JP5410734B2 - Process for producing refined sake enzyme - Google Patents

Description

  The present invention relates to a method for producing a refined sake enzyme-treated product that is useful for foods, cosmetics and the like and has excellent stability.

  The main ingredients of general sake are 80% water, 15% alcohol and 2% glucose, and the remaining 3% is sugars such as isomaltose, panose, salmon biose, cordobiose, maltose, glutamic acid, proline, Various ingredients said to be more than hundreds such as amino acids such as arginine and alanine, organic acids such as lactic acid, succinic acid and malic acid are included. Especially, the efficacy of α-ethyl glucoside which is a specific component of sake. As it becomes clear, the application of sake to foods, cosmetics, etc. is spreading (see Non-Patent Document 1). For example, a flavor enhancing / improving agent for foods and beverages comprising β-D-ethylglucoside (see Patent Document 1), an alcohol-stimulated odor mitigating agent containing ethyl-α-D-glucopyranoside as an active ingredient (see Patent Document 2), ethyl An anti-obesity composition containing α-D-glucoside as an active ingredient (see Patent Document 3), an anti-aging skin cosmetic containing ethyl glucoside, α-hydroxy acid and a polyhydric alcohol (see Patent Document 4) A skin-beautifying composition containing organic acid and ethyl glucoside (see Patent Document 5) has been proposed.

When appealing and applying the functionality of sake as described above to foods, cosmetics, etc., it is generally used in a concentrated form of sake. However, in the case of a sake concentrate, there has been a problem that storage stability is deteriorated as seen in browning over time due to the influence of glucose and the like contained in sake. Therefore, a method has been proposed in which alcohol is treated with glucose oxidase to convert glucose into gluconic acid or the like. For example, in a process for producing alcoholic beverages and sweet foods obtained by brewing a sugar raw material, a method for producing alcoholic beverages and sweet foods including a step of changing the content of glucose oxide (such as gluconic acid) by glucose oxidase (Patent Literature) 6), a method for producing sake that contains glucose oxidase in a large amount of sake and contains a large amount of gluconic acid, has a refreshing acidity, and has an excellent balance with flavor and is effective in maintaining health (see Patent Document 7) In a method for producing a seasoning containing a spirit such as mirin, a method for producing a seasoning containing a sake having a characteristic such that glucose oxidase is allowed to act and is difficult to undergo browning over time (see Patent Document 8), etc. Has been.
Journal of Japan Brewing Association, Vol. 99, no. 12, P836-841, 2004 Japanese Patent No. 2744595 Japanese Patent No. 2873408 JP 2002-119248 A JP-A-10-306010 JP-A-2005-314310 JP 2000-184878 A JP 2001-46047 A JP 2003-304860 A

The treatments with glucose oxidase described in Patent Documents 6, 7 and 8 are all treatments in the presence of alcohol such as liquors, and problems such as reaction not progressing and reaction efficiency are poor. There was a point.
Accordingly, an object of the present invention is to provide a method for efficiently producing a sake enzyme-treated product having excellent storage stability useful for foods, cosmetics and the like.

  As a result of intensive studies to solve the problems as described above, the present inventors have been able to efficiently convert glucose to gluconic acid by removing glucose from sake and then allowing glucose oxidase to act. As a result, the present invention has been completed.

Thus, according to the present invention, it is possible to provide a method for producing a processed product of a sake enzyme characterized by removing ethanol from sake and then treating with glucose oxidase.
Moreover, this invention can provide the said manufacturing method whose ethanol concentration of the sake concentrate at the time of processing with glucose oxidase is less than 1 mass%.
The present invention can also provide the production method described above, wherein the sake enzyme-treated product does not substantially contain glucose.
Furthermore, this invention can provide the said manufacturing method whose content rate of (alpha) -ethyl glucoside in refined sake enzyme processed material is 0.3 mass% or more.
Furthermore, the present invention can provide the above production method including a treatment for removing gluconic acid converted from glucose after treatment with glucose oxidase.

  The method for producing a refined sake enzyme product of the present invention can efficiently convert glucose in sake into gluconic acid. In addition, the sake enzyme-treated product obtained by the production method of the present invention is excellent in storage stability because deterioration of quality such as browning over time is suppressed.

Hereinafter, the manufacturing method of the sake enzyme processed material of this invention is demonstrated in detail.
The method for producing a sake enzyme-treated product of the present invention is characterized in that ethanol is removed from sake and then treated with glucose oxidase. The sake used in the present invention is not limited to ordinary sake, pure rice liquor, honjo sake, ginjo sake, etc., but can be used as long as it is generally used, but preferably brewed sake or pure rice liquor. Can be used. Particularly, sake containing 0.3% by mass or more, preferably 0.5% by mass or more of α-ethyl glucoside is suitable.

  Although the method of removing ethanol from sake in the present invention is not particularly limited, a method of concentrating sake can be preferably exemplified. The concentration method is not particularly limited, and a known general concentration method such as atmospheric pressure concentration or reduced pressure concentration can be adopted. However, ethanol in the sake concentrate is completely removed, and a substantially non-alcoholic sake is obtained. In order to obtain a concentrate, vacuum concentration is preferred. The ethanol concentration in the sake concentrate is less than 1% by mass, preferably less than 0.5% by mass, more preferably less than 0.2% by mass. When the ethanol concentration is 1% by mass or more, the reaction by glucose oxidase does not act efficiently, which is not preferable.

Next, a method of converting glucose in the concentrate into gluconic acid by allowing glucose oxidase to act on the sake concentrate concentrated to the above-mentioned specific concentration and from which ethanol has been removed will be described. The glucose oxidase used in the present invention is an enzyme that oxidizes glucose to produce gluconic acid, and examples thereof include enzymes derived from molds belonging to the genus Aspergillus and Penicillium. Such an enzyme can be obtained by liquid culture or solid culture of the microorganism described above, and can be used as either a crude enzyme or a purified enzyme, and a commercially available glucose oxidase enzyme agent (trade name: Hyderase 15 ( Amano Enzyme Co., Ltd.) and Sumiteam GOP (manufactured by Shin Nippon Chemical Industry Co., Ltd.)) can also be used. The amount of glucose oxidase added varies depending on the type of enzyme used, the degree of purification, the reaction conditions, etc., and cannot generally be stated, but usually 10 to 1000 u may be exemplified per 1 g of glucose mixed in the sake concentrate. it can. Here, 1 u (unit) refers to the amount of enzyme that converts 1 μmol of glucose to> gluconic acid at 37 ° C. for 1 minute.

  The enzyme reaction conditions are not particularly limited and vary depending on the type of glucose oxidase to be used. , About 5 to 24 hours. In the present invention, the treatment with glucose oxidase described above is preferably performed in the presence of salts. Treatment with glucose oxidase in the presence of salts is preferable because the reaction efficiency can be increased by suppressing the change in pH of the reaction solution due to gluconic acid produced as the reaction proceeds. Such salts are not particularly limited, and a wide range of salts can be used. Examples thereof include calcium carbonate, magnesium carbonate, and the like. It is preferable to control the pH by supplying an alkali such as sodium oxide. The amount of the salt used is not particularly limited and varies depending on the reaction conditions and cannot be generally specified. The sake enzyme-treated product obtained by the above method contains substantially no glucose because glucose is efficiently converted into gluconic acid. Incidentally, the phrase “substantially free of glucose” as used herein means that the kurcose content in the processed sake enzyme product is 0.2% by mass or less, preferably 0.1% by mass or less, more preferably 0.05% by mass. % Or less.

  Also, the sake enzyme-treated product obtained by the above method contains substantially the same amount of α-ethylglucoside as before the above treatment because glucose is efficiently converted to gluconic acid. . “Substantially the same amount is contained” means that the content of α-ethyl glucoside after the treatment is 90% or more than the same content before the treatment. Since α-ethyl glucoside is a very useful ingredient for foods and cosmetics, the content of α-ethyl glucoside in the sake enzyme-treated product obtained in the method for producing a product of this sake enzyme is 0.3% by mass or more. It is preferable that it is 0.5 mass% or more.

After completion of the reaction, the treated product of the sake enzyme can be purified by an appropriate purification means such as ethanol extraction, ion exchange resin treatment, activated carbon treatment, etc. to purify the active ingredient in the sake enzyme treated product.
For example, since the sake enzyme-treated product of the present invention contains excess gluconic acid (gluconate) generated from glucose, after the reaction is completed, the remaining salts are separated by an appropriate separation operation such as filtration, Water is removed using an appropriate concentration means such as vacuum concentration, a gluconate insoluble solvent (such as ethanol) is added, and the gluconate is separated by an appropriate separation means such as filtration. By recovering the solvent by employing an appropriate concentration means such as vacuum concentration, it is possible to obtain a preparation that can be expected to reduce the irritation to the skin when applied to cosmetics and the like.
Furthermore, the versatility as various preparations can be improved by including a lower alcohol or a polyhydric alcohol in the sake enzyme-treated product obtained as described above.

  In the sake enzyme-treated product obtained according to the present invention, glucose is converted into gluconic acid and substantially free of glucose, so that degradation of the sake enzyme-treated product over time such as browning is suppressed, and storage stability is improved. It is excellent and can be widely applied to foods and cosmetics. For example, beverages such as carbonated drinks, fruit juice drinks, fruit liquor drinks, milk drinks; frozen confectionery such as ice creams, sherbets, ice candy; Japanese / Western confectionery, chewing gums, breads, coffee, tea, tea Refined products such as tobacco, soups such as Japanese-style soups and Western-style soups; processed meat products such as ham and sausages; flavored seasonings, various instant beverages and foods, various snacks, etc. By adding an appropriate amount of the enzyme-treated product, foods and drinks to which the active ingredients contained in the sake-enzyme-treated product are added can be provided. In addition, for example, shampoos, hair creams, other hair cosmetic bases; siroy, lipstick, other cosmetic bases and cosmetic detergent bases, etc. By adding, it is possible to provide cosmetics to which the active ingredient contained in the processed enzyme product of sake is added.

 Hereinafter, the present invention will be described more specifically with reference to examples.

<Preparation of ethanol-free sake>
1000 g of commercially available sake (pure rice sake: hereinafter referred to as “Sake Sake A”) was concentrated under reduced pressure approximately twice to obtain 462.2 g of concentrated sake. To this concentrated sake was added ion exchange water in the same amount as the effluent (537.8 g) to prepare 1000 g of deethanol sake B. The analytical values of sake A and deethanol sake B are shown in Table 1.

  Using sake A and deethanol sake B, in Example 1 and Comparative Example 1 below, the influence of ethanol on deglucose by glucose oxidase was examined.

<Example 1>
After adding 800 g of deethanol sake B prepared as described above to a 2 L mini jar and adjusting the pH to 4.5 with a 30% by mass NaOH aqueous solution, 0.78 g (1170 u) of Hyderase 15 (trade name of glucose oxidase manufactured by Amano Enzyme) ) Was added after dissolving in 10.0 g of ion-exchanged water, and aerated and stirred at 40 ° C. (aeration rate: 0.2 L / min, stirring: 600 rpm). In addition, it reacted, adjusting with 30 mass% NaOH aqueous solution so that pH of a reaction liquid might be 4.2 +/- 0.2. Analytical values of the reaction solutions at 1 hour, 4 hours, 5 hours and 20 hours of reaction are shown in Table 2, and the change in the amount of residual glucose is shown in FIG.

<Comparative Example 1>
In Example 1, it reacted like Example 1 except using sake A instead of deethanol sake B. The analysis values of the reaction solutions at 1 hour, 2 hours, 3 hours, 4 hours, 18 hours, 19 hours and 20 hours of reaction are shown in Table 3, and the change in the amount of residual glucose is shown in FIG.

  As is clear from the results of FIG. 1, the sake enzyme-treated product (Example 1) produced by the production method of the present invention treated with glucose oxidase using deethanol sake B had almost no glucose remaining in the reaction at 5 hours. In contrast, the sake enzyme-treated product using Sake A (Comparative Example 1) had about 22% of the glucose amount before the reaction even after 20 hours of the reaction. Also, it can be seen that the content of α-ethyl glucoside is hardly changed even by the production method of the present invention (in Example 1 in which deethanolized sake B was treated with glucose coxidase, α-ethyl glucoside was 0 even after 20 hours. 37% by weight remaining (0.37% by weight before treatment; see Table 1), and in Comparative Example 1 in which sake A was treated with glucose oxidase, 0.36% by weight remained after 20 hours (0.38% by weight before treatment) ; See Table 1)).

<Sake enzyme-treated product according to the production method of the present invention (according to Example 1; hereinafter referred to as “Invention Product 1”) and a comparative product of sake enzyme-treated product (Comparative Example 1; hereinafter referred to as “Comparative Product”) 1)) stability comparison test>
Invention product 1 and comparative product 1 were filtered to remove residual salts, and water was removed under reduced pressure (45 ° C., 50 mmHg). Thereafter, ethanol is added and the gluconate is removed by filtration, and each is concentrated again 10 times under reduced pressure (until the mass becomes 1/10) to remove moisture and alcohol. Each was stored in a constant temperature bath at 60 ° C., and the degree of coloring over time was observed at an accelerated rate. As a coloring evaluation method, an ultraviolet / visible spectrophotometer was used, the absorbance was measured at a measurement wavelength of 430 nm, the amount of change in absorbance was determined by the following calculation formula, and the results are shown in Table 4.
Calculation formula: Amount of change in absorbance = (absorbance on day X)-(initial absorbance)

  As is apparent from Table 4, it can be said that the inventive product 1 produced by the production method of the present invention has a lower degree of coloring than the comparative product 1 and is superior in terms of stability.

Since the method for producing an enzyme-treated product of sake of the present invention can efficiently convert glucose in sake to gluconic acid, the resulting enzyme-treated product of purified sake has suppressed degradation of quality such as browning over time. Excellent storage stability. Therefore, application to various fields such as for foods and cosmetics can be expected.

It is a figure which shows the change of the amount of residual glucose at the time of glucose oxidase reaction.

Claims (5)

A method for producing an enzyme-treated product of refined sake, comprising preparing concentrated ethanol obtained by concentrating sake to deethanol purified sake having an ethanol concentration of less than 1% by mass , and then treating the deethanolized sake with glucose oxidase. The method for producing a purified enzyme product according to claim 1, wherein the glucose content in the purified enzyme product is 0.2% by mass or less . The method for producing a purified enzyme product according to claim 1 or 2, wherein the content of α-ethylglucoside in the purified enzyme product is 0.3% by mass or more. The method for producing a processed product of sake enzyme according to any one of claims 1 to 3 , comprising a treatment of removing gluconic acid converted from glucose after treatment with glucose oxidase. The refined sake enzyme processed material obtained by the manufacturing method of any one of Claims 1-4 .