JP2018046762A - BRANCHED α-GLUCAN MIXTURE SYRUP AND APPLICATION THEREOF - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sugar syrup easy to be handled, having no aging, small in concern of deterioration due to growth of microorganism and having low sweetness and an application thereof.SOLUTION: The above described problem is solved by providing a branched α-glucan mixture syrup constituted by a branched α-glucan mixture and water, having following (A) to (C) characteristic, and having solid concentration of 70 mass% to 75 mass%, and viscosity and moisture activity of less than 6,000 mPa s and less than 0.88 respectively, and an application thereof. (A) having a branched structure which is connected to a non-reduction terminal glucose residue which positions at an edge of linear glucan with glucose polymerization degree of 3 or more via a bond other than α-1,4 bond and has glucose polymerization degree of 1 or more. (B) weight average molecular weight is 1,000 dalton to 2,500 dalton and weight average molecular weight/number average molecular weight is less than 3. (C) water soluble dietary fiber content calculated by a high speed liquid chromatography method is 60 mass% or more.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a branched α-glucan mixture syrup and its use, and in particular, has a low sweetness, is less susceptible to deterioration due to microbial growth, and functions as a water-soluble dietary fiber when ingested by humans. The present invention relates to α-glucan mixture syrup and its use.

  Water activity (Water Activity, Aw) is a value that represents the proportion of free water in food that was introduced into the food science field by Scott in the 1950s. Water activity is defined by the ratio of the water vapor pressure (P) in a closed container containing food to the vapor pressure (Po) of pure water at that temperature, and is also 1/100 of the equilibrium relative humidity (ERH) of the food. Defined (Aw = P / Po = ERH / 100). For example, if the equilibrium relative humidity in an airtight container containing a specific food is 80%, the water activity of the food is 0.800.

  Each microorganism has a water activity range in which it can grow, and cannot grow below a certain water activity. The water activity is called minimum growth water activity and is used as an important index for preventing microbial deterioration of food. General bacteria such as Escherichia coli and Salmonella cannot grow with a water activity of less than 0.90, and yeast cannot grow with a water activity of less than 0.88. Therefore, except for special microorganisms, the water activity is less than 0.88. By controlling to this, deterioration due to microbial growth of food can be prevented.

  In the field of starch sugar, malto-oligosaccharide syrup has been known as the oldest and most familiar sweetener in history. Today, starch is made from syrup by changing the degree of saccharification (hydrolysis). A variety of maltooligosaccharide syrups have been produced. Each product has a different sugar composition, and functions such as sweetness, viscosity, hygroscopicity, osmotic pressure, browning, and sugar crystallization inhibiting action are appropriately selected and used depending on the application. As the maltooligosaccharide syrup, a product having a solid concentration of 70 to 80% by mass is usually manufactured, distributed and sold. However, the maltooligosaccharide has a higher viscosity of syrup as its glucose polymerization degree (molecular weight) increases. It becomes difficult to handle. On the other hand, if the solid concentration is lowered to reduce the viscosity of syrup, the water activity of syrup will increase and the concern of deterioration due to microbial growth will increase, so in the commercialization of maltooligosaccharide syrup The balance between viscosity and water activity is regarded as important.

  On the other hand, in the field of food, dextrin (starch partially decomposed product) with a relatively low degree of starch degradation (glucose equivalent, DE) has a low sweetness, is difficult to color, has a mild texture and is refreshing, It is used to add body feeling, viscosity, and shine to foods. However, dextrin has a higher degree of glucose polymerization (molecular weight) than malto-oligosaccharide, and it is difficult to handle when it is in the form of a high-concentration liquid product (syrup). Since it becomes cloudy and insolubilized, it is currently manufactured and sold exclusively in powder form. In addition, the powder product has a drawback in that, for example, when it is used for foods, it requires an operation of dissolving in water or a liquid food material each time, which takes time.

  On the other hand, Patent Documents 1 to 4 disclose a branched α-glucan mixture that functions as a water-soluble dietary fiber when ingested by humans, and the branched α-glucan mixture further includes the above-mentioned dextrin. It has little sweetness, is virtually tasteless, and is difficult to age even though it has a higher molecular weight than malto-oligosaccharides etc., so it can not be considered to make this a liquid product (syrup) with an increased solid concentration Absent. However, since the branched α-glucan mixture has a large molecular weight as described above, when it is made into a liquid product (syrup), it is naturally expected that the viscosity becomes high and handling becomes difficult. For this reason, a liquid product (syrup) of the branched α-glucan mixture has not been proposed yet.

International Publication No. WO2008 / 136331 Pamphlet International Publication No. WO2014 / 133060 Pamphlet International application PCT / JP2016 / 054884 Japanese Patent Application No. 2016-120585

  The present invention has been made in view of the above-mentioned current state of the prior art, and is a low-sweet saccharide syrup that does not impair the taste of other foods, and is equivalent to a conventional relatively low molecular weight maltooligosaccharide syrup. It is an object of the present invention to provide a saccharide syrup that is easy to handle even when the solid concentration is set to be low, does not age, has low water activity, and is less susceptible to deterioration due to the growth of microorganisms, and uses thereof.

  In order to solve the above-mentioned problems, the inventors of the present invention focused on the branched α-glucan mixture previously disclosed in Patent Document 1 and made it into a liquid product (syrup). Surprisingly, as a result of repeated research efforts, when the weight average molecular weight (Mw) of the above branched α-glucan mixture is controlled within a specific range, syrup (liquid product) obtained by dissolving this in water is compared with the conventional comparison. Even when the solid concentration is equal to or higher than that of a low molecular weight maltooligosaccharide syrup, that is, when the solid concentration is 70% by mass or more, it exhibits a viscosity that can be handled. The present inventors found that the water activity when stored at 25 ° C. was clearly lower than 0.88, although it was mainly composed of a branched α-glucan having a higher molecular weight than maltooligosaccharide syrup. Moreover, as a matter of course, the syrup (liquid product) has an excellent characteristic that it is low in sweetness and hardly aged like the above-mentioned branched α-glucan mixture as a main component. Based on this finding, the present inventors have developed a carbohydrate syrup that combines the advantages of both maltooligosaccharide syrup and dextrin, i.e., has a low sweetness, a viscosity that can be handled even when the solid concentration is increased, and aging. The present invention has been completed by establishing a branched α-glucan mixture syrup that has the advantage of being difficult and less susceptible to deterioration due to the growth of microorganisms, and that also retains the function as a water-soluble dietary fiber.

That is, the present invention is composed of a branched α-glucan mixture having the following characteristics (A) to (C) and water, the solids concentration is 70% by mass or more and 75% by mass or less, and the solids A solution for solving the above-mentioned problems by providing a branched α-glucan mixture syrup having a viscosity and water activity measured at 25 ° C. at a concentration of 70% by mass of less than 6,000 mPa · s and less than 0.88, respectively. Is:
(A) A non-reducing terminal glucose residue located at one end of a linear glucan having a glucose polymerization degree of 3 or more and having glucose as a constituent sugar and linked via an α-1,4 bond, other than α-1,4 bond Having a branched structure with a glucose polymerization degree of 1 or more linked through a bond;
(B) The weight average molecular weight (Mw) is 1,000 Daltons or more and 2,500 Daltons or less, and the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is less than 3. is there;
(C) The water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC method) is 60% by mass or more.

  Furthermore, this invention solves the said subject by providing the use to the food-drinks of branched alpha-glucan mixture syrup.

  The branched α-glucan mixture syrup of the present invention is not only a safe edible material, but also has a low sweetness, does not age despite its high solids concentration, and is a relatively low molecular weight commercially available in the past. Similar to maltooligosaccharide syrup, it has a viscosity that can be handled, and its water activity at 25 ° C is less than 0.88, so there is little fear of deterioration due to the growth of microorganisms, so it is extremely useful as a material for various foods and beverages. is there. The branched α-glucan mixture syrup exhibits a function as a water-soluble dietary fiber when ingested by humans.

It is a HPLC chromatogram which shows the saccharide | sugar composition of an example (test sample 3) of the branched alpha-glucan mixture syrup which concerns on this invention. It is a HPLC chromatogram which shows the saccharide | sugar composition of commercially available maltotetraose syrup.

The present invention comprises a branched α-glucan mixture having the following characteristics (A) to (C) and water, the solid concentration is 70% by mass to 75% by mass, and the solids concentration The invention relates to a branched α-glucan mixture syrup having a viscosity and water activity measured at 25 ° C. under a condition of 70% by mass of less than 6,000 mPa · s and less than 0.88, respectively:
(A) A non-reducing terminal glucose residue located at one end of a linear glucan having a glucose polymerization degree of 3 or more and having glucose as a constituent sugar and linked via an α-1,4 bond, other than α-1,4 bond Having a branched structure with a glucose polymerization degree of 1 or more linked through a bond;
(B) The weight average molecular weight (Mw) is 1,000 Daltons or more and 2,500 Daltons or less, and the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is less than 3. is there;
(C) The water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC method) is 60% by mass or more.

  The branched α-glucan mixture as used in the present specification is a branched α-glucan mixture obtained by allowing the same applicant as the present application to act on a specific enzyme on starch or a partially decomposed product of starch previously disclosed in Patent Document 1. In general, the branched α-glucan mixture generally has the structural characteristics shown in the above (A), that is, glucose polymerization in which glucose is the only constituent sugar and linked via α-1,4 bonds. It has a feature that it has a branched structure having a glucose polymerization degree of 1 or more linked to a non-reducing terminal glucose residue located at one end of a linear glucan having a degree of 3 or more via a bond other than α-1,4 bond. Yes. As used herein, “linear glucan having a degree of glucose polymerization of 3 or more linked via α-1,4 bonds” refers to maltooligosaccharides having a molecular weight of maltotriose or higher, maltodextrin, partially decomposed starch, etc. Of α-1,4 glucan. The “bond other than α-1,4 bond” in the feature (A) specifically means each bond of α-1,2, α-1,3, α-1,6, The “non-reducing terminal glucose residue” means a glucose residue located at the end of the glucan chain linked through α-1,4 bonds that does not exhibit reducing properties. Incidentally, as disclosed in Patent Document 1, α-glucosyltransferase essential for producing a branched α-glucan mixture mainly catalyzes α-1,4 glucosyl transfer and α-1,6 glucosyl transfer, and α -1,3 Glucosyl transfer is an enzyme that catalyzes although its frequency is low, and the branched structure in the obtained branched α-glucan mixture is mainly through α-1,6 bonds.

  Incidentally, the branched α-glucan mixture is usually literally various as expected from the production method disclosed in Patent Document 1 in which an enzyme having a specific α-glucosyl transfer action is allowed to act on a partially degraded starch. It is in the form of a mixture of a number of branched α-glucans having a branched structure and a degree of glucose polymerization (molecular weight). With the current starch sugar technology, except for those with a small degree of glucose polymerization, individual branched α-glucan molecules in the branched α-glucan mixture are completely separated and quantified to determine the sugar composition of the branched α-glucan mixture. In addition, it is impossible to determine the structure of each branched α-glucan molecule, that is, the binding mode of a glucose residue as a constituent unit for each branched α-glucan molecule. However, the structure of the branched α-glucan mixture can be characterized as a whole mixture by various physical methods, chemical methods or enzymatic methods commonly used in the field, and the branched α-glucan constituting the syrup of the present invention. The structure of the mixture can be first characterized by the characteristics of (A) above as a whole mixture.

  Furthermore, the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention can be characterized by its molecular weight and molecular weight distribution, and the branched α-glucan mixture usually has a weight average molecular weight (Mw) of 1. 3,000 Daltons to 2,500 Daltons, and a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is less than 3 (feature (B)). doing. In addition, a weight average molecular weight (Mw), a number average molecular weight (Mn), and Mw / Mn are obtained by subjecting a branched α-glucan mixture to molecular weight distribution analysis by, for example, gel filtration chromatography (GPC) widely used in the field. Can be sought. The weight average molecular weight (Mw) of the branched α-glucan mixture is the amount of action of liquefied or saccharified α-amylase used in combination with α-glucosyltransferase in the production process from starch, as shown in the examples described later. It can be controlled by increasing or decreasing the value. In general, starch sugars such as maltooligosaccharides increase the viscosity of a high-concentration aqueous solution as the weight average molecular weight (Mw) increases, and the water activity increases while the viscosity decreases as the weight average molecular weight (Mw) decreases. It has the feature to do. However, according to the findings uniquely found by the present inventors, the branched α-glucan mixture has a relatively low water activity when the weight average molecular weight (Mw) is regulated to 1,000 daltons to 2,500 daltons. Even as a high concentration aqueous solution (syrup) that remains at a value, the viscosity does not increase so much and it has an unexpected characteristic that moderate handling properties are maintained. On the other hand, when the weight average molecular weight (Mw) of the branched α-glucan mixture exceeds 2,500 daltons, the viscosity increases when handling the water activity in a syrup form having a high solid concentration so as to keep the water activity at a relatively small value. Is not preferable as a component of a liquid product. On the other hand, when the weight average molecular weight (Mw) of the branched α-glucan mixture is less than 1,000 daltons, the content of monosaccharides and disaccharides having no branched structure is relatively increased and the content of branched α-glucan is decreased. Therefore, it is not preferable.

  Moreover, based on a weight average molecular weight (Mw), the average glucose polymerization degree of the branched α-glucan contained in the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention can be calculated. Therefore, the branched α-glucan mixture can also be characterized by an average degree of glucose polymerization. The average glucose polymerization degree can be obtained by subtracting 18 from the weight average molecular weight (Mw) and dividing by the glucose residue amount 162, so that the weight average molecular weight (Mw) is 1,000 daltons or more and 2,500 daltons. The above-mentioned branched α-glucan mixture has an average degree of glucose polymerization of about 6 or more and 15 or less.

  As described above, the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention has a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) of less than 3. It is characterized by that. In general, as the degree of degradation of starch partially decomposed products increases, the variation in the size of the constituent glucan molecules decreases, and Mw / Mn decreases. Mw / Mn means that the molecular weight variation (dispersion degree) of the glucan molecules constituting the glucan mixture constituting the glucan mixture which is closer to 1, that is, the fluctuation degree of glucose polymerization degree (dispersion degree) is smaller. When the value of Mw / Mn of the glucan mixture is 3 or more, although the upper limit of the weight average molecular weight (Mw) is restricted to 2,500 daltons as described above, the comparison is made depending on the degree of variation in the molecular weight of the glucan molecule. There is a high possibility that glucan molecules with a large molecular weight will be mixed specifically, and the viscosity may not fall below a predetermined value when a high-concentration aqueous solution (syrup) in which water activity remains at a relatively small value. So undesirable. Therefore, the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention preferably has an Mw / Mn of less than 3, and further has a smaller variation in molecular weight and an Mw / Mn closer to 1. What is less than 2 is more preferable.

  Further, the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention has a feature that the water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC method) is 60% by mass or more (feature) (C)). “High-performance liquid chromatographic method (enzyme-HPLC method)” (hereinafter simply referred to as “enzyme-HPLC method”) for determining water-soluble dietary fiber content is the nutrition labeling standard of the Ministry of Health and Welfare Notification No. 146 in May 1996. , "Methods for analysis of nutritional components, etc. (methods listed in the first column of the first column of the nutrition labeling standard)", the method described in "Food fiber", the outline of which is described below. It is as follows. That is, a sample for gel filtration chromatography is prepared by decomposing the sample by a series of enzyme treatments with heat-stable α-amylase, protease, and glucoamylase, and removing proteins, organic acids, and inorganic salts from the treatment solution with an ion exchange resin. Prepare the solution. Next, it is subjected to gel filtration chromatography, and the peak areas of undigested glucan and glucose in the chromatogram are obtained. The respective peak areas and glucose in the sample solution obtained separately by the glucose oxidase method by a conventional method are obtained. The amount is used to calculate the water soluble dietary fiber content of the sample. Throughout this specification, “water-soluble dietary fiber content” means the water-soluble dietary fiber content determined by the “enzyme-HPLC method” unless otherwise specified.

  The water-soluble dietary fiber content indicates the content of glucan that is not degraded by α-amylase and glucoamylase, and the characteristic (C) is the structure of the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention. Is an index that characterizes the mixture as a whole by enzymatic techniques. Of course, the higher the water-soluble dietary fiber content, in other words, the higher the content of α-amylase and branched α-glucan that is not degraded by glucoamylase, the more digested when humans ingest it. Instead, it reaches the small intestine and functions as a water-soluble dietary fiber. The water-soluble dietary fiber content is an index indicating that the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention has an indigestible structure, that is, a complex branched structure. Since a glucan molecule having a simple branched structure is less susceptible to aging than a carbohydrate mainly composed of linear α-1,4 glucan such as starch, the numerical value of the water-soluble dietary fiber content is the branched α of the present invention. -Glucan mixture syrup suggests difficulty in aging when solids concentration is increased.

  The branched α-glucan mixture syrup of the present invention is usually in the range of 70% by mass to 75% by mass of the solid concentration, and the viscosity and water activity measured at 25 ° C. under the condition of the solid concentration of 70% by mass. Have characteristics of indicating less than 6,000 mPa · s and less than 0.88, respectively. As described above, according to the knowledge obtained by the present inventors, the weight average molecular weight (Mw) of the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention is 1,000 daltons or more and 2,500. When controlled within the Dalton range, the syrup of the branched α-glucan mixture has a viscosity of less than 6,000 mPa · s and a water activity of less than 0.88 under the conditions of a solid concentration of 70% by mass and 25 ° C. It is a carbohydrate syrup having both the advantages of malto-oligosaccharide syrup and dextrin, which has no difficulty in handling and no fear of deterioration due to microbial growth. When the solid content concentration of the branched α-glucan mixture syrup is less than 70% by mass, the viscosity decreases and handling becomes easy, but the water content increases relatively and the water activity increases to 0.88 or higher. It is not preferable from the viewpoint of deterioration due to the growth of microorganisms. On the other hand, when the solid content of syrup exceeds 75% by mass, the water activity of syrup is lowered and the fear of deterioration is reduced, but the viscosity is increased and handling inconvenience occurs.

  The branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention has, as a preferred embodiment thereof, isomaltose converted to 35% by mass or more and 50% by mass based on the digested solid by digestion with isomaltdextranase. It has the characteristic (characteristic (D)) of producing | generating below. The isomalt dextranase digestion referred to as feature (D) means that isomalt dextranase is allowed to act on a branched α-glucan mixture to cause hydrolysis. Isomalt dextranase is an enzyme to which enzyme number (EC) 3.2.1.94 is assigned, and α-1,2, α-1 adjacent to the reducing end side of the isomaltose structure in α-glucan. , 3, α-1,4, and α-1,6 linkages, it is an enzyme that has the characteristic of hydrolyzing. The isomaltoxtranase is preferably an enzyme derived from Arthrobacter globiformis (eg, Sawai et al., Agricultural and Biological Chemistry, Vol. 52, Vol. 2, pp. 495-501 (1988)).

  The ratio of isomaltose per solid in the digest produced by isomalt dextranase digestion is the isomaltose structure that can be hydrolyzed with isomalt dextranase in the structure of the branched α-glucan that constitutes the branched α-glucan mixture. And the feature (D) further characterizes the structure of the branched α-glucan mixture as a whole by enzymatic techniques.

  The structural feature of “isomaltose dextranase digestion produces isomaltose 35% by mass or more and 50% by mass or less per solid product of digestion” shown by characteristic (D) contains the branched α-glucan mixture. Thus, the branched α-glucan mixture syrup of the present invention exhibits indigestibility and has an important meaning when functioning as a water-soluble dietary fiber when ingested by humans. The ratio of the isomaltose structure in the branched α-glucan is also the starch or starch portion in which the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention is the raw material, as in the water-soluble dietary fiber content. This indicates that the degradation product has a complicated branched structure, and suggests that the branched α-glucan mixture syrup of the present invention is difficult to age when the solid concentration is increased.

Furthermore, a more preferable embodiment of the branched α-glucan mixture contained in the branched α-glucan mixture syrup of the present invention includes a branched α-glucan mixture having the following characteristics (E) and (F): This feature can be determined by methylation analysis.
(E) the ratio of α-1,4 linked glucose residues to α-1,6 linked glucose residues is in the range of 1: 2 to 1: 3;
(F) The sum of α-1,4-bonded glucose residues and α-1,6-bonded glucose residues occupies 60% or more of all glucose residues.

  As is well known, methylation analysis is a generally used method for determining the binding mode of monosaccharides constituting a polysaccharide or oligosaccharide (Ciucanu et al., Carbohydrate). * Research (Carbohydrate Research), Vol. 131, No. 2, pp. 209-217 (1984)). When methylation analysis is applied to analysis of glucose binding mode in glucan, first, all free hydroxyl groups in glucose residues constituting glucan are methylated, and then fully methylated glucan is hydrolyzed. Next, methylated glucose obtained by hydrolysis is reduced to form methylated glucitol from which the anomeric form has been eliminated, and further, a free hydroxyl group in this methylated glucitol is acetylated to give partially methylated glucitol acetate (note that , “Partially methylated glucitol acetate” is sometimes simply referred to as “partially methylated product”). By analyzing the resulting partially methylated product by gas chromatography, various partially methylated products derived from glucose residues that have different binding modes in glucan have a peak area that occupies the peak area of all partially methylated products in the gas chromatogram. % (%). Then, the abundance ratio of glucose residues having different binding modes in the glucan, that is, the abundance ratio of each glucoside bond can be determined from the peak area%. “Ratio” for partially methylated product means “ratio” of peak area in gas chromatogram of methylation analysis, and “%” for partially methylated product means “area%” in gas chromatogram of methylated analysis. Shall.

  The “α-1,4-bonded glucose residue” in the above features (E) and (F) means glucose bonded to other glucose residues only through hydroxyl groups bonded to the 1st and 4th carbon atoms. It is a residue and is detected as 2,3,6-trimethyl-1,4,5-triacetylglucitol in methylation analysis. In addition, the “α-1,6-bonded glucose residue” in the above features (E) and (F) binds to other glucose residues only through hydroxyl groups bonded to the 1st and 6th carbon atoms. It is detected as 2,3,4-trimethyl-1,5,6-triacetylglucitol in methylation analysis.

  Ratio of α-1,4-bonded glucose residue and α-1,6-bonded glucose residue obtained by methylation analysis, and α-1,4-bonded glucose residue and α-1,6-bond The ratio of the total glucose residues to the total glucose residues can be used as one of the indicators that characterize the structure of the branched α-glucan mixture as a whole by chemical techniques.

  In the above feature (E), “the ratio of α-1,4-bonded glucose residues to α-1,6-bonded glucose residues is in the range of 1: 2 to 1: 3” is defined by the branch α -2,3,6-trimethyl-1,4,5-triacetylglucitol and 2,3,4-trimethyl-1,5,6-tritium detected when the glucan mixture is subjected to methylation analysis It means that the ratio of acetylglucitol is in the range of 1: 2 to 1: 3. In addition, the definition of the above-mentioned feature (F) that “the total of α-1,4-bonded glucose residues and α-1,6-bonded glucose residues occupy 60% or more of all glucose residues” The branched α-glucan mixture was converted into 2,3,6-trimethyl-1,4,5-triacetylglucitol and 2,3,4-trimethyl-1,5,6-triacetylglucitol in methylation analysis. It means that the total with Toll accounts for 60% or more of partially methylated glucitol acetate. In general, starch or a partially decomposed product of starch does not have glucose residues bonded only at the 1- and 6-positions, and α-1,4-bonded glucose residues account for the majority of all glucose residues. From the above, the characteristics (E) and (F) mean that the branched α-glucan mixture has a completely different structure from the starch or starch partial decomposition product.

  As defined in the above features (E) and (F), the branched α-glucan mixture, in a preferred embodiment, has a considerable amount of “α-1,6-linked glucose residues” that are not usually present in starch. In addition to α-1,4-linked glucose residues and α-1,6-linked glucose residues, α-1,3-linked glucose residues and α-1,3,6-linked glucose It may have a residue as a constituent sugar. Here, “α-1,3-bonded glucose residue” means “bonded to other glucose (α-1,3-bonded) only through hydroxyl groups bonded to the 1st and 3rd carbon atoms”. “Glucose residues” and “α-1,3,6 linked glucose residues” are “bonded to other glucose via three hydroxyl groups bonded to the 1st, 3rd and 6th carbon atoms respectively” (Α-1,3,6 linked) glucose residue ”. The branched α-glucan mixture usually contains 0.5% or more and less than 10% of α-1,3-linked glucose residues and all α-1,3,6-linked glucose residues. It may be contained in 0.5% or more of glucose residues.

  In addition, the fact that “α-1,3-linked glucose residues are 0.5% or more and less than 10% of all glucose residues” means that when the branched α-glucan mixture is subjected to methylation analysis, This can be confirmed by the presence of 4,6-trimethyl-1,3,5-triacetylglucitol in an amount of 0.5% to less than 10% of the partially methylated glucitol acetate. In addition, the fact that “α-1,3,6-linked glucose residues are 0.5% or more of the total glucose residues” means that the branched α-glucan mixture is 2,4-dimethyl in methylation analysis. It can be confirmed by the presence of 0.5% or more and less than 10% of partially methylated glucitol acetate in -1,3,5,6-tetraacetylglucitol.

  The branched α-glucan mixture syrup of the present invention is not limited by its production method, and is composed of a branched α-glucan mixture having the characteristics of the above (A) to (C) and water, and the solid concentration is As long as the viscosity and water activity measured at 25 ° C. under the condition of 70% by mass to 75% by mass and a solid concentration of 70% by mass are less than 6,000 mPa · s and less than 0.88, respectively. It may be manufactured by any method. As an example of a suitable production method of the branched α-glucan mixture syrup of the present invention, a crude enzyme solution of α-glucosyltransferase and a commercially available liquefaction disclosed in Example 1 of Patent Document 1 are used as starch or a partially degraded starch. And a method of acting in combination with a glycated α-amylase agent.

  As disclosed in Patent Document 1, the α-glucosyltransferase has a starch polymerization degree (α-1,4 glucan) as a substrate and a glucose polymerization degree of 3 or more linked through α-1,4 bonds. A branched α-glucan mixture which is a glycosyltransferase which introduces a branched structure by mainly transferring α-1,6 glucose to a non-reducing terminal glucose residue located at one end of a linear glucan and which constitutes the syrup of the present invention In addition, it is used as an enzyme that imparts the features (A) and (C). Examples of the α-glucosyltransferase include Bacillus circulans PP710 (Independent Administrative Institution National Institute of Advanced Industrial Science and Technology, Patent Biological Depositary Accession No. FERM BP-10771) or Arthrobacter globiformis PP349 (FERM BP). -10770) -derived enzyme is preferably used, and in particular, the crude enzyme derived from Bacillus circulans PP710 (FERM BP-10771) disclosed in Example 1 of Patent Document 1 is added to α-glucosyltransferase. Since it also contains a special amylase important in increasing the water-soluble dietary fiber content of the branched α-glucan mixture, it can be suitably used as an enzyme for producing the branched α-glucan mixture syrup of the present invention.

  In order to control the weight average molecular weight (Mw) of the branched α-glucan mixture constituting the branched α-glucan mixture syrup of the present invention within the range of the characteristic (B), as an enzyme used in combination with the α-glucosyltransferase, Commercially available liquefied or saccharified α-amylase agents can be advantageously used. In the branched α-glucan mixture syrup of the present invention, after starch material is heated and gelatinized, the starch is decomposed to a specific degree of decomposition (DE) by acting a relatively large amount of the liquefied α-amylase agent. It can manufacture by making the crude enzyme liquid of the said alpha-glucosyltransferase act on the obtained liquefied starch. In this case, the liquefied starch is desirably controlled within the range of DE10 to 30, preferably DE15 to 25. In addition, the branched α-glucan mixture syrup of the present invention is used for the above α-glucosyl transfer to liquefied starch (usually controlled to be less than DE5) obtained by gelatinizing starch and then allowing a liquefied α-amylase agent to act. It can also be produced by allowing a saccharified α-amylase agent to act together with a crude enzyme solution of the enzyme. In this case, it is usually desirable to control DE20 to 35, preferably DE23 to 30, at the end of the enzymatic reaction. As the liquefied α-amylase, a commercially available liquefied α-amylase agent may be appropriately selected and used. For example, “Spitase HK / R” (manufactured by Nagase ChemteX Corporation), “Sumiteam L” (Shin Nihon) Chemical Industry Co., Ltd.), “Termamyl” (Novozyme Japan Co., Ltd.) and the like are preferably used. As the saccharified α-amylase, a commercially available saccharified α-amylase agent may be appropriately selected and used. For example, “Spitase PK6 / R” (manufactured by Nagase ChemteX Corporation) is preferably used. Furthermore, α-amylase that produces specific maltooligosaccharides such as maltotetraose-producing amylase, maltopentaose-producing amylase, and maltohexaose-producing amylase can also be advantageously used as the α-amylase.

  Furthermore, in the production of the branched α-glucan mixture syrup of the present invention, in addition to the above enzymes, starch debranching enzymes such as isoamylase and pullulanase, and cyclomaltodextrin glucanotransferase (CGTase, EC 2.4) as necessary. 1.1.9), starch branching enzyme (EC 2.4.1.18) and the like can be used in combination. In particular, CGTase, when used in combination with α-glucosyltransferase, similarly to the amylase contained in the crude enzyme solution of α-glucosyltransferase described above, causes branched α-glucan to branch to a higher degree due to its glycosyltransferase reaction, Since there exists an effect which raises the water-soluble dietary fiber content of a branched alpha-glucan mixture, it can be used conveniently. It is also possible to appropriately reduce the reducing power of the branched α-glucan mixture syrup by reducing the reducing end of the branched α-glucan by hydrogenation.

  The branched α-glucan mixture syrup of the present invention is produced by a production method in which α-glucosyltransferase and a liquefied or saccharified α-amylase are combined to act on starch or a partially degraded starch. The production method inevitably produces small amounts of monosaccharides (glucose) and disaccharides (maltose and isomaltose) that do not have a branched structure in the enzyme reaction solution (saccharified solution). It has a form that also contains disaccharides. However, the branched α-glucan mixture syrup of the present invention is generally composed of α-glucan having a branched structure and more than trisaccharides, as can be seen in Examples (Table 2, Table 4, etc.) described later. Therefore, it will contain 85 mass% or more per solid substance.

  The reaction solution (saccharified solution) containing the branched α-glucan mixture obtained by the above enzyme reaction was filtered through diatomaceous earth according to a conventional method and decolorized with activated carbon, and the H type and After desalting with OH-type ion resin and purifying, and finishing filtration, it is concentrated to a solid concentration of 70% by mass or more to obtain the branched α-glucan mixture syrup of the present invention. Furthermore, the sugar solution containing the branched α-glucan mixture may be subjected to fractionation by column chromatography or the like to obtain a branched α-glucan mixture syrup from which low molecular oligosaccharides have been removed. The branched α-glucan mixture syrup obtained by purification and concentration as described above is filled into a sealed container such as a metal can, tank, or various plastic containers to obtain a product. The branched α-glucan mixture syrup of the present invention can be used as a food additive, cosmetic additive or pharmaceutical additive.

  Since the branched α-glucan mixture contained in the branched α-glucan mixture syrup of the present invention has a water-soluble dietary fiber content of 60% by mass or more, the branched α-glucan mixture syrup of the present invention has a water-soluble dietary fiber-containing syrup. It can be advantageously used for general food and drink. Specific examples of foods and drinks that can be blended with the branched α-glucan mixture syrup of the present invention include alcoholic beverages such as synthetic alcohol, brewed sake, sake, fruit wine, sparkling wine, beer, carbonated beverages, milk beverages, jelly beverages, sports drinks , Vinegar beverages, soy milk beverages, iron-containing beverages, lactic acid bacteria beverages, green tea, tea, cocoa, coffee and other beverages, cooked rice, rice cake, bread, noodles, soup, miso soup, yogurt and other foods, soft candy, hard candy, gummi, Jelly, cookie, soft cookie, rice cracker, hail, fern, fertilizer, rice bran, bracken, manju, sea bream, silkworm, sheep gourd, brocade, jelly, pectin jelly, castella, biscuit, cracker, pie, pudding , Butter cream, custard cream, cream puff, waffle, sponge cake, hot cake, muffin Donuts, chocolate, ganache, cereal bar, chewing gum, caramel, nougat, flower paste, peanut paste, fruit paste, jam, marmalade and other confectionery, ice cream, sorbet, gelato and other confectionery, as well as soy sauce, powdered soy sauce, miso , Powdered miso, moromi, horsetail, flakes, mayonnaise, dressing, vinegar, three cups of vinegar, sushi vinegar, Chinese vinegar, Chinese soup, noodle soup, noodle soup, sauce, tomato sauce, ketchup, grilled meat sauce, grilled chicken sauce, fried powder, Various seasonings such as tempura powder, curry roux, stew base, soup base, dashi base, compound seasoning, mirin and new mirin, and cooked products are listed.

  In addition, the branched α-glucan mixture syrup of the present invention should be used for the purpose of adjusting the intestine, improving constipation, and preventing obesity as feed and feed for domestic animals, poultry, other bees, rabbits, fish and other domestic animals. You can also. In addition, tobacco, toothpaste, lipstick, lip balm, oral solution, tablets, troches, liver oil drop, mouth freshener, mouth fragrance, mouthwash, etc., cosmetics, solution, syrup, tube feeding, tablets , Capsules, troches, sublinguals, granules, powders, powders, emulsions, sprays, and other various compositions such as pharmaceuticals.

  Furthermore, the branched α-glucan mixture syrup of the present invention is an anti-lifestyle disease agent or an immunomodulator disclosed in Patent Documents 2 to 4, similar to the powder product of the branched α-glucan mixture disclosed in Patent Document 1. Needless to say, it can be used for applications such as blood sugar elevation inhibitors.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples.

<Preparation of branched α-glucan mixture syrup>
In this example, liquefied starch was mixed with a commercially available saccharified α-amylase agent together with a crude enzyme solution (including amylase) of α-glucosyltransferase disclosed in Example 1 of Patent Document 1, with the amount of enzyme action. Branched α-glucan mixture syrup was prepared by purifying the saccharified solution by acting differently, and various physical properties of the obtained branched α-glucan mixture syrup were measured.

<Preparation of branched α-glucan mixture syrup>

  After adding calcium chloride to 30% (w / v) corn starch milk to a final concentration of 1 mM, the pH is adjusted to 6.5, and a liquefied α-amylase agent (trade name “Spitase HK / R” is added thereto. ”, Sold by Nagase ChemteX Corporation), was allowed to react at 5 units per gram of solid matter and reacted at 100 ° C. for 20 minutes. The reaction was stopped by autoclaving the resulting reaction solution at 131 ° C. for 30 minutes. Next, sodium bisulfite was added to the resulting liquefied starch (DE3.4) as a preservative to a final concentration of 0.1% by mass, and then cooled to 52 ° C. The concentrated crude enzyme solution of α-glucosyltransferase prepared according to the method described in Example 1 was added in an amount of 11 units per gram of the solid, and further, a saccharified α-amylase agent (trade name “Neospirase PK6 / R”, Nagase ChemteX Co., Ltd.) was added at 10, 15 or 20 units per gram of solid, and allowed to act at 52 ° C. and pH 6.0 for 48 hours, respectively. Three reaction solutions with different amounts of saccharified α-amylase agent Got. The obtained three kinds of reaction solutions were heat-treated at 80 ° C. for 1 hour to stop the enzyme reaction and cooled to obtain a saccharified solution.

  Each saccharified solution is filtered through diatomaceous earth according to a conventional method, then decolorized using activated carbon, purified by desalting with H-type and OH-type ion resins, subjected to finish filtration, and concentrated to a solid concentration of 70% by mass. Then, a branched α-glucan mixture syrup having an amount of action per gram of solid of the saccharified α-amylase agent different from 10, 15 or 20 units was obtained, and used as test samples 1, 2 and 3, respectively. All of these test samples had a low sweetness and were stable syrup in which white turbidity and insolubilization due to aging were not observed even when held at a solid concentration of 70% by mass.

<Analysis of branched α-glucan mixture syrup>
For the test samples 1, 2 and 3 obtained above, that is, three kinds of branched α-glucan mixture syrups having different glycated α-amylase action amounts, the glucose equivalent (DE) and the solids concentration were respectively determined according to the following methods. , Water activity, viscosity, molecular weight distribution of branched α-glucan mixture in syrup, water-soluble dietary fiber content, isomaltose content in isomalt-dextranase digest, α-1,4-linked glucose residues and α-1 , 6-bonded glucose residues, α-1,4-bonded glucose residues and α-1,6-bonded glucose residues in total glucose residues, and sugar composition did.

<Glucose equivalent (DE) of starch liquor and branched α-glucan mixture syrup>
The glucose equivalent (DE) of the starch liquefaction liquid and the branched α-glucan mixture syrup was measured by the conventional Lane-Eynon method.

<Measurement of solid concentration of syrup>
The solid concentration of the branched α-glucan mixture syrup was measured by a conventional reduced pressure heating drying method (drying aid method). That is, an appropriate amount of diatomaceous earth as a drying aid was added to an aluminum weighing can, and about 1 g of a sample was added as a solid content, and the weight was measured. Next, an appropriate amount of water was added, and the mixture was stirred with an aluminum rod and then dried at 80 ° C. under normal pressure. When the water on the surface of the diatomaceous earth evaporated, the mixture was stirred again with an aluminum rod, vacuum-dried at 80 ° C. for 16 hours, allowed to cool in a desiccator for 45 minutes, and the weight was measured. The dry weight loss (mass%) of the diatomaceous earth itself is subtracted from the dry weight loss (mass%) to obtain the dry weight loss (mass%) of the sample, and the dry weight loss (mass%) of the sample is subtracted from 100 to the solid content concentration (mass%). ).

<Measurement of water activity of syrup>
The water activity (Aw) of the branched α-glucan mixture syrup was measured by a conventional method using a Conway type water activity measuring instrument standard unit (manufactured by Shibata Kagaku Co., Ltd.). That is, 0.5 g each of samples (branched α-glucan mixture syrup) adjusted to a solid content concentration of 70% by mass was conditioned to various relative humidity (RH) with various saturated salt solutions shown below. The sample was held at 25 ° C. for 24 hours, and the increase or decrease in the sample weight at each relative humidity was measured. A graph showing the relationship between the increase / decrease in the weight of the sample and the relative humidity was prepared, and the equilibrium relative humidity at which the increase / decrease in the sample weight was 0 (zero) was determined to obtain the water activity.
Saturated salt solution Relative humidity (RH)
Sodium chloride 75.2%
Potassium bromide 80.7%
Potassium chloride 84.2%
Barium chloride 90.1%
Potassium nitrate 92.4%

<Measurement of viscosity of syrup>
The viscosity of the branched α-glucan mixture syrup was measured at 25 ° C. using a cone plate viscometer (trade name “DV-II + Pro”, manufactured by Brookfield) for a sample adjusted to a solid concentration of 70% by mass.

<Measurement of molecular weight distribution>
The molecular weight distribution of the branched α-glucan mixture contained in the branched α-glucan mixture syrup, that is, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the weight average molecular weight (Mw) in number average molecular weight (Mn) The divided value (Mw / Mn) was changed to “TSKgel α-M (manufactured by Tosoh Corporation)” as an analytical column and “TSKgel α-3000 (manufactured by Tosoh Corporation)” was used, and the flow rate was 0.5 mL / min. Except for analysis under conditions, each was measured by molecular weight distribution analysis by gel filtration HPLC described in paragraph 0081 of Patent Document 1.

<Water-soluble dietary fiber content>
The water-soluble dietary fiber content of the branched α-glucan mixture in the branched α-glucan mixture syrup was measured by an enzyme-HPLC method according to the method described in paragraphs 0069 to 0075 of Patent Document 1.

<Isomaltose content in digested isomalt dextranase>
The isomaltose content in the isomalt dextranase digest of the branched α-glucan mixture in the branched α-glucan mixture syrup was measured according to the method described in paragraph 0079 of Patent Document 1.

<Methylation analysis>
Ratio of α-1,4-linked glucose residues to α-1,6-linked glucose residues in the branched α-glucan mixture in the branched α-glucan mixture syrup, and α-1,4-linked glucose residues The ratio of the total of glucose residues bonded with α-1,6 to the total glucose residues was measured by methylation analysis described in paragraph 0076 of Patent Document 1.

<Sugar composition>
The sugar composition of the branched α-glucan mixture syrup was measured by high performance liquid chromatography (HPLC). HPLC uses two columns of “MCIGEL CK04SS” (Mitsubishi Chemical Co., Ltd.) connected in series, pure water as the eluent, column temperature of 80 ° C., flow rate of 0.4 mL / min. The detection was performed using a differential refractometer RID-10A (manufactured by Shimadzu Corporation).

  Table 1 summarizes the preparation conditions and analysis results of the branched α-glucan mixture syrup (test samples 1, 2 and 3) obtained above. Table 1 also shows the results of a similar investigation on commercially available maltotetraose syrup (trade name “Tetrap”, lot number: 6B15, Hayashibara Sales Co., Ltd.) as a comparison target. Table 2 shows the sugar compositions of test samples 1, 2, 3 and commercially available maltotetraose syrup. Note that “DP” in Table 2 means the degree of polymerization of glucose (degree of polymerization). Furthermore, as examples of HPLC chromatograms at the time of sugar composition analysis, chromatograms of test sample 3 and commercially available maltotetraose syrup are shown in FIGS. 1 and 2, respectively.

  As seen in Table 1, in the branched α-glucan production reaction using liquefied starch as a raw material and allowing α-glucosyltransferase to act, only the action amount of the saccharified α-amylase used in combination is 10, 15 or 20 units / g- The three kinds of branched α-glucan mixture syrup prepared by changing the solids, that is, the branched α-glucan mixture contained in each of the test samples 1, 2 and 3, has a weight average molecular weight (Mw) of 1,540 to 1 , 830 daltons, and Mw / Mn is 1.88 to 1.91, and the degree of dispersion is small. Furthermore, the branched α-glucan mixture contained in the test samples 1, 2, and 3 showed a water-soluble dietary fiber content of 63.2 to 68.1% by mass, which was sufficient to function as a water-soluble dietary fiber. . The test samples 1 to 3 each have a water activity measured at 25 ° C. under a solids concentration of 70% by mass of less than 0.88, and the viscosity measured at 25 ° C. under a solids concentration of 70% by mass. However, the viscosity was 2,790 to 4,080 mPa · s, which was slightly higher, but in a range that could be handled as a syrup product. In addition, the branched α-glucan mixture contained in the test samples 1, 2 and 3 has an isomalt dextranase digest isomaltose content of 37.2 to 38.0% by mass, and α-1 by methylation analysis. , 4-bonded glucose residues and α-1,6-linked glucose residues in the ratio of 1: 2.3 to 1: 2.4, α-1,4-bonded glucose residues and α-1,6-bonded The ratio of the total glucose residues to the total glucose residues was 63.1 to 66.9%.

  On the other hand, the malto-oligosaccharide contained in the commercially available maltotetraose syrup shown together in Table 1 as a comparison object showed a weight average molecular weight (Mw) of 1,620 daltons and Mw / Mn of 2.75. The maltotetraose syrup has a viscosity of 1,850 mPa · s measured at 25 ° C. under the condition of a solid concentration of 70% by mass, a low viscosity that is easy to handle as a syrup product, and a solid concentration of 70 The water activity measured at 25% by mass was 0.88.

  Moreover, as can be seen in Table 2, the test samples 1, 2 and 3 have 59.16% by mass, 53.87% by mass and 50.16% by mass of the branched α-glucan having a glucose polymerization degree (DP) of 9 or more, The syrup contained 50.57% by mass and 50% by mass or more. On the other hand, as is apparent from Table 2, commercially available maltotetraose syrup as a comparison target is composed mainly of maltotetraose (DP4) as its name, and has a sugar composition of 50% by mass or more. It contained maltotetraose.

  In addition, in the weight average molecular weight (Mw), the branched α-glucan mixture contained in the test sample 3 was 1,540 daltons, and the maltooligosaccharide contained in the maltotetraose syrup was 1,620 daltons, which was almost the same value. However, as apparent from the comparison between Table 2 and FIGS. 1 and 2, the sugar composition was completely different.

  The result of this example is that the crude starch solution of α-glucosyltransferase and the saccharified α-amylase agent are used in combination with liquefied starch to have a viscosity that can be sufficiently handled as a syrup product. This shows that a branched α-glucan mixture syrup having a water activity at 0 ° C. of less than 0.88 and less concern about deterioration due to the growth of microorganisms and a water-soluble dietary fiber content of 60% by mass or more can be produced.

  The branched α-glucan mixture syrup obtained in this example has a solid concentration of 70% by mass to 75% by mass, exhibits a viscosity that can be handled even at a solid concentration of 70% by mass, and water activity at 25 ° C. Is less than 0.88, it is a branched α-glucan mixture syrup product that is less susceptible to deterioration due to microbial growth in the storage and distribution stages. In addition, this product is less susceptible to aging in spite of containing a polymer branched α-glucan mixture as compared with conventional maltooligosaccharide syrup, and can be suitably used for imparting a body feeling to food and drink. It combines the characteristics of both maltooligosaccharide syrup and dextrin. Furthermore, since the branched α-glucan mixture contained in this product functions as water-soluble dietary fiber when ingested by humans, this product should be used suitably for various foods and beverages for which water-soluble dietary fiber is desired. Can do.

<Preparation of branched α-glucan mixture syrup>
In this example, unlike Example 1, first, a liquefied starch having a different degree of hydrolysis was prepared by causing a liquefied α-amylase to act in a relatively large amount in advance on starch milk. Various physical properties of the branched α-glucan mixture syrup obtained by saccharification and purification by the method using only the crude enzyme solution (including amylase) of α-glucosyltransferase disclosed in Example 1 were measured. .

<Preparation of branched α-glucan mixture syrup>

  After adding calcium chloride to 30% (w / v) corn starch milk to a final concentration of 1 mM, the pH is adjusted to 6.5, and a liquefied α-amylase agent (trade name “Spitase HK / R” is added thereto. ”, Sold by Nagase ChemteX Corporation), reacted at 8.2, 20 or 30.4 units per gram of solid, reacted at 100 ° C. for 20 minutes, and autoclaved at 131 ° C. for 30 minutes to stop the reaction. By this operation, three types of liquefied starch having a glucose equivalent (DE) of 8.6, 17.6 or 25.4 and different degrees of hydrolysis were obtained. To the resulting liquefied starch, sodium bisulfite was added as a preservative to a final concentration of 0.1% by mass, and then cooled to 52 ° C., which was described in Example 1 of Patent Document 1. 11 units of a concentrated crude enzyme solution of α-glucosyltransferase prepared according to the above method was added per gram of the solid and allowed to act at 52 ° C. and pH 6.0 for 48 hours. The obtained reaction solution was heat-treated at 80 ° C. for 1 hour to stop the enzyme reaction and cooled to obtain a saccharified solution.

  The saccharified solution was purified by the same method as in Example 1 and concentrated to a solid concentration of 70% by mass to obtain three kinds of branched α-glucan mixture syrup prepared from liquefied starches having different degrees of hydrolysis. Samples 4, 5, and 6 were used. Each of these test samples is, similarly to the test samples 1 to 3 prepared in Example 1, having a low sweetness and stable and no turbidity or insolubilization due to aging is observed even when the solid concentration is 70% by mass. It was syrup.

<Analysis of branched α-glucan mixture syrup>
The same items as in Example 1 were measured for the three branched α-glucan mixture syrups (test samples 4, 5 and 6) having different liquefied α-amylase action amounts obtained above. The results are shown in Table 3. Table 4 shows the sugar composition of test samples 4, 5 and 6.

  As seen in Table 3, it is obtained by allowing only a crude enzyme solution of α-glucosyltransferase to act on a partially decomposed starch obtained by allowing a relatively large amount of liquefied α-amylase to act at the stage of liquefying the raw material starch. Among the three branched α-glucan mixture syrups, the branched α-glucan mixtures contained in the test samples 5 and 6 have weight average molecular weights (Mw) of 1,810 and 1,550 daltons, which are obtained in Example 1. The test samples 1 to 3 were almost in the same range, and Mw / Mn was also almost the same as 1.92 and 1.96. Furthermore, the branched α-glucan mixture contained in test samples 5 and 6 has a water-soluble dietary fiber content of 69.8% by mass and 65.0% by mass, which is substantially equivalent to test samples 1 to 3 obtained in Example 1. Met. Test samples 5 and 6 both showed a water activity of less than 0.88 measured at 25 ° C. under a solid concentration of 70% by mass, and the viscosity measured at 25 ° C. under a solid concentration of 70% by mass. Showed viscosity of 5,430 mPa · s and 3,180 mPa · s, respectively, in a range that can be handled as a syrup product. In addition, the branched α-glucan mixture contained in the test samples 5 and 6 has an isomalt dextranase digested isomaltose content of 40.7% by mass and 38.5% by mass, respectively. The ratio of 1,4-bonded glucose residues to α-1,6-bonded glucose residues was 1: 2.7, and α-1,4-bonded glucose residues were α-1,6-bonded. The ratio of the total glucose residues to the total glucose residues was 66.7% and 64.2%, respectively.

  On the other hand, as shown in Table 3, the test sample 4 has a relatively high molecular weight of the branched α-glucan mixture contained therein having a weight average molecular weight (Mw) of 3,170 daltons, and a water-soluble dietary fiber content. Was 81.7% by mass, but the viscosity measured at 25 ° C. at a solid concentration of 70% by mass was 17,700 mPa · s, which was so high that it could not be handled as a syrup product. Since it showed a viscosity, the test sample 4 was not suitable as a branched α-glucan mixture syrup.

  As can be seen in Table 4, test samples 5 and 6 showed substantially the same sugar composition as test samples 1, 2 and 3 produced in Example 1, but test sample 4 was branched with a glucose polymerization degree of 9 or more. It contained 80% or more of an α-glucan mixture and contained a relatively large amount of a polymer component.

  The results of the present example show that the branched α-glucan mixture syrup of the present invention acts on liquefied α-amylase in advance to decompose starch to a certain degree, and then acts on the crude enzyme solution of α-glucosyltransferase. It shows that it can also be manufactured by the method of making it. However, when the action amount of liquefied α-amylase is small and the degree of starch degradation is low, the branched α-glucan mixture becomes a relatively high polymer, and the highly viscous branched α-glucan mixture syrup is not suitable as a syrup product. It shows that it becomes.

  The above test samples 5 and 6 have viscosities in a range that can be handled even at a solid concentration of 70% by mass, and the water activity at 25 ° C. at the solid concentration is less than 0.88. It is a branched α-glucan mixture syrup product that is less susceptible to deterioration due to microbial growth. In addition, this product is less susceptible to aging in spite of containing a polymer branched α-glucan mixture as compared with conventional maltooligosaccharide syrup, and can be suitably used for imparting a body feeling to food and drink. It combines the characteristics of both maltooligosaccharide syrup and dextrin. Furthermore, since the branched α-glucan mixture contained in this product functions as water-soluble dietary fiber when ingested by humans, this product should be used suitably for various foods and beverages for which water-soluble dietary fiber is desired. Can do.

<Branched α-glucan mixture syrup>
The saccharified α-amylase agent (trade name “Neospirase PK6 / R”, sold by Nagase ChemteX Corporation) was replaced with maltotetraose-producing enzyme (manufactured by Hayashibara Co., Ltd.), and 5 units per 1 g of liquefied starch solid was allowed to act. Produced a branched α-glucan mixture syrup having a solid concentration of 70% by mass in the same manner as in Example 1. The resulting branched α-glucan mixture syrup had a viscosity of 2,350 mPa · s and a water activity of 0.86. The branched α-glucan mixture contained in this branched α-glucan mixture syrup was analyzed in the same manner as in Example 1. As a result, the weight average molecular weight (Mw) was 1,420 daltons, and Mw / Mn was 2.00. The dietary fiber content was 68.3% by mass. Moreover, the isomaltose content of the digest obtained by digestion with isomaltodextranase is 40.3% by mass, and the ratio of α-1,4-linked glucose residues to α-1,6-linked glucose residues is 1: 2.3, the sum of α-1,4-linked glucose residues and α-1,6-linked glucose residues was 62.6% of the total glucose residues.

  This product has low viscosity even at a solid concentration of 70% by mass, is easy to handle, and has a water activity of less than 0.88 at 25 ° C. Is a small syrup product. Moreover, since the branched α-glucan mixture contained in this product functions as water-soluble dietary fiber when ingested by humans, it can be suitably used for various foods and beverages for which water-soluble dietary fiber is desired to be blended.

<餡>
In accordance with a conventional method, water was added to 100 parts by mass of the raw red beans, boiled, astringent and extracted, and water-soluble impurities were removed to obtain about 210 parts by mass of red bean grains. Add 140 parts by mass of sucrose, 67 parts by mass of the same branched α-glucan mixture syrup and 40 parts by mass of water to the test sample 3 of Example 1, and boil it. It kneaded so that it might not break, and obtained about 350 mass parts of product cocoons. This product is stable without color burns and water separation, contains a lot of branched α-glucan mixture as water-soluble dietary fiber, has a good touch and taste, and is suitable as a confectionery material such as rice cake bread, bun, dumpling, chuo, and ice confectionery. It is.

<University 芋>
After washing the fully-ripened Satsuma mushroom (Venezuma), it was cut into 20 to 25 g per piece and exposed to water to avoid browning due to drying during operation. Next, steaming with steam (steam) in a steam kettle set at 80 ° C. for 20 minutes was allowed to cool naturally, and then the oil was prepared and drained by a conventional method. Separately, 15 parts by weight of sugar, 20 parts by weight of the same branched α-glucan mixture syrup as in the test sample 1 of Example 1, 15 parts by weight of soy sauce, 30 parts by weight of mirin, and an appropriate amount of salt are mixed into the obtained Satsuma mash. Add the seasoning sauce prepared over the fire, entangle it well until shimmering, and sprinkle with black sesame seeds to get a university bowl. This product is moderately sweeter than a normal university candy and is a university candy with a seasoning sauce that contains a branched α-glucan mixture as a water-soluble dietary fiber. A university student with color.

<Rice rice>
After washing 500 parts by mass of rice, 33 parts by mass of the same branched α-glucan mixture syrup and 700 parts by mass of water as in the test sample 2 of Example 1 were added and cooked in an electric rice cooker to prepare cooked rice. By blending a branched α-glucan mixture, this product was improved in graininess (food texture) and looseness when mixed with rice scoop. This product is easy to eat because the branched α-glucan mixture does not adversely affect the taste and aroma of the cooked rice and improves the texture.

<Soda drink>
Fructose-glucose liquid sugar 50 parts by mass, sugar 20 parts by mass, the same branched α-glucan mixture syrup 33 parts by mass as prepared in Example 2, citric acid 1 part by mass, sodium citrate 0.3 part by mass, fragrance 0.02 part by mass was mixed with 500 parts by mass of carbonated water and completely dissolved to give a carbonated beverage. Since the branched α-glucan mixture functions as water-soluble dietary fiber, this product can be ingested daily as a carbonated beverage containing water-soluble dietary fiber. In addition, the blended branched α-glucan mixture syrup has an effect of increasing the body feeling and flavor feeling of the carbonated beverage.

<Toothpaste>
45 parts by mass of dibasic calcium phosphate, 1.5 parts by mass of sodium lauryl sulfate, 25 parts by mass of glycerin, 0.5 parts by mass of polyoxyethylene sorbitan laurate, 10 parts by mass of the branched α-glucan mixture syrup obtained by the method of Example 3 Then, 0.02 part by mass of saccharin was mixed with 18 parts by mass of water to obtain a toothpaste. This product has good feeling after use without reducing the detergency of the surfactant.

Comparative example

<Properties of commercially available dextrin (starch partially decomposed product)>
For the purpose of comparing the physical properties of the branched α-glucan mixture syrup of the present invention with two commercially available dextrins, namely dextrin A (trade name “Paindex # 3”, lot number 603302B, sold by Matsutani Chemical Co., Ltd.) and About dextrin B (trade name “Paindex # 4”, lot number 506051E, sold by Matsutani Chemical Industry Co., Ltd.), each of which is dissolved by heating in pure water so that the solid concentration becomes 70% by mass. In the same manner as in Example 1, glucose equivalent (DE), solid concentration, water activity, molecular weight distribution of the branched α-glucan mixture in syrup, and water-soluble dietary fiber content were measured. The results are shown in Table 5.

  As can be seen in Table 5, the dextrins A and B had weight average molecular weights (Mw) of 1,960 and 2,580 daltons, respectively, and Mw / Mn of 3.26. In addition, the liquid product adjusted to a solid concentration of 70% by mass of dextrin A and B showed water activity at 25 ° C. of 0.89 and 0.91, respectively, both of which exceeded 0.88, After 24 hours required for the measurement of water activity, white turbidity and partial insolubilization due to aging of dextrin were observed, and syrup could not be handled at all. Furthermore, dextrins A and B produced by simply decomposing starch did not have water-soluble dietary fiber properties.

  In addition, as seen in the results of Examples 1 and 2 and the comparative example, the branched α-glucan mixture contained in the test sample 1 of Example 1 and the test sample 5 of Example 2 has substantially the same weight as dextrin A. Despite having an average molecular weight (Mw), it does not age even when it is increased to a solid concentration of 70% by mass, and exhibits a smaller water activity of less than 0.88, and is aged under the same conditions. Moreover, when it was made into a highly concentrated liquid product (syrup), it showed completely different physical properties from dextrin A having a relatively large water activity of 0.89.

  As described above, the branched α-glucan mixture syrup of the present invention has low sweetness, does not age even when the solid concentration is increased, and is equivalent to a conventional relatively low molecular weight maltooligosaccharide syrup having the same solid concentration? In addition, since it has a viscosity that can be handled even if it is equal to or higher than that, and its water activity is low, there is an advantage in handling, storage, and distribution that there is little risk of deterioration due to the growth of microorganisms even in liquid form. Therefore, it is useful as a food additive raw material, a cosmetic additive raw material, a food / beverage raw material, and a cosmetic raw material. Moreover, the branched α-glucan mixture syrup of the present invention also functions as a water-soluble dietary fiber when ingested by humans. Thus, the present invention that provides a carbohydrate syrup having excellent properties is a truly significant invention that makes a great contribution to the world.

1 and 2, the numbers (“1” to “8”) added to each peak mean the glucose polymerization degree (DP) of the saccharide showing each peak.

Claims (5)

A condition comprising a branched α-glucan mixture having the following characteristics (A) to (C) and water, a solid concentration of 70% by mass to 75% by mass, and a solids concentration of 70% by mass Branched α-glucan mixture syrup having a viscosity and water activity measured at 25 ° C. of less than 6,000 mPa · s and less than 0.88, respectively:
(A) A non-reducing terminal glucose residue located at one end of a linear glucan having a glucose polymerization degree of 3 or more and having glucose as a constituent sugar and linked via an α-1,4 bond, other than α-1,4 bond Having a branched structure with a glucose polymerization degree of 1 or more linked through a bond;
(B) The weight average molecular weight (Mw) is 1,000 Daltons or more and 2,500 Daltons or less, and the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is less than 3. is there;
(C) The water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC method) is 60% by mass or more. The branched α-glucan mixture syrup according to claim 1, wherein the branched α-glucan mixture has the following feature (D):
(D) Isomaltose is produced by digestion with isomalt dextranase to produce 35 to 50% by mass of the digested solid per solid. The branched α-glucan mixture syrup according to claim 1 or 2, wherein the branched α-glucan mixture has the following characteristics (E) and (F) in methylation analysis:
(E) the ratio of α-1,4 linked glucose residues to α-1,6 linked glucose residues is in the range of 1: 2 to 1: 3; and (F) α-1,4 linked The total of glucose residues and α-1,6-linked glucose residues occupies 60% or more of all glucose residues.   A food additive, cosmetic additive or pharmaceutical additive comprising the branched α-glucan mixture syrup according to any one of claims 1 to 3.   A food or drink comprising the branched α-glucan mixture syrup according to any one of claims 1 to 3.

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