, comprising an oligosaccharide having four monosaccharide residues at the non-reducing end, each of which has two adjacent α-1,6-bonded branches on an α-1,4-bonded main chain. [Effects of the Invention]

[0014] The aroma adjuster according to the present invention makes it possible to adjust the aroma of food and beverage compositions such as alcoholic beverages. [Brief explanation of the drawings]

[0015] [Figure 1] Figure 1 shows the chromatograms of commercially available sake and its refined product measured in Example 1 below. The upper part of the chromatogram shows the peaks of standard samples of glucose, maltose, and maltotriose. [Figure 2] FIG. 2 is a graph showing the results of the sensory evaluation (SD method) in Example 2 below. [Figure 3] Figure 3 is a graph showing the results of HS-GC / MS analysis in Example 4 below. Specifically, the graph shows the amounts of isoamyl acetate, ethyl caproate, and isoamyl alcohol remaining after a certain period of time has passed since oligosaccharides purified from sake (sake oligosaccharides: SAOs) were added to an ethanol solution containing isoamyl acetate, ethyl caproate, and isoamyl alcohol. The control shows the amounts of isoamyl acetate, ethyl caproate, and isoamyl alcohol remaining when no SAOs were added. [Figure 4] Figure 4 is a graph showing the results of HS-GC / MS analysis in Example 5 below. Specifically, the graph shows the amount of ethyl caproate remaining after a certain period of time under constant temperature conditions (17°C, 35°C, 50°C) after adding SAOs to an ethanol solution containing ethyl caproate and isoamyl acetate. The control shows the amount of ethyl caproate remaining without the addition of SAOs. [Figure 5]Figure 5 is a graph showing the results of HS-GC / MS analysis in Example 5 below. Specifically, the graph shows the amount of isoamyl acetate remaining after a certain period of time under constant temperature conditions (17°C, 35°C, 50°C) after adding SAOs to an ethanol solution containing ethyl caproate and isoamyl acetate. The control shows the amount of isoamyl acetate remaining when no SAOs are added. [Figure 6] Figure 6 is a graph showing the results of HS-GC / MS analysis in Example 6 below. Specifically, the graph shows the amounts of ethyl caproate and isoamyl acetate remaining after a certain period of time when SAOs, dextrin, or glucose was added to an ethanol solution containing ethyl caproate and isoamyl acetate. The graph also shows the amounts of ethyl caproate and isoamyl acetate remaining after a certain period of time when no sugar was added. [Figure 7] Figure 7 is a graph showing the results of HS-GC / MS analysis in Example 7 below. Specifically, the graph shows the amounts of ethyl caproate and isoamyl acetate remaining after a certain period of time after adding DP6-1 to an ethanol solution containing ethyl caproate and isoamyl acetate. Controls show the amounts of ethyl caproate and isoamyl acetate remaining when SAOs or no sugar was added. [Figure 8] Figure 8 is a graph showing the results of HS-GC / MS analysis in Example 8 below. Specifically, the graph shows the amounts of ethyl caproate and isoamyl acetate remaining after a certain period of time when DP6-1 was added to an ethanol solution containing ethyl caproate and isoamyl acetate at concentrations of 0.32 mass%, 0.63 mass%, or 1.25 mass%. The control shows the amounts of ethyl caproate and isoamyl acetate remaining when no sugar was added. DETAILED DESCRIPTION OF THE INVENTION

[0016] 1. Aroma adjuster One aspect of the present invention provides an aroma modifier comprising an oligosaccharide with a degree of polymerization of 3 or more obtained by saccharification of a starch raw material. The aroma modifier of the present invention makes it possible to adjust the aroma of food and drink compositions such as alcoholic beverages that contain ester compounds as aroma components.

[0017] The starch raw material that can be used in the present invention is not limited as long as it can produce oligosaccharides that can be aroma-adjusted by saccharification, and is preferably one used in the production of alcoholic beverages. Examples of starch raw materials include, but are not limited to, rice, wheat, barley, buckwheat, barnyard millet, foxtail millet, corn, potato, sweet potato, taro, pea, kidney bean, adzuki bean, mung bean, pumpkin, cassava (tapioca), sorghum (milo), sago, and dates. Preferred starch raw materials include rice, corn, and potato.

[0018] The enzyme used in the saccharification of starch raw materials is preferably α-amylase, which cleaves α-1,4-glycosidic bonds but does not hydrolyze α-1,6 bonds. The saccharification of starch raw materials may also be performed using glucoamylase in addition to α-amylase. By using glucoamylase in addition to α-amylase, it is possible to obtain large amounts of oligosaccharides (e.g., oligosaccharides represented by the following formula (i)) containing four monosaccharide residues (adjacent branches composed of four monosaccharide residues), each having two adjacent α-1,6-bonded branches on the α-1,4-bonded main chain. Other known glycosidases, such as α-glucosidase, pullulanase, galactosidase, cellulase, and β-glucosidase, can also be used as appropriate.

[0019] Saccharification of starch raw materials using α-amylase or glucoamylase can be carried out in accordance with known methods. As an example, the saccharification method using powdered Yamadanishiki rice as the starch raw material is described below. Powdered Yamadanishiki rice (0.5 g) is suspended in 20 mL of 20 mM acetate buffer (pH 5.0), boiled for 30 minutes, and then autoclaved for 30 minutes to form a gel. The resulting gel sample is cooled to 55°C, and α-amylase (e.g., 1,000 U of PPA (Merck KGaA, Darmstadt, Germany)) is added and digested at 55°C for 24 hours. Next, glucoamylase (for example, 40 U of GLA derived from Rhizopus sp. (Toyobo, Osaka, Japan)) is added, and the mixture is digested at 40°C for 24 hours. The resulting sample is then boiled for 10 minutes to inactivate the enzyme, thereby completing the saccharification treatment. The saccharification treatment is not limited to the above-mentioned method. Furthermore, a person skilled in the art can appropriately determine the saccharification treatment conditions for other starch raw materials. By saccharifying starch raw materials with α-amylase and / or glucoamylase, it is possible to obtain oligosaccharides with a degree of polymerization of 3 or higher, which have aroma-modifying properties, in the post-saccharification sample. The post-saccharification sample can also be used as an extract or purified product by subjecting it to an extraction process using activated carbon or a purification process using liquid chromatography to concentrate oligosaccharides with a degree of polymerization of 3 or higher.

[0020] The alcoholic beverages that can be used in the present invention are not limited as long as they are made partly from starch-rich grains (such as rice and wheat) or potatoes (such as sweet potatoes). Examples of such alcoholic beverages include sake, beer, whiskey, and shochu, and commercially available products can be used. As used herein, fermentation products or by-products obtained by the production of alcoholic beverages refer to products that have undergone saccharification treatment of starch obtained in the production process of alcoholic beverages, and include saccharified liquid, mash, yeast starter, wort, sake lees, distiller's lees, etc. For example, methods for purifying oligosaccharides from sake are known, and purification can be performed with reference to the method described in Example 1 below or to References 1 and 2 (Honda, C., Katsuta, R., Yamada, M., Kojima, Y., Mamiya, A., Okada, N., Kawamura, T., Totsuka, A., Shindo, H., Hosaka, M., Nukada, T., and Tokuoka, M.: Carbohydr. Polym., 251, 116993 (2021)). Furthermore, those skilled in the art can similarly purify oligosaccharides from other alcoholic beverages or fermentation products or by-products obtained during the production of alcoholic beverages using known techniques.

[0021] As used herein, "oligosaccharide" refers to a linear or branched saccharide composed of 3 to 20 monosaccharide residues. The oligosaccharides used in the present invention may be any that can be purified from alcoholic beverages, and there are no limitations on the monosaccharide residues that make up the oligosaccharide or their bonding patterns. Oligosaccharides with a degree of polymerization of 3 or higher may be used alone or as a mixture of two or more oligosaccharides, as long as they are effective in adjusting the aroma. Oligosaccharides with a degree of polymerization of 3 or higher may also be used together with monosaccharides or disaccharides, as long as they are effective in adjusting the aroma.

[0022] The oligosaccharide contained in the aroma modifier of the present invention preferably has a degree of polymerization of 3 or more. The degree of polymerization is a value corresponding to the number of monosaccharides contained in the oligosaccharide. The degree of polymerization of the oligosaccharide used in the present invention is preferably 3 to 20, more preferably 3 to 8.

[0023] In one embodiment, the oligosaccharide is at least one oligosaccharide selected from the group consisting of oligosaccharides shown in the following formulae (i) to (viii): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0024] The oligosaccharides represented by the formulas (i) to (viii) above are known to be contained in sake and also in starch extracted from plants such as potato and corn (Honda et al., Carbohydrate Research, Volume 519, 2022, 108628, https: / / doi.org / 10.1016 / j.carres.2022.108628.). Therefore, the oligosaccharides represented by the formulas (i) to (viii) above may be recovered from plant-derived starch or chemically synthesized.

[0025] In a preferred embodiment, the oligosaccharide portion comprises an oligosaccharide containing four monosaccharide residues (adjacent branches each consisting of four monosaccharide residues) with two adjacent α-1,6-linked branches on the α-1,4-linked main chain. Examples of such oligosaccharides include those represented by the above formulas (i), (ii), and (iv). The oligosaccharide used in the present invention preferably has adjacent branches each consisting of four monosaccharide residues, as this enhances the aroma-modifying effect. In a more preferred embodiment, the oligosaccharide portion comprises four monosaccharide residues (adjacent branches each consisting of four monosaccharide residues) each having two α-1,6-linked branches adjacent to the non-reducing terminal region of the α-1,4-linked main chain. Examples of such oligosaccharides include the oligosaccharide represented by formula (i) above. The monosaccharide residues constituting the adjacent branch composed of four monosaccharide residues are preferably glucose.

[0026] In one embodiment of the aroma modifier of the present invention, oligosaccharides with a degree of polymerization of 3 or more can be produced by the following production method: (a) a process for removing ethanol from alcoholic beverages; (b) a step of adsorbing oligosaccharides contained in alcoholic beverages onto activated carbon; (c) recovering the oligosaccharides adsorbed on the activated carbon; (d) isolating oligosaccharides having a degree of polymerization of 3 or more from the recovered oligosaccharides; A method comprising: The production method can be carried out by referring to Example 1, Reference 1, Reference 2, etc. below, as described above. Furthermore, each of steps (a) to (d) can be performed by a known method, and each of steps (a) to (d) can be performed based on the contents disclosed in the present specification and publicly known information. In a preferred embodiment, the alcoholic beverage in steps (a) and (b) is sake.

[0027] As used herein, the term "aroma" refers to the perceived scent or smell resulting from volatile compounds (aroma components) emitted from compositions, including food and beverages, and other substances. The volatile compounds constituting the aroma in the present invention can include ester compounds. The ester compounds are not limited to those in the present invention. Examples of ester compounds include ester compounds used in the food industry. Examples of ester compounds used in the food industry include, but are not limited to, ethyl acetate, isobutyl acetate, ethyl butyrate, isoamyl acetate, ethyl caproate, ethyl caprylate, ethyl caprate, ethyl pelargonate, ethyl laurate, phenylethyl acetate, ethyl myristate, ethyl lactate, phenylethyl alcohol, ethyl succinate, ethyl malate, diethyl succinate, and diethyl malate. In a preferred embodiment, the ester compound is ethyl caproate or isoamyl acetate.

[0028] As used herein, "aroma adjustment" refers to adjusting the intensity and timing of the aroma perceived by the consumer's sense of taste of a food or beverage composition by capturing or releasing aroma components contained in the composition. The aroma adjuster of the present invention can suppress the volatilization of aroma components by capturing aroma components, thereby reducing the aroma perceived by consumers. Furthermore, the aroma adjuster of the present invention can enhance the aroma perceived by consumers by releasing the captured aroma components.

[0029] There is no limit to the temperature at which the aroma modifier of the present invention can be used, as long as it is capable of adjusting the aroma components. When capturing aroma components, it is preferably used at 35°C or below, and more preferably at 30°C or below. Temperatures above 50°C are undesirable, as this weakens the aroma component capturing effect. On the other hand, for example, the aroma modifier of the present invention can intensify the aroma by heating aroma components captured at 17°C or below to 35°C or above.

[0030] 2.Composition for food and beverages Another aspect of the present invention provides a composition for food or beverage, which comprises the above-mentioned aroma modifier. According to the composition for food and beverages of the present invention, it is possible to provide a composition for food and beverages with an adjusted aroma.

[0031] The composition for food and drink may be in any form, such as liquid, paste, gel-like solid, powder, etc., and includes, for example, nutritional supplements (supplements), tablet confectionery; liquid food (nutritional food for tube feeding); wheat flour products such as bread, macaroni, spaghetti, noodles, cake mix, fried chicken powder, breadcrumbs, etc.; instant noodles, cup noodles, retort / prepared foods, canned foods, microwave foods, instant soup / stew, instant miso soup / cleaning liquid, canned soup, freeze-dried foods, other instant foods, etc. Instant foods; canned agricultural products, canned fruit, jams and marmalades, pickles, boiled beans, dried agricultural products, cereals (processed grain products), and other processed agricultural products; canned seafood, fish ham and sausages, fish paste products, seafood delicacies, and tsukudani (simmered fish dishes) and other processed seafood products; canned livestock products and pastes, livestock ham and sausages, and other processed livestock products; processed milk, milk drinks, yogurt, lactic acid bacteria drinks, cheese, ice cream, infant formula, cream, and other dairy products; butter, margarine, and other dairy products , vegetable oils and other oils and fats; basic seasonings such as soy sauce, miso, sauces, tomato processed seasonings, mirin, vinegars and other types of seasonings; cooking mixes, curry bases, sauces, dressings, noodle soups, spices, and other complex seasonings and foods; frozen foods such as raw frozen foods, semi-cooked frozen foods, and cooked frozen foods; caramel, candy, chewing gum, chocolate, cookies, biscuits, cakes, pies, snacks, crackers, Japanese sweets, rice snacks, bean snacks, desserts Examples of suitable food and beverage compositions include confectioneries such as tart confectioneries, jellies, and other sweets; carbonated drinks, natural fruit juices, fruit juice drinks, soft drinks containing fruit juice, fruit juice pulp drinks, fruit drinks containing fruit pieces, vegetable drinks, soy milk, soy milk drinks, coffee drinks, tea drinks, powdered drinks, concentrated drinks, sports drinks, nutritional drinks, alcoholic drinks, and other beverages; other commercially available foods such as baby food, sprinkles, and ochazuke nori seaweed; infant formula; enteral nutritional foods; and functional foods (foods for specified health uses, foods with nutrient functions). These compositions may also contain food additives commonly used in the production of foods and beverages (thickening agents, gelling agents, emulsifiers, preservatives, leavening agents, sweeteners, coloring agents, flavoring agents, etc.). These food and beverage compositions can be produced according to known methods.

[0032] In a preferred embodiment, the food and beverage composition is a beverage composition, including, for example, alcoholic beverages such as sake, beer, wine, distilled spirits, liqueurs, and cocktails, carbonated beverages, natural fruit juices, fruit juice drinks, soft drinks with fruit juice, fruit pulp drinks, fruit drinks with fruit pieces, vegetable beverages, soy milk, soy milk drinks, coffee drinks, tea drinks, powdered drinks, concentrated drinks, sports drinks, energy drinks, and other beverages. The content of the aroma modifier in the composition for food or beverage of the present invention may be within a range that provides the desired effect depending on the form of the composition, and is not limited to, for example, 0.1 to 5% by mass, preferably 0.3 to 1.25% by mass.

[0033] 3. Ester compound scavengers Another aspect of the present invention provides an ester compound scavenger comprising a purified alcoholic beverage product containing oligosaccharides with a degree of polymerization of 3 or more. Another aspect of the present invention provides an ester compound capture agent comprising at least one oligosaccharide selected from the group consisting of oligosaccharides represented by formulas (i) to (viii). The ester compound scavenger of the present invention can capture an ester compound contained in a specific solid or liquid composition and inhibit the volatilization of the ester compound, and therefore can also be used as an aroma adjuster.

[0034] The oligosaccharides that can be used in the ester compound scavenger of the present invention may be the same as those used in the aroma modifier described above. The oligosaccharides may be derived from plant starch or may be chemically synthesized.

[0035] The method of using the ester compound scavenger of the present invention is not limited as long as it captures the ester compound and suppresses its evaporation, and it can be used in food and drink compositions, cosmetics, pharmaceuticals, detergents and other daily necessities.

[0036] The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the following examples. [Example]

[0037] Unless otherwise specified, the reagents used in this example were from Fujifilm Wako Pure Chemical Industries, Ltd.

[0038] Example 1: Purification of sake oligosaccharides In this example, oligosaccharides contained in sake were purified as follows.

[0039] 1-1. Purification of sake oligosaccharides 1,000 ml of commercially available sake was deethanolized using a rotary evaporator (EYELA N-1100) and then filled to 1,000 ml with Milli-Q water. The mixture was then mixed with 80 g of chromatographic activated carbon (Fujifilm) and stirred thoroughly. The mixture was then vacuum filtered using a chromatography filter paper (ADVANTEC No. 590) and a Buchner funnel. The remaining activated carbon was washed three times with 1,000 ml of 5% ethanol solution, and the oligosaccharides were extracted with 1,000 ml of 40% ethanol solution. The extract was then concentrated to approximately 400 ml using a rotary evaporator. To remove any contaminating activated carbon, the sample was centrifuged at 3,300 rpm in a centrifuge (KOKUSAN H-40α) for 15 minutes. The supernatant was collected and used as the crude oligosaccharide sample. This was further concentrated using a rotary evaporator and dissolved in 50% ethanol so that the total sugar content was 30%. This was filtered through a 0.45 μm pore syringe filter (DISMIC-13HP ADVANTEC) and used as a sample. This was then fractionated by liquid chromatography under the following conditions.

[0040] 1-2. Liquid chromatography conditions HPLC: LC-20AD (Shimadzu Corporation) Fraction collector: CHF-122SC (ADVANTEC) Column: Shodex Asahipak NH2P-90 20F (20 mm x 300 mm, particle size 9 μm, Showa Denko K.K.) Mobile phase: 70% ethanol Flow rate: 5.0 mL / min Sample introduction volume: 100 μl

[0041] 1-3.Results Using the liquid chromatography conditions described above, fractions containing trisaccharides or more were collected to remove glucose and disaccharides. The chromatogram of the collected sample is shown in Figure 1. In this way, 5.5 g of a mixture of oligosaccharides with a degree of polymerization of 3 or higher was purified from commercially available sake and designated sake oligosaccharides (SAOs). The resulting sake oligosaccharides were used in subsequent experiments.

[0042] (Example 2: Analysis of the influence of SAOs on sake flavor using sensory evaluation (semantic differential method: SD method)) In this example, the sake oligosaccharides obtained in Example 1 or glucose was added to a model sake, and the effect on flavor was examined by sensory evaluation (SD method). 2-1. Model sake The model sake used contained the components in the concentrations shown in Table 1 in water. [Table 1]

[0043] 2-2. Panelists Two sensory evaluations were conducted with four panelists, male and female, in their twenties from the Laboratory of Alcoholic Beverage Production Science, Department of Brewing Science, Faculty of Applied Biosciences, Tokyo University of Agriculture, who passed the basic five taste discrimination test.

[0044] 2-3. Preparation of sensory evaluation samples Samples for sensory evaluation were prepared by adding the sake oligosaccharides or glucose obtained in Example 1 to model sake with the composition shown in Table 1. Isoamyl acetate and ethyl caproate were used from Tokyo Chemical Industry Co., Ltd. Sake oligosaccharides or glucose were added to a final concentration of 1.25% by mass. This concentration is based on the average concentration of oligosaccharides with a degree of polymerization of 3 or higher contained in six commercially available sake samples listed in Reference 1, which is 1.25% by mass. Five ml of the prepared sample for sensory evaluation was poured into an amber glass (DURALEX AMBER / 210cc), covered with a glass petri dish, and left overnight at 15°C before use.

[0045] 2-4. Sensory evaluation Sensory evaluation was performed on the 14 items shown in Figure 2. The sensory evaluation test was conducted on two samples (one with 1.25% glucose and one with 1.25% SAOs) in comparison with a control sample (a sample without added sugar), with a score of 7 on both extremes.

[0046] 2-5.Statistical analysis The statistical software EZR (Jichi Medical University Saitama Medical Center) was used. Steele's multiple comparison test was used to test for statistical significance.

[0047] 2-6.Results Evaluations by four panelists revealed that the addition of SAOs significantly increased the perception of two items, "the aroma is not vibrant" and "the aroma is not pleasant," at a risk level of 5% (Figure 2). There were no significant differences in these items when glucose was added, indicating the influence of sake oligosaccharides on the aroma. This is thought to be due to the SAOs' suppressing effect on the volatilization of aroma components.

[0048] Example 3: Analysis of the effects of SAOs on aroma components using sensory evaluation (two-point discrimination method) In this example, the sake oligosaccharides obtained in Example 1 or glucose was added to a model sake, and the effect on flavor was examined by sensory evaluation (two-point discrimination method).

[0049] 3-1. Sample preparation A sample containing 1.25% by mass of SAOs was prepared using an aqueous solution containing each component at the concentrations shown in Table 2. A control sample was prepared without any additives. Each solution was poured into 20 ml of an amber glass dish, covered with a glass petri dish, and left to stand for 10 minutes before being used for sensory evaluation. [Table 2]

[0050] Sensory evaluation The panelists were 12 male and female students in their 20s. The two-point discrimination test involved using an additive-free sample as a control and asking participants to choose the stronger scent of two samples based on the scent perceived in the control.

[0051] statistical analysis Statistical analysis was performed using a two-point discrimination test table (one-sided test). A statistically significant difference was determined to be p<0.05.

[0052] result Ten out of 12 panelists responded that the sample without added SAOs had a stronger aroma, and a significant difference was observed at a risk level of 5% in the evaluation of aroma intensity between the sample with added SAOs and the control sample. This confirmed the suppression of volatilization of aroma components by sake oligosaccharides, as shown in Example 2.

[0053] Example 4: Evaluation of the aroma volatilization suppression effect of sake oligosaccharides by instrumental analysis In this example, the aroma components in the solution were measured by headspace-gas chromatography / mass spectrometry (HS-GC / MS) to determine the amount of ester remaining after a certain time period following the addition of oligosaccharides, and the difference in the amount of ester volatilization was investigated.

[0054] 4-1. Sample preparation Esters (isoamyl acetate, ethyl caproate) and isoamyl alcohol were dissolved in 15% (v / v) ethanol to a final concentration of 10 ppm. To this sample, SAOs were added to a final concentration of 1.25% by mass (1.25% SAOs), and a sample without SAOs (no addition) was prepared.

[0055] 4-2. Volatilization test 20 ml of the prepared sample was placed in a 50 ml cylindrical glass container and stirred at 300 rpm for 60 minutes at room temperature (25°C) using a magnetic stirrer (SRS111AA ADVANTEC). 1.8 ml of the sample was sampled every 20 minutes and used as the analytical sample.

[0056] 4-3.HS-GC / MS analysis The residual esters in the solution were analyzed using a HS-GC / MS system connected to a headspace sampler (7697A, Agilent Technologies Inc., Santa Clara, CA, USA), a gas chromatography system (7890N, Agilent Technologies Inc.), and a mass-selective detector (5975C VL, Agilent Technologies Inc.). A DB-WAX capillary column (0.32 mm i.d. × 60 m, 0.25 μm film thickness, Agilent Technologies Inc.) was used. 1.8 ml of sample and 0.2 ml of 0.25% n-amyl alcohol solution as an internal standard were placed in a 20 ml vial and sealed with a silicone rubber stopper covered with an aluminum cap. After incubation at 50 °C for 30 min, the solution was introduced into the GC / MS. Helium was used as the carrier gas. The injection temperature was 230 °C, and the oven temperature was raised to 50 °C for 5 min, then increased to 230 °C at a rate of 10 °C / min, and held there for 5 min. From the obtained chromatogram, the peak areas of ethyl caproate (elution time 13.2 minutes), isoamyl acetate (elution time 11.1 minutes), and isoamyl alcohol (elution time 12.8 minutes) were divided by the peak area of ​​n-amyl alcohol (elution time 13.5 minutes) to obtain relative values. The retention rate (%) was calculated by dividing the relative values ​​at 20 minutes, 40 minutes, and 60 minutes by the relative value at 0 minutes, which was set to 100%.

[0057] 4-4.Results The volatilization-inhibiting effect of SAOs on two types of esters (ethyl caproate and isoamyl acetate) and isoamyl alcohol was investigated. Volatilization was performed by stirring for 60 minutes, and the changes in the remaining esters and alcohols over time were examined using HS-GC / MS. The addition of SAOs increased the amount of ethyl caproate and isoamyl acetate remaining in the sample, indicating that volatilization was inhibited (Figure 3). On the other hand, no volatilization inhibition was observed for isoamyl alcohol with the addition of SAOs. These results demonstrate that sake oligosaccharides have an ester volatilization-inhibiting effect.

[0058] Example 5: Evaluation of the aroma volatilization suppression effect of sake oligosaccharides by instrumental analysis (analysis of the effect of temperature) In this example, the aroma components in the solution were measured by headspace-gas chromatography / mass spectrometry (HS-GC / MS) to determine the amount of ester remaining after a certain time period following the addition of oligosaccharides, and the difference in the amount of volatilization was investigated.

[0059] 5-1. Sample preparation Ethyl caproate and isoamyl acetate were dissolved in 15% (v / v) ethanol to a final concentration of 10 ppm. To this sample, SAOs were added to a final concentration of 1.25% by mass (1.25% SAOs), and a sample without SAOs (no addition) was prepared.

[0060] 5-2. Volatilization test 20 ml of the prepared sample was placed in a 50 ml cylindrical glass container and stirred with a magnetic stirrer (SRS111AA ADVANTEC) at 300 rpm for 60 minutes at temperatures of 17°C, 35°C, and 50°C. 1.8 ml of the sample was sampled every 20 minutes and used as the analytical sample.

[0061] 5-3.Results The volatilization-inhibiting effect of SAOs on two types of esters (ethyl caproate and isoamyl acetate) was investigated at 17°C, 35°C, and 50°C. The esters in the samples were volatilized by stirring for 60 minutes, and the time-dependent changes in the remaining esters were examined by HS-GC / MS. At 17°C and 35°C, the addition of SAOs increased the amount of ethyl caproate and isoamyl acetate remaining in the samples, indicating that volatilization was suppressed (Figures 4 and 5). However, no volatilization suppression by SAOs was observed at 50°C. These results indicate that the volatilization-inhibiting effect of sake oligosaccharides on these esters was greater at lower temperatures and weakened at higher temperatures.

[0062] Example 6: Evaluation of the aroma volatilization suppression effect of sake oligosaccharides by instrumental analysis (effect of type of sugar) The SAOs used in the above examples were purified from sake with a degree of polymerization of 3 or higher, and contained oligosaccharides with various structures. Therefore, in this example, we investigated whether dextrin, which also contains oligosaccharides with various structures, and glucose, a monosaccharide, would have the same effect.

[0063] 6-1. Sample preparation and volatilization test In addition to SAOs, the volatilization suppression effect of adding dextrin and glucose was examined. The above sugars were added to 15% (v / v) ethanol water containing 10 ppm each of ethyl caproate and isoamyl acetate, and the volatilization test was carried out in the same manner as in Example 4. The test was carried out at room temperature (25°C).

[0064] 6-2.Results The addition of dextrin and glucose did not affect the residual amounts of ethyl caproate and isoamyl acetate, and the volatilization was the same as that of the sample without added sugar (Figure 6). These results suggest that sugars in general do not have an inhibitory effect on ester volatilization, but rather that some structural element characteristic of SAOs influences the inhibition of ester volatilization. Furthermore, these results are consistent with the results of the sensory evaluation using the SD method in Example 2, where the addition of glucose to the sample did not significantly affect the aroma.

[0065] Example 7: Evaluation of the aroma volatilization suppression effect of sake oligosaccharides by instrumental analysis (effect of DP6-1) In this example, we investigated whether DP6-1 alone could suppress volatilization similar to SAOs, since DP6-1 has been discovered as an oligosaccharide with a unique structure among sake oligosaccharides (Reference 2). The structural formula of DP6-1 is shown below. [ka]

[0066] 7-1. Sample preparation and volatilization test DP6-1 was a sample purified from sake according to the method of Reference 2. The above sugars were added to 15% (v / v) ethanol water containing 10 ppm each of ethyl caproate and isoamyl acetate, and the volatilization test was carried out in the same manner as in Example 4. The test was carried out at room temperature (25°C).

[0067] 7-2.Results DP6-1 was shown to have a volatilization suppression effect similar to that of SAOs (Figure 7). Because DP6-1 is also contained in SAOs, it was shown that part of the volatilization suppression effect of SAOs is due to DP6-1.

[0068] Example 8: Evaluation of the aroma volatilization suppression effect of sake oligosaccharides by instrumental analysis (effect of SAOs concentration) In this example, the effect of lowering the final concentration of SAOs added to the sample was investigated.

[0069] 8-1. Sample preparation and volatilization test The SAOs concentrations were set to three levels: 0.32 mass%, 0.63 mass%, and 1.25 mass%. The volatilization test was carried out in the same manner as in Example 5, except that the temperature was room temperature (25°C) and the final concentrations of ethyl caproate and isoamyl acetate were 10 ppm.

[0070] 8-2.Results Compared to the case where SAOs was added at 1.25%, the amount of ethyl caproate and isoamyl acetate remaining in the solution decreased as the amount added decreased (Figure 8). In other words, it was shown that the volatilization suppression by SAOs was weakened when the amount added was 1.25% or less.

Claims

1. An aroma adjuster comprising an oligosaccharide with a degree of polymerization of 3 or more obtained by saccharification of a starch raw material.

2. The aroma modifier according to claim 1, An aroma modifier comprising an extract or purified product of alcoholic beverages or fermentation products or by-products obtained in the production of alcoholic beverages.

3. The aroma modifier according to claim 1, A fragrance adjuster that suppresses the volatilization of ester compounds.

4. The aroma adjusting agent according to claim 3, The aroma adjuster is characterized in that the ester compound is at least one compound selected from the group consisting of ethyl acetate, isobutyl acetate, ethyl butyrate, isoamyl acetate, ethyl caproate, ethyl caprylate, ethyl caprate, ethyl pelargonate, ethyl laurate, phenylethyl acetate, ethyl myristate, ethyl lactate, phenylethyl alcohol, ethyl succinate, ethyl malate, diethyl succinate, and diethyl malate.

5. The aroma modifier according to claim 1, The aroma modifier, wherein the oligosaccharide with a degree of polymerization of 3 or more is an oligosaccharide with a degree of polymerization of 3 to 8.

6. The aroma modifier according to claim 1, The aroma modifier, wherein the oligosaccharide having a degree of polymerization of 3 or more is at least one oligosaccharide selected from the group consisting of oligosaccharides represented by the following formulas (i) to (viii): 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】

7. The aroma modifier according to claim 6, An aroma modifier, wherein the oligosaccharide is an oligosaccharide having at least one adjacent branch selected from the group consisting of oligosaccharides represented by formulas (i), (ii), and (iv).

8. The aroma modifier according to claim 7, An aroma modifier, wherein the oligosaccharide is an oligosaccharide represented by formula (i):

9. The aroma modifier according to claim 1, The oligosaccharide having a degree of polymerization of 3 or more a step of saccharifying the starch raw material to obtain a saccharified solution; a step of adsorbing oligosaccharides contained in the saccharified solution onto activated carbon; recovering the oligosaccharides adsorbed on the activated carbon; a step of isolating oligosaccharides having a degree of polymerization of 3 or more from the recovered oligosaccharides; An aroma modifier which is an oligosaccharide obtained by a method comprising the steps of:

10. The aroma modifier according to claim 2, The oligosaccharide having a degree of polymerization of 3 or more removing ethanol from the alcoholic beverage or a fermentation product or by-product obtained by the production of the alcoholic beverage; a step of adsorbing oligosaccharides contained in the alcoholic beverage or a fermentation product or by-product obtained by the production of the alcoholic beverage onto activated carbon; recovering the oligosaccharides adsorbed on the activated carbon; a step of isolating oligosaccharides having a degree of polymerization of 3 or more from the recovered oligosaccharides; An aroma modifier which is an oligosaccharide obtained by a method comprising the steps of:

11. A composition for food or beverage, comprising the aroma modifier according to any one of claims 1 to 10.

12. An ester compound capture agent comprising a refined alcoholic beverage product containing an oligosaccharide having a degree of polymerization of 3 or more.

13. An ester compound capture agent comprising at least one oligosaccharide selected from the group consisting of oligosaccharides represented by the following formulas (i) to (viii): 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】

Images