JP3445487B2 - Sake that is difficult to color or synthetic sake - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hardly colored sake or synthetic sake. [0002] Hitherto, studies on the coloring of sake produced during storage and aging have been actively conducted, and at present, the causative substance or the coloring mechanism has been almost completely elucidated. As shown in Table 1, it has been found that mainly five factors are involved in the coloring of sake. [Table 1] With the development of manufacturing technology, among these factors, raw materials such as flavin, metals such as iron, copper, and manganese are almost completely eliminated in the management of feed water, the improvement of fermentation tanks, or the manufacturing process before shipment. Can now be removed. Deferifericrysin, which is produced by koji molds during koji making, has hardly been a problem due to selection of excellent koji molds. Further, among the causative substances of sunlight coloring, flavin, deferifericrysin, and metals can be removed or eliminated as described above. Best of all, this can be prevented if you manage to avoid prolonged exposure to sunlight. However, most of the substances causing coloring due to aging are sugars and amino acids which are the main components of sake, and it is impossible to remove them. Many of the coloring substances due to aging are due to chemical reactions, and the only way to prevent them is to control them at low temperatures. Management before shipment is still possible, but management during the distribution process is very difficult. In addition, this aging coloring
It is closely related to quality deterioration such as aged scents, and also occupies the largest proportion of the coloring of sake. For the above reasons, it is said that the coloration or quality deterioration of sake cannot be avoided to some extent, and no effective prevention method has yet been found. On the other hand, ethyl-α-D-glucoside is known to be contained in trace amounts as a saccharide component of sake, and it has been revealed that this component has a characteristic of combining sweetness and bitterness. In addition, demands for flavors are also increasing due to the recent diversification of consumer preferences for alcoholic beverages. However, sake has a restriction on the liquor tax law in the raw materials used and the production method, so that it is difficult to produce sake having different tastes with ethyl-α-D-glucoside by the conventional production method, and ethyl-α- D-glucoside-rich sake has not been found in the past. SUMMARY OF THE INVENTION An object of the present invention is to provide a hard-to-color sake which has been difficult for many years by providing a high content of ethyl-α-D-glucoside, It is to provide a different new type of sake. Means for Solving the Problems Heretofore, ethyl-α-
Although the taste of D-glucoside is known, its physical properties are not well known. Then, the present inventors examined the physical properties of ethyl-α-D-glucoside in detail, and as a result, found that the thermal stability at each pH was extremely excellent and that the Maillard reaction did not occur at all. . All of these physical properties show a great effect on suppressing coloring. Therefore, ethyl-α-D-
As a result of intensive studies such as heating and storage after the addition of glucoside, it was discovered for the first time that ethyl-α-D-glucoside has a great effect on suppressing coloring of sake. Thus, the present inventors have further studied diligently and found that ethyl-α-D
-Sake production technology containing a high content of glucoside was established, and the present invention was completed. That is, the present invention is a sake or a synthetic sake containing ethyl-α-D-glucoside as an active ingredient. Preferably, the ethyl-α-D-glucoside is
0.5% (% by weight, the same applies hereinafter) or more. Also,
Preferably, the sake or the synthetic sake of the present invention has a glucose content of 1% or less. Here, sake and synthetic sake refer to sake and synthetic sake defined by the Sake Tax Law. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A major cause of aging and coloring of sake is Maillard, which finally produces melanoidin by a complex chemical reaction of reducing amino acids (mainly glucose) contained in sake with amino acids. It is due to the reaction. Melanoidin increases steadily at higher temperatures and longer times. For example, when commercial liquor is stored at 60 ° C. for 2 weeks, the absorbance at 430 nm is around 0.005 before storage, but increases to 0.041 to 0.103 after storage, and is clearly visible to the naked eye. Can be confirmed to change to yellowish brown. In order to suppress the Maillard reaction in sake, the content of glucose or amino acids may be reduced, but if the content is reduced, the taste is greatly adversely affected. The ethyl-α-D-glucoside, which the present inventors focused on, is a non-reducing sugar in which the reducing terminal of glucose is ethylated and is a non-reducing glycoside, so that the Maillard reaction does not occur. For example, the absorbance at 430 nm when glucose is added to acetate buffer (pH 5.0) containing 1% glycine as an amino acid so as to have a final concentration of 10% and autoclaved at 121 ° C. for 30 minutes is about 4 nm. However, when the same concentration of ethyl-α-D-glucoside was added, no increase in absorbance was observed. Further, the ethyl-α-D-glucoside in the solution for the reaction was converted to HP
Analysis by LC revealed that it had not been decomposed at all and had very high stability in an acidic solution and did not cause oxidative decomposition. This result means that no other coloring substance, furfural, is produced. From the above,
Ethyl-α-D-glucoside was found to be a very chemically stable carbohydrate that did not contribute to coloration. Therefore, in order to confirm whether or not the same behavior is exhibited in sake, a synthetic sake containing no sugar is prepared.
Each of glucose alone, ethyl-α-D-glucoside alone, or both glucose and ethyl-α-D-glucoside simultaneously added was subjected to autoclaving at 121 ° C. to compare the coloring degree. As a result, the liquor to which only glucose was added increased in the degree of coloring according to the glucose concentration, whereas the liquor to which only ethyl-α-D-glucoside was added hardly colored even when the amount of addition was changed. . Even more surprisingly, the degree of coloring of the liquor to which both glucose and ethyl-α-D-glucoside were added was suppressed by 30% or more compared to the liquor to which glucose was added alone. Although the details of this reason have not been elucidated, it has been found that ethyl-α-D-glucoside not only does not contribute to coloring but also has an effect of suppressing coloring involving glucose. Thus, it has been found that increasing the ethyl-α-D-glucoside content can suppress the aging coloration of sake, and that the glucose content can be reduced to further enhance the effect. [0010] Thus, the present inventors have established several methods for controlling the aging and coloring of sake. One is a method of directly adding a saccharide containing ethyl-α-D-glucoside, and the other is a method of producing sake by adding an enzyme agent. "Glucose" in the Liquor Tax Law is defined as, for example, crystalline glucose, highly hydrolyzed starch such as purified glucose, and fully purified,
In the case where glucose and dextrin coexist,
If the content of pure glucose in the solids exceeds 50/100, it is said to be treated as glucose. A method for producing ethyl-α-D-glucoside-containing glucose that satisfies this definition is known, and in the sake or synthetic sake according to the method of the present invention which is directly added, such known ethyl-α-D-glucoside is used as ethyl-α-D-glucoside. α-D-glucoside-containing glucose can be used. For example, Tokiko 6-30
No. 608, the product of the method for producing ethyl-α-D-glucoside is effective. The product produced by this method has an ethyl-α-D-glucoside content of 50% or less;
The production of "glucose" under the Liquor Tax Law, which contains more than 50% glucose, is quite possible. This ethyl-α-D-
By using glucoside-containing glucose as an auxiliary material, it is possible to produce sake having a high content of ethyl-α-D-glucoside. The amount of ethyl-α-D-glucoside to be added may be determined as appropriate, but it can be found in a small amount (0.3% or less, most often 0.2% or less) in commercially available sake.
HPLC analysis), the concentration in sake is preferably 0.5% or more in order to expect an effect. The case where an enzyme agent is added is as follows. The enzyme agent to be used is desirably α-glucosidase derived from Aspergillus oryzae or Aspergillus niger. For example, α-glucosidase “Amano” (manufactured by Amano Pharmaceutical Co., Ltd.) can be used as a commercially available enzyme preparation.
The enzymatic agent may be added at any time as long as it is during the mash, the addition, the intermediate preparation, the preparation and the mashing period after the preparation.
When considering the D-glucoside production efficiency, it is 2 to 2 after charging.
It is good to add it up to 3 days, preferably at any time until preparation. The amount of enzyme added is 10,000 rice
There is no particular limitation as long as it is less than one-first. In producing sake, there is almost no need to change conventional production methods, raw materials used, etc., except for the addition of α-glucosidase. Further, the glucoamylase titer of the koji is preferably lower. This is because if the glucoamylase titer is low, the glucose content contained in the sake can be expected to decrease, and the coloring prevention effect can be further enhanced.
By producing by this method, ethyl-α-
The D-glucoside concentration is expected to be 1% or more. Further, as a result of the coloring test, there was an inhibitory effect of 20% or more as compared with the sake without the enzyme agent added. Further, the present inventors have proposed a transformant of a filamentous fungus into which an α-glucosidase gene has been incorporated, for example, a recombinant obtained by self-cloning the α-glucosidase gene of Aspergillus oryzae (Japanese Patent Laid-Open No. 9-9968).
Was used to make koji, brewed sake, and examined the fate of ethyl-α-D-glucoside, glucose and oligosaccharides during the moromi period. The details are shown in the following examples.The α-glucosidase titer of koji using a recombinant is as follows.
The glucoamylase titer and the α-amylase titer are 20 to 50 times higher than the control parent strain koji.
%. When a small preparation test was performed using this koji, ethyl-α-D-glucoside had a concentration (1.5 to 3%) that could not be obtained by ordinary production methods, whereas glucose and other oligosaccharides Sugar was hardly detected. In addition, the results of the coloring test showed that the control effect was 70% or more as compared with the control sake. From the above, in order to produce a sake having a high content of ethyl-α-D-glucoside, it is necessary to increase the α-glucosidase titer and to produce a sake having a high content of ethyl-α-D-glucoside and a low content of glucose. For this purpose, it is effective to keep the glucoamylase and α-amylase titers low to some extent, particularly to lower the glucoamylase titers. Based on this finding, for example, by lowering the koji ratio from the usual 20% to about 5 to 15% and adding an α-glucosidase agent according to the above-mentioned rules, ethyl-α-D-glucoside can be obtained. It is possible to obtain a sake which is characterized by a high content and a low glucose content and is hardly colored. Furthermore, when a sensory test of ethyl-α-D-glucoside-rich sake was conducted, it was determined that there was a refreshing sweetness and a mild bitterness, and that the whole had a rich and rich flavor,
The evaluation was clearly different from conventional sake.
As described above, it has been found that ethyl-α-D-glucoside itself is a taste component, and it is not only difficult to color, but also a new type of sake can be obtained in taste. EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Example 1 Maillard reaction of saccharides 50 mM acetate buffer (pH 5.0) or 50 mM phosphate buffer (pH 5.0) containing 10% of various saccharides and 1% of glycine
H7.0) after autoclaving for 30-60 minutes.
Table 2 shows the absorbance at 0 nm (10 mm cell). [Table 2] As shown in Table 2, glucose and maltose, which are reducing sugars, are clearly colored with the passage of time, whereas ethyl-α-D-glucoside is almost the same as trehalose, which is a non-reducing sugar. No coloring due to the Maillard reaction occurs. Further, as a result of analyzing the ethyl-α-D-glucoside solution after 60 minutes at pH 5.0 by HPLC, it was found that the thermal stability was very high without any decomposition. Example 2 Coloring Test with Synthetic Sake After preparing a synthetic sake having the components shown in Table 3, a synthetic sake was prepared by adding glucose and ethyl-α-D-glucoside to the concentrations shown in Table 4. A coloring test by an autoclave was performed in the same manner as in Example 1. [Table 3] [Table 4] As shown in Table 4, the degree of coloring clearly increases as the concentration is increased and the time is increased by the addition of glucose, but almost no coloring is caused by the addition of ethyl-α-D-glucoside regardless of the concentration or the time. I didn't see it. In addition, when glucose and ethyl-α-D-glucoside coexist, 30 times more than when glucose alone is added.
% Or more. Example 3 Sake Brewing Sake Production Condition by Addition of α-Glucosidase Agent Yeast No. 7 yeast was used, total rice 400 g, pumping water ratio 140%, temperature was constant at 15 ° C., and the following Table 5 The two-stage small charging test was performed using the charging compound as shown in Table 1. In addition, about the koji, the koji for ordinary liquor using the five million stone of 70% of the milled rice ratio is used, and the enzyme titer is as shown in Table 6 below. The small preparation test was carried out for a group to which no enzyme was added as a control and a group to which a total of 50 U of α-glucosidase “Amano” was added. [Table 5] [Table 6] The abbreviations shown in the column of enzyme titer in Table 6 are as follows:
It is as follows. AGL: α-glucosidase, G
LA: glucoamylase, TAA: α-amylase, A
P: acid protease, ACP: acid carboxypeptidase Sake production is performed based on the above charging conditions,
On the 15th day, the upper tank was performed. The sake sample in the upper tank was passed through a filter having a pore size of 0.45 μm, and then treated with activated carbon to obtain a sake sample. The general analytical values of the sake samples are shown in Table 7 below. [Table 7] FIG. 1 shows the change of the sugar component during the mashing period in the preparation of the enzyme-free section, and FIG. 2 shows the change of the sugar component during the mashing period in the preparation of the enzyme addition section. As is clear from FIG. 1 and FIG. 2, the final production amount of ethyl-α-D-glucoside was about 8 times (in the non-enzyme-added section 2.65 mg / ml,
The difference was 20.50 mg / ml). From this, it was found that by adding the α-glucosidase agent to the usual preparation, it is possible to produce a sake having a high content of ethyl-α-D-glucoside. Next, the ethyl-α-D-glucoside-rich sake and the control sake were
The sample was subjected to a coloring test in an autoclave at 121 ° C. Table 8 shows the results. [Table 8] As is apparent from Table 8, ethyl-α-D
-Staining of the glucoside-rich sake was suppressed compared to the control sake. In addition, the glucose content of both is almost equal (ethyl-α-D-glucoside-rich sake: 5.
Taking into account that 9 mg / ml and control sake: 6.5 mg / ml), it is considered that the coloring suppression effect due to the coexistence of ethyl-α-D-glucoside is clearly present. In order to make the sake more difficult to color,
Again, low glucose is essential. Example 4 Production of koji by α-glucosidase high-producing strain Koji production was carried out using the α-glucosidase-high producing strain under the conditions described below. The control was performed simultaneously using a parent strain of α-glucosidase high-producing strain as a control. 50 rice
% Polished rice and 2 spores per 1 kg of rice
× 10 ⁹ cells were inoculated and cultured at 32 ° C. and 95% humidity for 55 hours. Table 9 below shows the enzyme titer of each koji. [Table 9] As shown in Table 9, the α-glucosidase-producing strain produced about 15 times more α-glucosidase in the koji than the parent strain, while
It was reduced to about 0%. Example 5 Sake Brewing Sake Production Conditions by α-Glucosidase High-Producing Strain Koji produced in Example 4 was used, and the yeast used was No. 7 yeast. The total rice was 400 g, the pumping water ratio was 140%, The temperature was kept constant at 15 ° C., and a two-stage small charging test was performed with the charging compound as shown in Table 5 above. Sake production was performed based on the above charging conditions, and the upper tank was placed on the 15th day. The sake sample in the upper tank was passed through a filter having a pore size of 0.45 μm, and then treated with activated carbon to obtain a sake sample. The general analytical values of the sake samples are shown in Table 10 below. [Table 10] FIG. 3 shows the change of the sugar component during the mash period during the preparation using the parent strain koji, and FIG. 4 shows the change of the sugar component during the mash period during the preparation using the α-glucosidase high-producing strain koji. Indicate fate. As apparent from FIGS. 3 and 4, in the preparation of the parent strain koji, the content of ethyl-α-D-glucoside was 2.0 mg / ml, and the glucose content was 10.0 mg / ml. On the other hand, in the preparation of the α-glucosidase high-producing strain koji, ethyl-α-
The D-glucoside content was 31.3 mg / ml, the glucose content was 1.7 mg / ml, and the sake was almost 15 times the ethyl-α-D-glucoside content and contained almost no glucose. Therefore, it was anticipated that this sake might have a different flavor from conventional sake and would be difficult to color. Therefore, these sakes were subjected to an autoclave (121 ° C.) and a coloring test was performed. Table 11 shows the results. [Table 11] As shown in Table 11, the sake having a high content of ethyl-α-D-glucoside and a low content of glucose exhibited a 74% color-suppressing effect as compared with the control sake. Compared to the ethyl-α-D-glucoside-rich sake of Example 3, the color-suppressing effect is remarkable, and the sake that is hardly colored is also the ethyl-α-D-glucoside-rich and glucose-containing sake. It turned out that. Example 6 Sensory tests Sensory tests were performed on the sake produced in Examples 3 and 5 by a panel of 10 persons using a 5-point method. The average score of each result is shown in Tables 12 and 13. [Table 12] [Table 13] The sake having a high content of ethyl-α-D-glucoside had all better results than the control sake, and the evaluation of taste was particularly excellent. As a specific comment,
"Not too sweet, just right", "Refreshing sweetness",
"Bitterness after sweetness", "unusual and interesting",
"Bitterness produces mellowness." Ethyl-α-D-glucoside itself is a taste component having both sweetness and bitterness. By containing 1% or more, it was clearly identified in the sensory evaluation of taste. In addition, in the sake of Example 5, an adverse effect on the taste due to a decrease in glucose content was also expected, but conversely, since the content of ethyl-α-D-glucoside was high, it was covered by the evaluation and obtained a considerable evaluation. Was. The high content of ethyl-α-D-glucoside makes it possible to provide a hard-to-color sake, which has been difficult for many years, and to reduce the glucose concentration to provide more effective coloring. Could be suppressed. This is a great advantage in quality control after shipping. In addition, sake having a high content of ethyl-α-D-glucoside is a new type of sake having an excellent flavor and can meet the demands of consumers.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the fate of a sugar component during a mash period during preparation of an enzyme-free section in sake brewing in Example 3. FIG. 2 is a graph showing the fate of a sugar component during a mash period during preparation of an enzyme addition section in sake brewing in Example 3. FIG. 3 is a graph showing the fate of a sugar component during a mash period during preparation using a parent strain koji in sake brewing in Example 5. FIG. 4 is a graph showing the fate of sugar components during the mashing period during preparation using α-glucosidase high-producing strain koji in sake brewing in Example 5.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Chieko Kumagai 4-9, Iizazu, Iizazu-cho, Nishinomiya-shi, Hyogo Inside the Ozeki Research Institute (56) References JP-A-4-112766 (JP, A) Kaihei 7-67615 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C12G 1/00-3/12 JICST file (JOIS)

Claims (1)

(57) [Claim 1] Ethyl-α-D-glucoside is 1.5 to
Sake or synthetic sake containing 3.0% and glucose of 1% or less.