JP2006211989A - GEL-LIKE FOOD, LIQUID FOOD AND DRIED FOOD CONTAINING alpha-1,4-GLUCAN - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide gel-like food, liquid food and dried food intended for solving such problems that conventionally known amylose obtained from natural starch or starch highly containing amylose is not suitable for food production based on gelatinization and thickening action manifested through melting amylose in water and coating film action manifested through drying amylose. <P>SOLUTION: The new gel-like food, liquid food and dried food are produced by using α-1,4-glucan enzymatically synthesized with glucan phosphorylase. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gel-like food, a liquid food, and a dried food characterized by containing enzyme-synthesized α-1,4-glucan.

  As α-1,4-glucan, amylose is known, exists in nature, and has also been attempted to be synthesized by an enzymatic reaction. These amyloses exhibit various physical properties and their use in food production has been studied, but their disadvantages are their insolubility in water at room temperature, etc. In addition, it was not suitable for the production of foods based on the film effect that is exhibited by drying it.

  Several methods are known for obtaining amylose from natural starch. For example, natural starch is allowed to act on an enzyme that specifically cleaves only α-1,6-glucosidic bonds (eg, isoamylase or pullulanase; these are known as debranching enzymes) to cause branching. There is a method (so-called starch enzymatic decomposition method) for obtaining amylose by decomposing. There is also a method in which only amylose is separated by precipitating an amylose / butanol complex from starch paste.

However, the following problems have been pointed out for amylose obtained from natural starch in this way. :
(A) Amylose contained in natural starch usually has a wide dispersity (Mw / Mn) of 1.3 or more. These amyloses are mixed with (i) low molecular weight amylose with high crystallinity and low water solubility, (ii) high molecular weight amylose with high binding power, and (iii) swellable amylose with an intermediate molecular weight. To do. Therefore, these various molecular weight amyloses inhibit each other and negate the superior properties of other amyloses with different molecular weights.
(B) The molecular weight of amylose contained in natural starch is usually several tens kDa to several hundred kDa, and water solubility cannot be expected; and (c) separation of amylose from natural starch is complicated and difficult to handle. The rate is also low and cannot be an industrial process.
(D) Even if it can be obtained, heating in excess of 100 ° C. is required to dissolve in water, and there are limitations to industrial use.

  A natural starch with a high amylose content, called high amylose corn starch or amylose-rich starch, has been developed and used as a food material. However, this starch has a high gelatinization temperature, cannot be dissolved in water, and has a limited range of use.

  For the above reasons, it seems that the application of amylose obtained from natural starch to food did not progress.

  Several methods (enzyme synthesis methods) for synthesizing α-1,4-glucan by linking glucose residues by the action of an enzyme are known.

  As an example, there is a method in which amylosucrase (EC 2.4.1.4) is allowed to act using sucrose as a substrate (hereinafter abbreviated as AMSU method). Α-1,4-glucan obtained by the AMSU method has a low degree of polymerization. Even α-1,4-glucan produced using highly purified amylosucrase is reported to have a molecular weight of 8,941 Da (Montalk et al., FEBS Letters 471, pp. 219-223). (2000); Non-Patent Document 1). In this method, only α-1,4-glucan having a low polymerization degree and low solubility in water can be produced, and high molecular weight amylose having high solubility in water cannot be produced. It is also impossible to control the molecular weight of amylose.

  As another method of enzyme synthesis, there is a method using glucan phosphorylase (α-glucan phosphorylase, EC 2.4.1.1; usually referred to as phosphorylase). In such a method, only phosphorylase is allowed to act on a substrate (glucose-1-phosphate) and its glucosyl group is transferred to a primer (for example, maltoheptaose) (referred to as GP method) and phosphorylase. There is a method of synthesizing G-1-P from sucrose by using sucrose phosphorylase and transferring the glucosyl group of G-1-P to a primer (referred to as SP-GP method) (for example, International Publication No. WO02 / No. 097107 pamphlet (Patent Document 1)).

However, this pamphlet discloses that insoluble amylose is expected to work in the same way as dietary fiber and can be expected to be used in health foods, but other functions that amylose exerts in foods are disclosed. , Nothing is disclosed. There is no suggestion or disclosure regarding the gelling function, thickening function, and film-forming function by adding pure amylose, which has been subjected to enzyme synthesis, to foods. Thus, the function given to food of pure amylose, particularly the function given to food of amylose having a specific molecular weight, has not been studied.
International Publication No. WO02 / 097107 pamphlet (pages 127-134) Montalk et al., FEBS Letters 471, 2000, pp. 219-223.

  The problem to be solved by the present invention is that gel foods and liquid foods having new and good physical properties and textures, which cannot be obtained with existing food materials such as amylose obtained from natural starch and starch with high amylose content Is to produce dry food.

The present inventors diligently studied and arrived at the present invention whose main feature is to use an enzyme-synthesized α-1,4-glucan that is readily soluble in water at room temperature and can be used industrially.
The α-1,4-glucan used in the present invention contains α-1,4-glucan enzymatically synthesized by glucan phosphorylase as an active ingredient.
In one embodiment, the α-1,4-glucan may have a degree of polymerization of 600 or more and less than 37000.
In one embodiment, the α-1,4-glucan may have a polymerization degree of 600 or more and less than 37000, and a dispersion degree of 1.25 or less.
In one embodiment, the α-1,4-glucan contains a modified product, and the modification may be a chemical modification selected from the group consisting of esterification, etherification, and crosslinking.

  It becomes possible to produce a novel food based on gelation, thickening action, and film forming action that is exhibited by drying by adding α-1,4-glucan to food.

(Definition of terms)
(Dispersity Mw / Mn)
Except for special cases such as proteins, a high molecular compound has a molecular weight that is not single but has a certain range regardless of whether the high molecular compound is natural or non-natural. Therefore, in order to show the degree of dispersion of the molecular weight of the polymer compound, the molecular weight distribution Mw / Mn is usually used in the field of polymer chemistry. The molecular weight distribution Mw / Mn is represented by the ratio of the number average molecular weight Mn to the weight average molecular weight Mw (that is, Mw ÷ Mn). The molecular weight distribution is an index of the breadth of the molecular weight distribution of the polymer compound. In the case of a polymer compound having a completely single molecular weight, Mw / Mn is 1, and Mw / Mn becomes a value larger than 1 as the molecular weight distribution increases. The “molecular weight distribution” is sometimes referred to as “dispersion degree”, and these “molecular weight distribution” and “dispersion degree” are synonymous in this specification. In this specification, the term “molecular weight” refers to a weight average molecular weight unless otherwise specified.

(Α-1,4-glucan)
The term “α-1,4-glucan” is a saccharide having D-glucose as a constituent unit and having at least two saccharide units linked only by α-1,4-glucoside bonds. Say. However, in this specification, α-1,4-glucan means α-1,4-glucan that is enzymatically synthesized by glucan phosphorylase (EC 2.4.1.1), and is present in amylose in plant starch. And α-1,4-glucan produced by enzymatic degradation of starch. α-1,4-glucan is a linear molecule. α-1,4-glucan is also called linear glucan. The number of sugar units contained in one molecule of α-1,4-glucan is called the degree of polymerization. In this specification, the term “degree of polymerization” refers to the weight average degree of polymerization unless otherwise specified. In the case of α-1,4-glucan, the weight average degree of polymerization is calculated by dividing the weight average molecular weight by the molecular weight 162 of glucose units.

In view of the above problems, the present inventors have added α-1,4-glucan that is enzymatically synthesized by glucan phosphorylase, so that gel foods, liquid foods, dried foods having good physical properties and texture are obtained. The present invention was completed by finding that food can be provided.
α-1,4-glucan can be produced by a method known in the art. Examples of the enzyme synthesis method include a method using glucan phosphorylase (α-glucan phosphorylase, EC 2.4.1.1; usually referred to as phosphorylase). Phosphorylase is an enzyme that catalyzes a phosphorolysis reaction.

An example of an enzyme synthesis method using phosphorylase is that phosphorylase is allowed to act, and the glucosyl group of glucose-1-phosphate (hereinafter referred to as G-1-P) as a substrate is used as a primer, for example, maltoheptaose. This is a method of transferring (hereinafter referred to as GP method). In the GP method, since G-1-P which is a raw material is expensive, it is expensive to industrially produce α-1,4-glucan, but a sugar unit is linked to an α-1,4-glucoside bond. There is a remarkable advantage that 100% linear α-1,4-glucan can be obtained by sequential binding only with the use of a simple compound. The GP method is known in the art.

Another example of an enzyme synthesis method using phosphorylase uses sucrose as a substrate, for example, maltooligosaccharide as a primer, and sucrose phosphorylase (EC 2.4.1) in the presence of inorganic phosphate. .7) and glucan phosphorylase simultaneously act to synthesize α-1,4-glucan enzymatically (hereinafter referred to as SP-GP method). The SP-GP method can be manufactured by freely controlling the molecular weight of 100% linear α-1,4-glucan as well as the GP method, and by using an inexpensive sucrose as a raw material, the production cost can be reduced. It has the advantage that it can be made lower. The SP-GP method is known in the art. An efficient production method of the SP-GP method is described in, for example, International Publication No. WO02 / 097107 pamphlet. The high molecular weight α-1,4-glucan used in the present invention can be produced according to the method described in this pamphlet.

The “primer” refers to a substance that functions as a starting material for glucan synthesis. Oligosaccharides can be used as such primers. As the primer, it is preferable to use a maltooligosaccharide such as maltotriose, maltotetraose, maltopentaose, maltohexaose, or amylose (α-1,4-glucan). As the primer, a single compound may be used, or a mixture of two or more compounds may be used.

The α-1,4-glucan synthesized enzymatically using the GP method and / or the SP-GP method has the following characteristics:
(1) Narrow molecular weight distribution (Mw / Mn is 1.1 or less);
(2) Those having an arbitrary degree of polymerization (about 60 to about 37000) can be obtained by appropriately controlling the production conditions;
(3) is completely linear and has no slight branching structure found in amylose fractionated from natural starch;
(4) Consisting of glucose residues as in natural starch, α-1,4-glucan, its degradation intermediate, and even the final degradation product are not toxic to the living body; and ( 5) If necessary, chemical modification similar to starch is possible.
The high molecular weight α-1,4-glucan synthesized enzymatically by the GP method and / or the SP-GP method is preferably used in the present invention due to the above characteristics.

These α-1,4-glucans may be modified or unmodified. Here, “modified product” refers to a product obtained by chemically modifying an object. Examples of such modifications include esterification, etherification and crosslinking.

  Esterification is, for example, reaction of α-1,4-glucan with an esterification reagent (eg, acid anhydride, organic acid, acid chloride, ketene or other esterification reagent) in various solvents or without solvent. Can be done. By such esterification, for example, acylated esters such as acetate ester and propionate ester are obtained.

  Etherification can be performed, for example, by reacting α-1,4-glucan with an etherifying agent (for example, alkyl halide, dialkyl sulfate, etc.) in the presence of an alkali. By such etherification, for example, carboxymethyl ether, hydroxypropyl ether, hydroxymethyl ether, methyl ether, ethyl ether can be obtained.

  Crosslinking can be performed, for example, by reacting α-1,4-glucan with a crosslinking agent (formalin, epichlorohydrin, glutaraldehyde, various diglycidyl ethers, various esters, etc.).

  By applying such chemical modification alone or in combination, the hydrophilicity, hydrophobicity, solubility in water, viscosity and the like of α-1,4-glucan can be changed. These chemically modified α-1,4-glucans can be selected according to the characteristics of the target food.

The average degree of polymerization of α-1,4-glucans used in the present invention is preferably 600 or more and less than 37,000. When the average degree of polymerization is 600 or less, solubility in water cannot be expected. Further, the effects of gelation, thickening and film formation cannot be obtained. On the other hand, α-1,4-glucans having an average degree of polymerization of 37,000 or more are difficult to synthesize enzymes and have little possibility of realization.
When the molecular weight distribution of α-1,4-glucans is wide, water-soluble and insoluble α-1,4-glucans are mixed, but the degree of dispersion is 1.25 or less. In the case of 4-glucans, since only α-1,4-glucans soluble in water can be added, it is easy to use for foods. If the degree of dispersion is greater than 1.25, α-1,4-glucans having different characteristics are mixed and the characteristics of α-1,4-glucans having different molecular weights are canceled, which is not preferable. . The degree of dispersion is more preferably 1.0 to 1.2, and still more preferably 1.0 to 1.15.

In the present invention, an enzyme-synthesized amylose having an arbitrary degree of polymerization / dispersion is used so as to give physical properties and texture suitable for the target food. Furthermore, when it is desirable to mix α-1,4-glucans having different degrees of polymerization, two or more α-1,4-glucans can be added.

The α-1,4-glucan in the present invention can be used in a composition for food or drink or a composition for food additives. In the present invention, α-1,4-glucan is used, but naturally, other foods, food raw materials, and food additives are added. In this case, there is no problem even if any kind is added alone or in combination.

The gel food in the present invention is characterized by containing α-1,4-glucan, and the form thereof may be any form as long as it is a food group exhibiting a gel state. For example, Western confectionery such as jelly, pudding, bavaroa, mousse, yogurt, tofu, Koya tofu, harsame, mutton, willow and the like can be mentioned. There is no problem even if they are frozen or thawed after freezing.

The thickened liquid food according to the present invention is characterized by containing α-1,4-glucan, and the form thereof is any food group that exhibits a thickened liquid state. Form may be sufficient. For example, sauces such as curry, white sauce and dessert sauce, cream, flower paste, dressing, soy sauce, sauce, soup, stew, soup, viscous beverage, mayonnaise, ketchup and other seasoning liquids, koji, kuzuyu . There is no problem even if they are frozen or thawed after freezing.

The food to be dried after coating the surface in the present invention may be in any form as long as it is a food group that has been coated and then dried. Moreover, there is no problem even if other foods or food raw materials are adhered, adhered or added after coating. There are various forms of use, for example, use as a coating agent, a brightener, a film-forming agent, a coating agent, an antioxidant coating agent, an adhesive, a binder, an adhesive, a seasoning agent, a molding agent, etc. .

The α-1,4-glucan can be easily dissolved in water at room temperature, and any known method may be used. Moreover, when adding, even if it adds to what step in the composition for food-drinks or the composition for food additives, an effect can be exhibited. Furthermore, with existing water-soluble gelling agents, thickeners, coating agents, brighteners, film-forming agents, coating agents, antioxidant coating agents, adhesives, binders, adhesives, seasonings, molding agents, etc. Can be used in an equivalent way.

  Although the dissolution concentration of α-1,4-glucan can be set widely, the gel food of claim 1 covers the surface of 1% to 15% by weight, claim 2 and claim 3. The concentration of the dissolved solution is preferably 0.1 to 10% by weight. Outside this range, it may not be possible to produce the food as desired.

When used as a coating agent, brightener, film-forming agent, coating agent, antioxidant coating agent, adhesive, binder, adhesive agent, seasoning agent, molding agent, etc., a method for coating the food surface is known. For example, there are spray coating method, handle method, dipping method, brush coating and the like.

Any method may be used for drying the food of the present invention, and examples thereof include a natural drying method, a heat drying method, a vacuum drying method, and a spray drying method.
Hereinafter, specific examples will be described.

(jelly)
Water was added to 15 parts by weight of sugar, 2 parts by weight of powdered coffee extract, and 3 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, dispersion degree 1.05) to make a total amount of 100 parts by weight and mixed well. As a control, corn starch 5 parts by weight or corn starch amylose 5 parts by weight was used instead of α-1,4-glucan. Each mixture was heated in boiling water for 15 minutes and then stored at 4 ° C. overnight, and the resulting jelly was subjected to sensory evaluation. As a result, corn starch amylose was not gelled, and corn starch was very fragile jelly, but α-1,4-glucan was rich in elasticity and had a good texture as jelly. , 4-glucan was able to prepare a novel gel food.

(Tofu-like food)
To 100 parts by weight of soy milk, 3 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, dispersion degree 1.05) was added and dissolved and mixed well. As a control, corn starch 5 parts by weight or corn starch amylose 5 parts by weight was used instead of α-1,4-glucan. Each mixed solution was heated in boiling water for 15 minutes and then stored at 4 ° C. overnight. The obtained tofu-like food was subjected to sensory evaluation. As a result, corn starch amylose was not gelled, and corn starch was a very fragile food, but α-1,4-glucan had a good texture as tofu and was not inferior to α-1,4. -A novel gel-like food could be prepared with glucan.

(Curry sauce)
30 parts by weight of fats and oils were put into a preheated open heating kettle to dissolve the fats and oils. At this time, the product temperature of the dissolved fat was about 60 ° C. Next, 30 parts by weight of wheat flour and 5 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, dispersion degree 1.05) are added to the dissolved oil and fat, and the mixture is reached over about 50 minutes while mixing. Wheat flour roux was produced by heating to a product temperature of 130 ° C.
In the flour roux obtained in the above process, curry powder 8 parts by weight, sugar 10 parts by weight, salt 9 parts by weight, sodium glutamate 2 parts by weight, meat powder 3 parts by weight, sauce powder 2 parts by weight and caramel 1 part by weight Sequentially added and cooled and mixed until the product temperature reached 60 ° C. over about 50 minutes to produce curry roux. The cooling was cooling by adding raw materials and forced cooling by a cooling pot. A solid roux was obtained by filling the resulting curry roux into a container and cooling to 20 ° C.
The obtained curry roux (solid roux) was cooked by a conventional method to obtain curry sauce. As a result of eating this curry sauce, the texture of the curry sauce was given a smoothness compared to the curry sauce to which α-1,4-glucan was not added. In terms of flavor and fragrance, there was no difference from curry sauce to which α-1,4-glucan was not added, and a novel liquid food could be produced.

(Coating agent)
2 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, degree of dispersion 1.05) is dissolved in 98 parts by weight of water, and 20 parts by weight of raw peanuts are put in this solution for 3 minutes. Drained and roasted in a hot air oven at 150 ° C. for 10 minutes. This was stored under an atmosphere of 40 ° C. for 3 weeks, and the aroma was evaluated by sensory sensation. As a control, corn starch or a non-immersed product was similarly examined. As a result, the fragrance of the α-1,4-glucan soaked product was best maintained.

(Brightener, seasoning)
The washed rice was dipped in water, and thereafter, rice confectionery having a diameter of 10 cm and a thickness of 8 mm was prepared by conventional methods such as draining, crushing, steaming, kneading, molding, drying, aging, and baking. A seasoning solution was prepared by adding 100 parts by weight of soy sauce, 15 parts by weight of sugar, 2 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, dispersion degree 1.05) as a brightener and flavoring agent. This was uniformly applied to rice crackers and dried with hot air to obtain soy sauce-flavored rice crackers. As a control, corn starch amylose or α-1,4-glucan-free seasoning liquid was used instead of α-1,4-glucan. As a result of the appearance and sensory evaluation of rice crackers, rice crackers in the α-1,4-glucan seasoning liquid are superior in gloss and soy sauce flavor, and α-1,4-glucan is glossy. It was effective as an agent and a seasoning agent.

(Adhesive)
A biscuit dough consisting of 300 parts by weight of flour, 40 parts by weight of sugar, 20 parts by weight of margarine, 6 parts by weight of butter, 2 parts by weight of sodium chloride, 1 part by weight of sodium bicarbonate, 0.5 part by weight of emulsifier and 75 parts by weight of water is formed into noodles. Then, it cut | disconnected by 10 cm unit, and was set as cut | disconnected dough. As an adhesive, 2 parts by weight of α-1,4-glucan having a molecular weight of 1000 kDa (polymerization degree 6170, dispersion degree 1.05) was dissolved in 100 parts by weight of 5% aqueous sodium phosphate solution, and the cut dough was immersed in this adhesive liquid. About 4 mm of rough black pepper grains were evenly adhered and baked. As a control, instead of α-1,4-glucan, amylose made of corn starch or α-1,4-glucan-free adhering solution was used.
As a result of rubbing the appearance and the surface of the baked biscuits by hand three times and evaluating the dropping condition of the grains, only when α-1,4-glucan is used as an adhesive, there is no problem in appearance, and even if it is rubbed by hand It was difficult to peel off and was good with almost no drop of particles, and α-1,4-glucan was effective as an adhesive.

In the present invention, a novel gel-like food, liquid food, and dried food can be produced by adding α-1,4-glucan enzymatically synthesized by glucan phosphorylase to a food as an active ingredient. is there.

Claims (6)

Gelled food containing α-1,4-glucan enzymatically synthesized by glucan phosphorylase Liquid food thickened by α-1,4-glucan Dried food film formed by α-1,4-glucan The foodstuff according to any one of claims 1 to 3, wherein the polymerization degree of the α-1,4-glucan is 600 or more and less than 37,000. The degree of polymerization of the α-1,4-glucan is 600 or more and less than 37000, and the degree of dispersion is 1.25 or less. The food according to any one of claims 1 to 3. The α-1,4-glucan contains a modified product, and the modification is a chemical modification selected from the group consisting of esterification, etherification, and cross-linking. Food listed in one