JPH04148661A - Bitterness elimination of beta-glucooligosaccharide - Google Patents

Abstract

PURPOSE:To eliminate bitterness of a beta-glucooligosaccharide as a dietary sweetener or an enteric flora-improving substance and imparting mild sweetness by subjecting the beta-glucooligosaccharide to reducing treatment. CONSTITUTION:A reducing catalyst (preferably Raney nickel, platinum carbon, ruthenium carbon or palladium carbon) is added to an aqueous solution containing a beta-gloucooligosaccharide (preferably cellobiose, sophorose, laminaribiose, gentiobiose, 4-O-beta-D--gentiooligosy-D-glucose, 6-O-beta-D- gentiooligosyl-D-glucose) and subjected to reducing treatment under a condition of 50--200kg/cm<2> hydrogen pressure, at 80-170 deg.C to eliminate bitterness of the beta-glucooligosaccharide.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for removing bitterness from β-glucooligosaccharide, which can be used as a dietary sweetener or as an intestinal flora improving substance in foods, beverages, medicines, etc.

"Conventional technology" In the production of various food and drink products, sugar, starch syrup, glucose,
Various carbohydrates such as maltose and high fructose sugar have been used as sweeteners. However, these carbohydrates are glucose or sugars in which glucose is bound to an a-glucoside, and are broken down in the body and become a source of calories, so if consumed in excess, they can lead to obesity and lead to adult diseases such as diabetes. There was a problem. Non-caloric synthetic sweeteners such as aspartame have also been developed. However, since synthetic sweeteners are not natural products, there were concerns about their safety for humans.

On the other hand, in recent years, it has been known that the flora (bacterial flora) in the intestine is related to human health, and interest in intestinal bacteria is increasing. It is one of the bacterial species,
It is known that it plays a variety of beneficial physiological roles in humans and animals, such as inhibiting the growth of putrefactive bacteria and pathogenic bacteria in the intestines. Bifidobacteria decrease or disappear with various diseases and aging, so various attempts have been made to increase the number of Bifidobacteria in the intestines.

Under these circumstances, bifidobacteria-proliferating oligosaccharides have recently been in the spotlight, and fructooligosaccharides, konjac oligosaccharides, isomalto-oligosaccharides, galactooligosaccharides, etc. have been reported as having a bifidobacterium-propagating effect.

By the way, glucooligosaccharides consisting of β-glucoside bonds (hereinafter referred to as β-glucooligosaccharides) are carbohydrates obtained by combining glucose with β-1,6 bonds and/or β-1,4 bonds. - Glucoside bonds cannot be broken down by enzymes in the body, so they can be used as low-calorie carbohydrates. The applicant has also discovered that these β-glucooligosaccharides have a growth-promoting effect on bifidobacteria and lactic acid bacteria, and has already proposed an intestinal flora-improving substance consisting of β-glucooligosaccharides (specifically Ganpei 2-61
(See No. 935).

[Problems to be Solved by the Invention] However, β-glucooligosaccharides have a unique bitter taste, which adversely affects the flavor of some foods, so there is a problem that the scope of application is limited. there were.

Therefore, an object of the present invention is to provide a method for removing the bitter taste of β-glucooligosaccharide so that it can be freely added to foods, beverages, and medicines.

[Means for Solving the Problems] The present inventors have conducted various studies on β-glucooligosaccharide useful as a Daiecley sweetener and an intestinal flora improving substance. As a result, the reduced product has lost its bitter taste and has a good and mellow taste. They discovered that it exhibits a sweet taste and completed the present invention.

That is, the method for removing bitterness from β-glucooligosaccharides of the present invention is characterized by subjecting β-glucooligosaccharides to reduction treatment.

Hereinafter, the present invention will be explained in more detail by giving specific examples.

The β-glucooligosaccharides used in the present invention are produced by allowing β-glucosidases derived from various microorganisms to act on glucose and/or β-glucooligosaccharides to maximize the ultimate functions of condensation and transfer that β-glucosidase possesses. This allows for easy production with high yield. About this method.

Japanese Patent Application Laid-Open No. 1-222779, which was previously proposed by the present inventors,
This is explained in detail in Japanese Patent Application No. 1-41289.

To give an overview of this production method, it is possible to use β-glucosidase derived from various microorganisms.1 For example, the filamentous fungus Trichoderma viridii (Tr
ichodern+a viridel, Trichoderma rees
eil, Trichoderma coningii-ITricho
derea dazzling u1. Aspergillus niger (P.
wood-decaying fungi such as Polyporus turihiferii (enicillium), Chrysosporium lignorum (Chr sos), etc.
oriura danwanganki), Schizophyllum commune 1shizo h flus commune), etc.
In addition, the bacteria Pseudomonas fluorescens 1Ps
eudo*onasfluorescens var,
cellulosal, Cellulomonas uda (Cell
ulomonas udal, Clostridium thermocellum
ocelluml, Ruminococcus albus fRu
Enzymes originating from microorganisms such as minococcus albusl are preferably used. All of these microorganisms are known and can be easily obtained and enzymes can be prepared from them.

Moreover, D-glucose and/or β-glucooligosaccharide are used as the substrate. Here, the β-glucooligosaccharide used as a substrate means cellobiose, gentiobiose, or gentiooligosaccharide with a higher degree of polymerization. When β-glucooligosaccharide is used as a substrate, β-glucooligosaccharide with a higher degree of polymerization can be obtained by this enzymatic reaction. Particularly preferably, at least one selected from glucose, cellobiose, and gentiobiose is used as the substrate.

In this way, β-glucosidase can be converted into glucose and/or β-glucosidase.
-When acting on glucooligosaccharide, as a reaction product,
Various β-glucooligosaccharides such as cellobiose, gentiobiose, 4-0-β-D-gentioligosyl-D-glucose, and 6-0-β-D-gentiooligosyl-〇-glucose are obtained. Here, 4-0-β-〇-gentioligosyl-〇-glucose means 4-0-β-D-
Genthiobiosyl-glucose, 4-0-β-D-
It means gentiotriosyl-D-glucose or one with a higher degree of polymerization. In addition, 6-0-β-D-gentiooligosyl-〇-glucose means 6-0-β-
〇-Genthiobiosyl-D-glucose (gentiotriose), 6-0-β-D-gentiotriosyl-D-glucose (gentiotetraose) or a gentio-oligosaccharide with a higher degree of polymerization.

These reaction products vary depending on the enzyme used, but when glucose or cellobiose is used as a substrate, there is a tendency for a mixture of several types of the above-mentioned β-glucooligosaccharides to be produced. In addition, when gentiobiose is used as a substrate, 6
-0-β-〇-gentiobiosyl-D-glucose, 6
Only gentiooligosaccharides such as -0-β-D-gentiotriosyl-D-glucose tend to be produced.

In addition, to explain the enzyme reaction conditions, the substrate concentration is
Although not particularly limited, usually 1 to 90% (solid amount/volume)
is preferable, and 5 to 80% (solid amount/volume) is more preferable.Also, the higher the enzyme concentration with respect to the substrate, the better, but it is usually preferable to use 0 reaction temperature and reaction pl per 1 g of substrate. (This can be carried out under the optimum reaction conditions for the enzyme used.) Usually, the reaction temperature is 3.
0 to 80°C is preferable, and 50 to 70°C is more preferable.
The reaction pH is preferably about 3 to 8. The reaction time may be set to the time required for the desired β-glucooligosaccharide to be sufficiently produced and accumulated.1 Normally, the appropriate time is about 2 minutes to 72 hours.The reaction method is carried out by adding an enzyme to the substrate. ＾Good,
Alternatively, the enzyme may be adsorbed onto a suitable immobilizing agent to obtain an immobilized enzyme, and the reaction may be carried out in a continuous reaction using this immobilized enzyme.The reaction product thus obtained may be further fractionated by various methods. It is also possible to separate and purify various β-glucooligosaccharides.

In the present invention, the β-glucooligosaccharide obtained as described above is subjected to a reduction treatment. The reduction process is catalytic reduction (hydrogenation), which has traditionally been used in the production of sugar alcohols.
The law is adopted 6 e.g.

An aqueous solution of β-glucooligosaccharide having a concentration of 40 to 60% by weight is prepared, and a metal reduction catalyst such as Raney nickel, platinum carbon, ruthenium carbon, palladium carbon, etc. is added to this aqueous solution. Then, the hydrogen pressure was set to 50 to 200 Kg/cm', and the temperature was set to 80 to 170°C.
After the reaction is complete, add activated carbon to remove the catalyst, pass through an ion exchange resin to desalt, and if necessary concentrate or dry the β- A reduced product of glucooligosaccharide can be obtained.

The reduced product of β-glucooligosaccharide obtained in this way is
The bitterness characteristic of β-glucooligosaccharides has disappeared, and the product has a mellow sweetness. therefore.

It can be used as a dietary sweetener in various foods and medicines, and because of its high moisturizing properties, it can be effectively used as a moisturizer for foods, as well as a crystallization inhibitor, and a shine and body-imparting agent. Furthermore, the reduced product of β-glucooligosaccharide has a growth-promoting effect on bifidobacteria and lactic acid bacteria, and can also be used as a functional carbohydrate for health foods that improves intestinal flora.

When adding the reduced product of β-glucooligosaccharide as a sweetener to foods or medicines, if the sweetness is slightly insufficient, other sweeteners such as sucrose, starch syrup, glucose, etc.
It may be used in combination with at least one selected from maltose, high fructose sugar, honey, sorbitol, maltitol, lactitol, L-asparatylphenylalanine methyl ester (aspartame), saccharin, glycyrrhizin, steviocyto, and the like.

The reduced β-glucooligosaccharide has a 1M taste, a salty taste,
It blends well with various substances that have other tastes such as astringency and umami, so for example, soy sauce, miso, mayonnaise, dressing, vinegar, Chinese food, tempura soup, sauce, ketchup, etc.
Yakiniku sauce, curry roux, stew base, soup base, dashi base.

Can be used in various seasonings such as compound seasonings and mirin.

In addition, various Japanese sweets such as rice crackers, arare, rice cakes, manju, tsuiro, red bean paste, sheep's meal, jelly, castella, hard candy, bread, biscuits, crackers, kutsky, pies, pudding, putter cream, cream puffs, and sponge cakes. , various Western sweets such as donuts, chocolate, chewing gum, caramel, and hard candies; frozen confections such as ice cream and sorbet; syrups such as fruit pickled in syrup and watertight; pastes such as flower paste, peanut paste, and fuller paste. , processed fruit products such as jam, marmalade, syrup pickles, sugar fruit, pickles such as fukujinzuke, senmaizuke, and rakkyosei, meat products such as ham and sausage, fish products such as kamaboko and chikuwa, various delicacies, and tsukudani. In addition, various foods and drinks such as alcoholic beverages such as beer, liqueur, and alcohol, soft drinks such as coffee cocoa, juice, carbonated drinks, stamina drinks, lactic acid drinks, and lactic acid bacteria drinks, and instant food and drinks such as instant juice and instant coffee. It can also be used as a luxury item.

Furthermore, the reduced product of β-glucooligosaccharide may be mixed with other physiologically active substances such as dietary fiber, lactic acid bacteria, bifidobacteria, vitamins, etc. to be used as health foods, medicines, etc. In addition, it can be used as feed, food, etc. It can be added to all products for oral use such as cosmetics.

Note that the amount of the reduced β-glucooligosaccharide added to raw materials for various foods, beverages, pharmaceuticals, etc. is not particularly limited, but it is preferably 0.5 to 50% by weight, and 1.0 to 50% by weight.
More preferably, the content is 30% by weight.

"Action and Effect" According to the present invention, by reducing the β-glucooligosaccharide, the bitter taste of the β-glucooligosaccharide can be eliminated and a mellow sweetness can be imparted. This reduced product has effects as a dietary sweetener and an intestinal flora improving substance, similar to β-glucooligosaccharide. Therefore, it can be widely used as a material for various foods and medicines.

It can provide effects as a dietary sweetener and an intestinal flora improving substance.

"Example" The present invention will be explained in detail below using examples.

Example 1 f) To 300 g of D-glucose, β-glucosidase purified from a crude cellulase preparation "Meicelase" (trade name, manufactured by Meiji Seika Co., Ltd.) originating from Trichoderma viride 4 was added.5. 8 XIG' units (500 μl) added glucose approx. 60%, w/vl, pH 5.0, temperature 6
After the reaction was completed at 0°C for 48 hours, the reaction was stopped by heat treatment at 100°C for 5 minutes, and after decolorizing and deionizing with activated carbon by a conventional method, the mixture was heated for 5 minutes at 72% 1m/II.
The mixture was concentrated under reduced pressure. Table 1 shows the results of analyzing the sugar composition of the obtained concentrate by high performance liquid chromatography.

The analysis conditions for high performance liquid chromatography are as follows.

Column: 5CR-101 manufactured by Shimadzu Corporation Detector: Differential refractometer Column temperature: 55°C Column flow rate: 0.8 ml/win (b) Next, the reaction product sugar solution obtained in (a) was poured into a tube with an inner diameter of 2 cm, With jacket of length 120 cr (6
0°C) Column with cation exchange resin rDowex 99J
(Na''' type, manufactured by Dow Chemical Company), the above sugar solution was loaded to a solid content of 5 to 7% (v/v) based on the amount of resin, and the space velocity (SV, hr-' ) 0.35, and the gentio-oligosaccharide fraction was collected. The sugar composition of both of these fractions is shown in Table 1. The yield was 98% of the gentio-oligosaccharide content, and this operation was repeated 10 times. About 40
g of gentio-oligosaccharide was obtained. This was freeze-dried and powdered.

(Hereinafter, blank space) Table 1 (c) Oligosaccharide syrup with a β-glucooligosaccharide content of 80% or more obtained as described above (solid content 50%)
) 200-β into a 500 μ β volume autoclave, expand and add 12 g of Raney nickel catalyst, close the flange, and then fill with hydrogen at room temperature until the pressure reaches 120 kg/cl1m. The temperature was raised while stirring at a rate of 130° C. for 4 hours, the mixture was allowed to cool, and the reaction solution was taken out. To this reaction solution, 2 g of activated carbon was added, stirred, filtered, and then desalted with an ion exchange resin to obtain a reduced β-glucooligosaccharide.

In order to determine the hydrogenation rate of this reduced product, the amount of reducing sugar in the oligosaccharide solution before and after the reduction treatment was measured by the Somogyi-Nelson method, and as a result, 99.4% was reduced.

A sensory test was conducted on the oligosaccharide solution before and after the reduction treatment by seven experienced panelists. Sugar solution concentration is 5.0.0.1.0.05.0.025.0.005%
Judgment was made based on the number of people who found it bitter.

The results are shown in Table 2.

From the results in Table 2 and above, it can be seen that at the tested concentrations, no one felt bitterness in the sugar solution after reduction treatment, and it can be seen that bitterness has been removed from the reduction treatment product of β-glucooligosaccharide.

Example 2 The oligosaccharide syrup in (c) of Example 1 was replaced with oligosaccharide syrup having a β-glucooligosaccharide content of 45% or more (solid content 50%) 200sβ, and the rest was carried out in the same manner as in Example 1 to prepare β-glucooligosaccharide. A reduced sugar product was obtained. When the hydrogenation rate of this reduced product was measured in the same manner as in Example 1, it was found that 99.1% was reduced. This reduced product also had no bitter taste and had a good taste.

Example 3 (Manufacture of hard candy) β obtained in Example 1 (c) was added to 500 g+1 of 50% sucrose aqueous solution.
- 1 piece of Shirabu containing reduced glucooligosaccharide
00 g was heated and dissolved, and then heated and concentrated under reduced pressure until the water content was 2% or less. 5 g of citric acid and a small amount of lemon flavor and coloring were mixed with this and molded according to a conventional method to obtain a hard candy. Ta.

Honjima was a hard candy with good taste and no bitterness.

Example 4 (manufacture of jelly) 36 g of gelatin, 1 piece of jojiro! ! A jelly was prepared by a conventional method using 84 g of the reduced β-glucooligosaccharide prepared in Example 2, 28 g of Shirabu containing the reduced product of β-glucooligosaccharide, 420 g of wine, and 413 g of water. That is, gelatin is swollen in advance with a blended amount of 172 water, and caster sugar and the above-mentioned Shirabu are added to the remaining water, heated and dissolved to bring it to a boil, and the swollen gelatin is added to this and brought to a boil again. Cool this solution with ice water, add wine when it reaches 50℃, cool it further, and when it starts to thicken, dispense it into cups.
The product was covered with a lid and solidified in a refrigerator at 5°C.

Honjima has just the right amount of sweetness and has a luxurious taste.Patent applicant: Nihon Shokuhin Kako Co., Ltd. Patent attorney
Shigeru Matsui

Claims (5)

[Claims] (1) A method for removing bitterness from β-glucooligosaccharides, which comprises subjecting β-glucooligosaccharides to a reduction treatment. (2) The β-glucooligosaccharide is cellobiose, sophorose, laminaribiose, gentiobiose, 4-
selected from the group consisting of ¥O¥-β-¥D¥-gentiooligosyl-¥D¥-glucose and 6-¥O¥-β-¥D¥-gentiooligosyl-¥D¥-glucose A method for removing bitterness from at least one type of β-glucooligosaccharide according to claim 1. (3) The above 4-\O\-β-\D\-gentiooligosyl-\D\-glucose is 4-\O\-β-\D\-
Genthiooligosyl-￥D￥-glucose, 4-￥O￥
-β-￥D￥-gentiooligosyl-￥D￥-glucose and those with a higher degree of polymerization, the above-mentioned 6-￥O￥
-β-\D\-gentiooligosyl-\D\-glucose is 6-\O\-β-\D\-gentiooligosyl-
￥D￥-glucose (gentiotriose), 6-￥O
¥-β-¥D¥-gentytriosyl-¥D¥-glucose (gentiotetraose) and a method for removing bitterness from β-glucooligosaccharide according to claim 2, which has a higher degree of polymerization . (4) Adding a reduction catalyst to the aqueous solution containing the β-glucooligosaccharide and hydrogen pressure of 50 to 200 kg/cm^2,
β- according to any one of claims 1 to 3, wherein the reduction treatment is performed at a temperature of 80 to 170°C.
Method for removing bitterness from glucooligosaccharides. (5) The method for removing bitterness from β-glucooligosaccharide according to claim 4, wherein the reduction catalyst is at least one selected from Raney nickel, platinum carbon, ruthenium carbon, and palladium carbon.