JPH0331294A - New oligosaccharide and production thereof - Google Patents

Abstract

NEW MATERIAL:An oligosaccharide prepared by separating the oligosaccharide from an acid-saccharified dextrose. USE:A culture raw material, a Lactobacillus bifidus-proliferating factor, a low cariogenic edulcorant and low-calonic edulcorant. PREPARATION:For example, corn starch is mixed with water to form a starchy milk, to which is added oxalic acid to adjust its pH to 1.7 and heated at a temperature of 140 deg.C for 40min to carry out saccharification. The resultant product is then neutralized, filtrated and treated with an ion-exchanger to purify and afford an acid-saccharified dextrose. Then the product is diluted, passed through a strong acid cation exchange resin and fractionated and an active fraction is further subjected to fractionation, ion-exchange purification, activated charcoal treatment, concentration, etc., to afford a disaccharide having alpha-binding and beta-binding or an oligosaccharide compound of the disaccharide having the alpha-binding and beta-binding.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel oligosaccharide and a method for producing the same, and more specifically, its use in foods and drinks as a sweetener with a unique taste, or as an active agent. , pharmaceutical culture raw materials,
The present invention relates to a novel oligosaccharide that can be effectively used as a bifidobacteria growth factor, a low axial sweetener, a low calorie sweetener, etc., and a method for producing the same.

<Prior Art> In recent years, with the progress and development of enzyme chemistry, glycosyltransferases and hydrolases of microbial origin have been searched for, and new saccharides are being actively developed. The basis of this technological flow is the conversion from the acid saccharification method to the enzymatic method. For example, industrial glucose production has now completely shifted from acid saccharification methods to enzymatic methods.

In other words, in glucose production using the acid saccharification method, ■
Formation of β-linked oligosaccharides such as gentibiose that have a bitter taste. ■ Lower yield of glucose. ■Necessity is necessary to obtain high-purity glucose.

The reality is that it has not been implemented due to the following problems.

<Problems to be Solved by the Invention> The present inventors investigated the properties of various oligosaccharides and found that r! The present inventors have discovered that oligosaccharides obtained by chromatographic separation from II-containing glucose have excellent properties that oligosaccharides obtained by novel transferases, hydrolases, etc. do not have.

In other words, the present invention seeks to actively apply oligosaccharides produced as by-products such as gentibiose, which have been a problem during the production of acid-saccharified glucose, and this technical idea has no precedent and is unique to this book. Invention is the first.

Means for Solving the Problems The present invention was completed by proactively applying the acid saccharification method in the current situation of developing new saccharides by enzymatic methods.

The present invention will be explained in detail below.

(Manufacture of glucose containing oligosaccharides by acid saccharification method) Starch is a high-molecular carbohydrate produced by photosynthesis in plants, and is made from a polymer of glucose.

This glucose bond is an α-1.4 and α-1.6 glucoside bond, and theoretically, when heated with f4 acid, it is easily hydrolyzed to glucose. However, under the hydrolysis conditions used industrially, starch molecules do not form a homogeneous solution even at very low concentrations, and some parts of the starch molecules form micelles that are difficult to undergo hydrolysis. If the concentration of starch, acid, or reaction temperature is high, the conversion of raw glucose occurs to produce nigerose, gentibiose, and other types, making it difficult to completely convert starch into glucose. .

That is, after starch hydrolysis by the acid saccharification method, it contains a considerable amount of oligosaccharides in addition to the product glucose, and the acid saccharified grape tang is useful as a raw material for oligosaccharides. Acid saccharification of S powder is hydrolysis due to the catalytic action of hydrogen ions, and glucose and oligosaccharide condensates are produced in various ratios depending on the degree of progress of hydrolysis. Specific factors that influence the degree of decomposition include the type and concentration of starch, the type and amount of acid used, the decomposition method and equipment, temperature and time. The starch to be used may be corn starch, potato starch, Ser4 starch, tapioca starch, etc., but there is no restriction as long as it is a starch commonly used for saccharification.

The concentration of the charged starch milk is about 10 to 40% by weight of solids. Examples of acids used include hydrochloric acid, sulfuric acid, and oxalic acid, but oxalic acid is generally used. In the case of oxalate saccharification, the calcium oxalate produced when calcium carbonate is used as a neutralizing agent has large precipitated particles, so it is easy to use, and its solubility is extremely low, so the color and transparency of the sugar content are good, and it is resistant to ion exchange. The load is also small.

In the case of the pressurized method, the amount of acid used is approximately 0.1 to 2.0% by weight relative to starch (as 4!! water). There are two decomposition methods: normal pressure and pressurization, but acid saccharification at normal pressure requires a large amount of acid and takes a long time, so pressure saccharification is usually used. Ru. There are two types of pressurized saccharification: single-can type (batch type) equipment and continuous type equipment, both of which can be used. The saccharification temperature and time depend on the decomposition equipment, but are usually 130 to 160°C and 10 to 80 minutes. The acid saccharification reaction solution obtained under these conditions has a DE (glucose equivalent) of 75 to 95 (glucose content per solid) of 7.
It contains 0 to 85% by weight, and 15 to 30% by weight of other substances other than glucose such as nigerose, gentibiose, and other substances (per solid basis). This acid saccharification reaction solution is then neutralized, filtered,
It undergoes ion exchange purification, activated carbon purification, and concentration to become an acid-saccharified glucose solution, that is, a glucose solution containing oligosaccharides. This oligosaccharide is characterized by containing nigerose, gentibiose, etc., which are difficult to contain in the oxygen saccharification method.

(Manufacture of high-purity oligosaccharides by chromatographic separation) Chromatographic separation is an excellent means of separating oligosaccharides whose main components are nigerose and gentibiose in a very hot and inexpensive manner. Exchange resins are suitable.The strongly acidic cation exchange resins used in the present invention are of the sulfonic acid type, such as Diaion 5.
KIB, Diaion SK 102, Diaion 5K
104, Diaion SK 106, Diaion 5K
IIO, Diaion 5K112, Diaion 5K1
16.Diaion FROI (product name, Mitsubishi Kasei I)
Or Amberlight [R-116, Amberlight IR-118, Amberlight I R-120R17
7 Amber Light XT1022E, 7 Amber Light xT47
1E, Amberly) G102 (all product names, manufactured by Organo) or DOWEX 50WX2, DOWEX 50WX4, DOWEX 50WX8, DOWEX 8
8 (The above product names, Dow Chemical Company! etc. are suitable,
The 0 min + 11 device, which is used as an alkali metal type or alkaline earth metal type before use, is composed of a stock solution tank, an exfoliating solvent tank, a liquid feed pump, a separation tower, a detector, a separation separation separation mechanism, and a control mechanism. Therefore, the operation for efficiently separating glucose and oligosaccharides requires a raw tIl sugar concentration of 30 to 30.
80% by weight, temperature 30-80°C, liquid passing rate = SVO, 0
A condition of 1 to 1°0 is preferred. The separated high-purity oligosaccharides are filtered, ion exchange purified, activated carbon purified, and concentrated to obtain high-purity oligosaccharides, but if necessary, they can be made into powder by spray drying.

<Examples> Examples of the present invention are shown below, but the present invention is not limited to these examples.

Reaction example 1 (Content IIk of acid saccharified glucose containing oligosaccharide
A single can type canner (pressurized can) equipped with a 3Q stirrer (30r, p, m) was used. Silicic acid was added to 2000 mQ of water to adjust the pH to 1.7.

Add 1400g of cornstarch to this to make starch milk,
Saccharification was carried out at a temperature of 140°C. The time required to reach the saccharification temperature of 140°C was 25 minutes. After the temperature rose to 140℃, rotate the stirrer to ensure uniform saccharification progress.
It was saccharified for minutes. After saccharification, add calcium carbonate to pH 5.
, neutralized to 6, filtration, ion exchange purification, activated carbon purification,
Acid-saccharified glucose containing oligomers was prepared by concentrating.

Table 1 shows the properties of the acid-saccharified glucose obtained above.
It is written in

Table 1 DPI is a monosaccharide consisting mainly of glucose. DP2 has α-linked disaccharides such as nigerose, cornbiose, isomaltose, maltose, α-
Trehalose is an oligosaccharide consisting of β-linked disaccharides such as gentibiose, laminaribiose, sophorose, cellobiose, and β-trehaleptase. DP3
The above are oligosaccharides consisting of maltotriose, maltotetraose, etc. The following analyzer was used for the above component analysis.

Analyzer High performance liquid chromatography■
■ (Organization) Waters Shimadzu LC4A type 590 type
(Shimadzu Corporation) (Column) (Solvent) SCRIOIN (Shimabara Corporation) Water Zorbax Nll2 (DuPont) i't) Nitrile: Water = 70: 30.

Table 2 Example 1 (Preparation of high-purity acid-saccharified oligosaccharides by chromatographic separation) The acid-saccharified glucose containing oligosaccharides obtained by the operation in Reaction Example 1 was diluted to a predetermined concentration, and the acid-saccharified glucose containing the oligosaccharides obtained by the operation in Reaction Example 1 was diluted to a predetermined concentration, and the acid-saccharified glucose containing the oligosaccharides obtained by the operation in Reaction Example 1 was diluted to a predetermined concentration. The mixture was separated into A section and 8 sections. The division is α bond,
Contains 20% oligosaccharide based on two types of β-bonds or two types of α- and β-bonds per serving.
This is a category containing the above. Category 8 contains glucose as a main component and is a category that is removed from products.

Category F is the category for the target product, which is adjusted to oligosaccharide syrup by filtration, ion exchange purification, activated carbon treatment, and concentration.

The properties of the oligosaccharide syrup obtained above are shown in Table 2. The above separation conditions are as follows.

Packing agent: Diaion FROI (Na type) (manufactured by Mitsubishi Kasei Corporation) Separation column: 40 mm l X2000 mmH (resin ff1211) Loaded sugar amount: 154 g/BX65 (1 step) Min H temperature = 66°C Liquid passing rate: SVo, 05 DPI is a monosaccharide consisting primarily of glucose.

The two types of α-linkages in DP2 are nigerose, cordibiose, isomaltose, maltose, and α-trehalose, and the two types of β-linkages are gentibiose, laminaribiose, sophorose, cellobiose, and β-
It is an oligosaccharide consisting of trehalose.

The following i settings were used for the above component analysis.

Analytical instrument High performance liquid chromatography (1)
■ (Model) Waters Shimajun LC4A type 590 (Shimabara Manufacturing) (Column) 5CRIOIN
Zorbax NHp (Shimabara Manufacturing) (DuPont) (solvent)
water ? Setnik 1 ku 1 = 70:
30 <Effects of the Invention> According to the present invention detailed above, α-
bond, two types with β-bond or α-bond, β
- It is possible to provide an industrial manufacturing method for efficiently and economically producing a syrup containing two types of oligosaccharides with high purity as main components.

The oligosaccharide syrup obtained by this production method can be used as a sweetener with a unique taste in foods and drinks, or as an active agent as a culture raw material for pharmaceuticals, bifidobacteria growth factors, low cariogenic sweeteners, and low calorie. It is a novel highly functional saccharide that can be used effectively in many fields, including as a sweetener.

Claims (1)

[Claims] 1. A novel oligosaccharide obtained by separating oligosaccharide from acid-saccharified glucose. 2. A method for producing oligosaccharides, which comprises separating oligosaccharides from acid-saccharified glucose. 3. The separated oligosaccharide is a disaccharide having α-bonds and β-bonds, or an oligosaccharide whose main component is a disaccharide having α-bonds and β-bonds, and the composition ratio is 20% per solid. The oligosaccharide according to claim 1, wherein the oligosaccharide is at least % by weight. 4. The separated oligosaccharide is a disaccharide having α-bonds and β-bonds, or an oligosaccharide whose main component is a disaccharide having α-bonds and β-bonds, and the composition ratio is 20% per solid. 3. The method for producing an oligosaccharide according to claim 2, wherein the amount is at least % by weight. 5. α-linked disaccharides include nigerose, cordibiose,
4. The oligosaccharide according to claim 3, wherein the oligosaccharide is isomaltose, maltose, or α-trehalose, and the β-linked disaccharide is gentibiose, laminaribiose, sophorose, cellobiose, or β-trehalose. 6. α-linked disaccharides include nigerose, cordibiose,
5. The method for producing an oligosaccharide according to claim 4, wherein the oligosaccharide is isomaltose, maltose, or α-trehalose, and the β-linked disaccharide is gentibiose, laminaribiose, sophorose, cellobiose, or β-trehalose. 7. The method for producing oligosaccharides according to claim 2, which uses a strongly acidic cation exchange resin as a separating agent.