JPH11155520A - Use for sweetening, etc. or sweetening, etc., and foods and drinks or drugs with sweetening, etc. - Google Patents

Abstract

(57) [Summary] [Problems] Non-caloric or near zero calorie, non-reducing and excellent in stability, high solubility in water, low sweetness, and sweetness containing carbohydrate which does not easily cause diarrhea Provision of agents and the like. SOLUTION: Di-β-D-fructofuranose 1,2
': Sweetener or sugar content enhancer containing 2,1' dianhydride (hereinafter referred to as β-DFA) as an active ingredient, use of β-DFA for imparting sweetness to foods, drinks or medicines or increasing sugar content. And foods and drinks or medicines which are sweetened or have an increased sugar content by containing β-DFA.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sweetener containing a specific saccharide, its use for imparting sweetness, etc., which can be used particularly in the food and pharmaceutical fields, and the use of the specific saccharide to impart sweetness, etc. Related to food and drink or medicines.

[0002]

2. Description of the Related Art Hitherto, difructose dianhydride (hereinafter referred to as DFA) has been known as DFAI (α-D
-Fructofuranose β-D-Fructofuranose 1,
2 ′: 2,1 ′ dianhydride), DFAII (β-D
-Fructofuranose β-D-Fructofuranose 1,
2 ': 2,3' dianhydride), DFAIII (α-
D-fructofuranose β-D-fructofuranose 1,2 ′: 2,3 ′ dianhydride), DFAIV (β
-D-fructofuranose β-D-fructofuranose 2,6 ′: 6,2 ′ dianhydride), diheterolebrosan I (α-D-fructopyranose β-D-fructopyranose 1,2 ′: 2,1) 'Dianhydride), diheterolebrosan II (α-D-fructofuranose β-
D-fructopyranose 1,2 ′: 2,1 ′ dianhydride), diheterolebrosan III (β-D-fructofuranose β-D-fructopyranose 1,2 ′: 2)
1 'dianhydride), diheterolebrosan IV (β-
D-fructopyranose β-D-fructopyranose 1,2 ′: 2,1 ′ dianhydride) and the like are known (Nippon Nogeikagaku Kais).
hi 63 (1989), 1136-1140, C
arbohydrate Research, 136
(1985), 53-65).

Also, di-α-D-fructofuranose 1,2 ′: 2,1 ′ dianhydride (α-DFA) and di-β-D-fructofuranose 1,2 ′: 2,1 ′
Dianhydride (β-DFA) is Carbohydra
te Research, 287 (1996), 18
3-202 describe Compound Nos. 10 and 15, respectively.

[0004] Regarding the taste quality of DFAs, DFAI and DFA which can be produced enzymatically from inulin.
III is known to have a sweet taste (JP-A-63
-269962).

[0005] From the viewpoint of prevention of obesity and the like, at present, sweeteners with as low a calorie as possible are required. Erythritol, a kind of sugar alcohol, is the only carbohydrate having a non-caloric sweetness known at present. Most of this carbohydrate is absorbed from the intestinal tract and excreted in urine as it is without being metabolized. However, erythritol exhibits a high endothermic effect when dissolved, so that it feels cool in the mouth when eaten. For this reason, it was sometimes difficult to use the product for which cooling sensation was not desirable. In addition, since it is a monosaccharide of tetracarbon sugar, there is a problem that the freezing point drop is too large when used in frozen desserts. Disaccharide sugar alcohols such as maltitol used as a sweetener are not decomposed by digestive enzymes, but are converted to organic acids by intestinal bacteria and absorbed into the body.
Carbohydrates treated as kcal / g and having non-caloric sweetness higher than disaccharides are not known at present.

[0006]

As described above, sweeteners that are as low in calories as possible are now generally required. Many sugars are known and used as having a sweet taste. When adding sugar to food,
The function of the saccharide is to impart a preservative effect (for example, syrup, jam) or a so-called body feeling (for example, a body feeling of a cake), in addition to imparting a taste such as sweetness. From such a viewpoint, it may be necessary to increase the sugar content without significantly changing the taste quality of the food, for example, without significantly increasing the sweetness. Since the preservative effect is derived from the water activity of the added saccharide solution, the saccharide preferably has high solubility in water. In addition, food additives such as sweeteners are generally required to be stable to heat and acids and have low reactivity with other substances in foods. In addition, the demand for sweetened foods is a trend of recent demand, and it is required to replace a part of a normal sweetener, for example, a part of sucrose with a sweetener of lower sweetness.

The present invention meets this demand, and is non-caloric or almost zero in calories, non-reducing and low in reactivity, excellent in heat, acid and alkali stability, and high in water solubility. To provide a sweetener or the like containing a specific saccharide having a low degree of sweetness and further having no laxative action or its use for imparting sweetness and the like, and to provide a food or drink or a medicine imparted with a sweetness by the specific saccharide. Aim.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides non-caloric or almost zero calorie, non-reducing and excellent stability, high solubility in water, low sweetness,
Di-β-D-fructofuranose 1,2 ′ represented by the following chemical formula as a carbohydrate that hardly causes diarrhea:
A sweetener or a sugar content increasing agent containing 2,1 ′ dianhydride (hereinafter referred to as β-DFA) as an active ingredient;
Alternatively, the present invention relates to the use of β-DFA for imparting sweetness to foods or drinks or medicines or increasing the sugar content. The invention further provides
The present invention relates to a food or drink or a medicine which is imparted with sweetness or has an increased sugar content by containing β-DFA.

[0009]

Embedded image

Note that a plurality of inventions in the claims of the present application are substantially related to each other by the same invention.
According to the provisions of Paragraph 5 of the Article, concurrent writing in one application is permitted. Regarding the above-mentioned same invention, as an example of the same invention, “Concrete made of A” is described on page 58 of “How to Write a Patent Specification for Chemistry and Biotechnology” by Mutsuo Watanabe, published by the Japan Institute of Invention and Innovation. Examples of "reinforced admixtures" and "reinforced concrete products containing A", and "insect repellents consisting of A", "insect repellent methods using A", and "insect repellent furniture treated with A" are described. .

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As understood from its structural formula, β-DFA is non-reducing and has low reactivity with other substances in foods such as amino acids. Furthermore, it is excellent in stability against heat, acid and alkali. The sweetness and solubility in water of β-DFA are shown in Table 1 in comparison with other disaccharides. Sweetness is 5w
The measurement was performed at 20 ° C. with 10 panelists using a sucrose solution of 10 / v% or 10 w / v% as a standard solution. Measuring method was reported by Starch Sugar Technology Research Association, No. 14, p44 (1956)
According to.

[0012]

[Table 1]

From Table 1, it can be understood that β-DFA is a disaccharide having a very low degree of sweetness of about 15, despite its extremely high solubility in water. -It is understood that DFA is a very suitable substance for increasing the sugar content without significantly changing the taste quality of the food.

When the digestibility of β-DFA by various digestive enzymes was examined, it was not decomposed at all (Example 1). In addition, although absorption in the intestinal tract was tested by the rat small intestine inversion sac method, it was not absorbed (Example 2). In addition, as a result of examining the assimilation property of intestinal bacteria in the large intestine, none of the bacteria was assimilated (Example 3). In addition, when the amount of residual sugar by stool culture was examined, no decrease in β-DFA was observed (Example 4). Furthermore, when the maximum non-effective amount of β-DFA was examined, it was 0.7 g / kg body weight or more (Example 5). However, since maltitol was 0.3 g / kg body weight, the laxative effect was extremely low. It can be understood as a carbohydrate.

[0015] The sweetener or sugar content enhancer of the present invention is β
It may consist solely of DFA or may be in a form mixed with auxiliary or other active ingredients, for example other sweetening ingredients. As the auxiliary component, water, commonly used excipients / binders, and the like can be used. As an excipient, in addition to sucrose, lactose, fructose, sorbitol, maltitol, etc., which are also used as sweeteners, polysaccharides such as soluble starch, dextrin, gum mannan, pectin, alginic acid, gelatin, low molecular weight polypeptide, etc. Protein,
Salts such as calcium carbonate and calcium phosphate, citric acid,
It can be used by appropriately selecting from acids such as malic acid and fumaric acid. As the binder, guar gum, gum arabic, dextrin and the like can be appropriately selected and used as needed. In addition, flavors, essences, vitamins, seasonings and the like can be appropriately selected and used as needed. Examples of other sweet components include sugars such as glucose, fructose, and sucrose used for imparting sweetness, oligosaccharides such as isomaltooligosaccharide, sugar alcohols such as sorbitol and maltitol, aspartame, stevioside, and saccharin. . In addition, other taste components include components that impart a taste, astringency, umami, bitterness, and the like from sourness and salt.

The sweetener or sugar content enhancer of the present invention comprises
It can be used in various forms, for example, as powders, granules, syrups and the like. The most common form of the sweetener or sugar enhancer is a concentrated aqueous solution (syrup).

The content of β-DFA in the sweetener or sugar content enhancer of the present invention is not particularly limited as long as it can impart an effect of imparting sweetness to foods and drinks or medicines or increasing the sugar content. However, in general, 5 to 100 w / w% is preferable, 30 to 100 w / w% is more preferable, and 5 to 100 w / w% is more preferable.
0-100 w / w% is even more preferred. In addition, when the sweetener or the sugar-content increasing agent of the present invention contains other solid components (excipients, other sweeteners, etc.), the calorie of the sweetener or the sugar-content increasing agent as a whole is reduced. Β-D contained in the preparation to reduce the sweetness
The ratio of the amount of β-DFA to the total amount of FA and other solid components is generally 10, 30, 40, 50, 60 or 70 w / w% as the preference increases in the order given.
It is preferable that it is above.

The present sweetener or sugar content enhancer can be widely used for imparting sweetness and / or increasing the sugar content of foods, drinks or medicines ingested or administered by humans and other animals. Examples of the food and drink include various seasonings (for example, soy sauce, miso, mayonnaise, dressing, tempura, ketchup, grilled meat sauce, curry roux, stew ingredients, soup ingredients, dash ingredients, etc.), and various Japanese sweets (eg, , Rice crackers, hail, rice cakes, buns, uiro, sheep, jelly, castella, candy, etc., and various Western confectionery (eg, biscuits, crackers, cookies, pies, puddings, cream puffs, sponge cakes, donuts, chocolate, chewing gum, etc.) ), Breads, ice confectionery (eg, ice cream, sherbet, etc.), syrups (eg, fruit syrup pickles, etc.), pastes (eg, fruit paste, peanut paste, etc.), jams, marmalades, pickles (eg, , Fukujinzuke, Senmaizuke,
Rakikyo pickles, etc.), meat paste products (eg, ham, sausage, etc.), fish meat paste products (eg, kamaboko, bamboo rings, etc.), various delicacies, tsukudani, alcoholic beverages, coffee, cocoa, juice, carbonated beverages, stamina drinks,
Lactic acid drinks, lactic acid bacteria drinks, instant foods and drinks (for example,
Instant juice, instant coffee, etc.). Examples of the drug include powders, tablets,
In addition to solutions, syrups and the like, dentifrices, gargles and the like can be mentioned.

The amount of the present sweetener or sugar content-increasing agent can be arbitrarily used to the extent necessary for imparting sweetness or increasing the sugar content for the food, drink or drug of interest. Although the specific amount used varies depending on the food or drink or the drug, it is usually the individual food or drink that the sweetener or sugar content enhancer imparts sweetness or the sugar content is increased by the sweetener or sugar content enhancer. Alternatively, in medicine, about 0.5 to about 85 w /
It is preferable to select from a range that gives a content of about 5.0% to about 70% w / w.

The method of using the present sweetener or the sugar content-increasing agent in a target product for imparting sweetness and / or increasing the sugar content may be performed in the same manner as a usual sweetener. For example, at the time of production of foods or beverages or medicines, or at the time of their ingestion, they can be incorporated into the target product by using an appropriate method such as mixing, kneading, dissolving, dipping, penetrating, spraying, spraying, or pouring. .

Next, a method for producing β-DFA will be described.
70-90% w / w% fructose aqueous solution with pH 2.5-
3.5, 110-150 ° C, preferably 130-140
C. and at atmospheric pressure for 1 to 180 minutes, preferably 20 to 60 minutes to form a condensate in which DFAs account for about 50% w / w, and then adjust the pH of the treatment solution to 2 before boiling water bath The mixture is kept for 30 to 60 minutes to decompose condensates other than DFA into fructose. Next, the treatment liquid is passed through a Na-type cation exchange resin column to obtain a fraction of DFAs and a fraction of fructose. The fractions of DFAs are passed through a column for reversed phase chromatography to separate each peak, and a β-DFA fraction is obtained as one of the peak fractions. (Reference Example 1).

[0022]

Next, the present invention will be described specifically with reference to examples and reference examples. In the following Examples and Reference Examples,% indicating the concentration represents w / w%, unless otherwise specified. Example 1 (Degradability of β-DFA by various digestive enzymes) 1) α-amylase 1% β-DFA (50 mM containing 1 mM CaCl)
PH6 when maleic acid buffer or salivary amylase is used.
0 and the use of pancreatic amylase (pH 6.9), 1 unit of human salivary amylase (manufactured by Sigma) and 1 unit of porcine pancreatic amylase (manufactured by Sigma) were added to 1 ml each, and the mixture was reacted at 37 ° C. for 2 hours. Analyzed by HPLC. In each case, 99% or more of β-DFA remained. * 1 unit is the amount of enzyme that produces a reducing power equivalent to 1 μmol of glucose per minute when reacted at 37 ° C. using 1% soluble starch as a substrate.

2) Stomach acid 0.2M HC per 1 ml of 2% β-DFA aqueous solution
1 m of l-KCl buffer (pH 1.0, 1.5, 2.0)
l, and reacted at 37 ° C. for 3 hours.
The reaction was stopped by adding 0.3 ml, and the remaining rate was determined by HPL.
Analyzed in C. At any pH, 99% or more of β-DFA remained. 3) Small intestinal mucosa localization enzyme Rat small intestine acetone powder (manufactured by Sigma) was suspended (100 mg / ml) in physiological saline, homogenized, and centrifuged, and the supernatant was used as an enzyme solution. 1% β-DFA
After adding 1 unit of the enzyme solution to (25 mM maleate buffer (pH 6.0)) and reacting at 37 ° C. for 4 hours, the residual ratio was analyzed by HPLC. As a result, 99% or more of β-DFA remained. Was. * 1 unit is the amount of enzyme that degrades 1 μmol maltose per minute when reacted at 37 ° C. using 1% maltose as a substrate. H in the above 1) to 3) and Example 4 described later.
The PLC conditions were as follows. Column: YMC-Pack ODS-AQ (4.6 × 2
50 mm) (manufactured by YMC) Mobile phase: distilled water Flow rate: 0.5 ml / min Detection: RI

Example 2 (Digestion and Absorption of β-DFA in the Intestinal Tract) Digestion and absorption were examined using the inverted small intestine of rats. After breeding 4-week-old male SD rats on the commercial solid feed CE-2 (CLEA Japan) for about 2 weeks, they are fasted overnight, sacrificed by decapitation, and laparotomized. Was taken out. Immediately, the small intestine having a length of 5 cm taken out was turned over, and 2 ml of PBS (phosphate buffered saline) was removed.
Was ligated, and the both ends were ligated to form a reversal small intestine. 14m
Invert the small intestine into a test tube (18 mm inner diameter) containing 10 ml of a PBS solution of β-DFA, maltose or sucrose prepared at M concentration (adjust the NaCl concentration of PBS so as to be isotonic with PBS). The solution in the test tube was allowed to stand still for 20 minutes while passing a mixed gas of 95 v / v% oxygen-5 v / v% carbon dioxide through a Teflon thin tube. The PBS and sugar solutions in PBS were all kept at 37 ° C. for operation.

The test tube fluid (mucosal side) and the inverted small intestinal lumen fluid (serosa side) were collected, respectively, and heated in a boiling water bath for 10 minutes to inactivate the enzyme detached from the intestinal tissue. Glycerin is quantitatively added to both solutions to make a constant volume, desalted with amphoteric ion exchange resin MB-3 (organo), filtered through a membrane filter, and saccharide composition is determined by high performance liquid chromatography using glycerin as an internal standard. did. In the solution on the mucosal side, maltose was reduced by 38% and sucrose was reduced by 21%, whereas β-DFA was reduced by only 2%, which was considered to be within the range of operation loss. On the other hand, in the solution on the serosal side, maltose and sucrose
Monosaccharides, which are thought to be due to absorption, increased, while β-
No monosaccharide was detected by DFA. From the above, it was suggested that maltose and sucrose could be digested and absorbed in the small intestine, while β-DFA might not be digested and absorbed.

Example 3 (Assimilation of β-DFA by intestinal bacteria) Fresh bacteria cultured on an agar medium were isolated from peptone containing 0.5% of each sugar solution.
Yeast-field solution (PYF) medium was inoculated with each strain at 10 CFU / tube, and cultured at 37 ° C. for 48 hours under anaerobic conditions. Judged. As is clear from Table 2 showing the results, β
-DFA was not assimilated by any of the strains examined.

[0027]

[Table 2]

Example 4 (Residual rate of β-DFA in stool culture) The feces of two healthy adult males and two females were collected once each,
Mix well. 3 g of this was diluted with 27 ml of degassed phosphate buffer (pH 6.8) to prepare a fecal solution. This was dispensed into two tubes of 6 ml each, and 6% β
-0.2 ml of DFA or 6% maltitol was added. Immediately thereafter and after anaerobic cultivation for 6 hours, 1.2 ml thereof was collected and treated in a boiling water bath for 5 minutes. This was centrifuged (5,000 g × 10 minutes), and the supernatant 1
The mixture was passed through a pretreatment solid-phase extraction column Sepp C18 (manufactured by Waters), and further extruded with 2.5 ml of water. The treated solution was further desalted with both ion-exchange resins MB-3 (manufactured by Organo Corporation), and then made up to 5 ml, filtered through a membrane filter, and analyzed by HPLC. As a result of comparing the amount of sugar before and after the culture, it was found that maltitol had 42 w / w%.
Was 97% w / w with β-DFA.
% Residual rate.

Example 5 (Maximum no-effect level of β-DFA in healthy volunteers) Three healthy adult male volunteers were treated with β
Aqueous solutions containing -DFA were administered as drinking water at 0.3, 0.5 and 0.7 g / kg body weight, respectively, as β-DFA. No diarrhea occurred in any group.
Therefore, the maximum no-effect level is considered to be 0.7 g / kg body weight or more.

Example 6 Sweetener Preparation Example 1 A low sweetener was prepared by mixing 50 g of β-DFA syrup (25% moisture) and 50 g of maltitol syrup (25% moisture). This sweetener had a degree of sweetness of 25, but was non-reducing similarly to sucrose, and had water activity and osmotic pressure similar to sucrose.

Example 7 Preparation of Sweetener Example 2 A sweetener was prepared by mixing 50 g of β-DFA syrup (25% moisture) and 0.13 g of α-glycosylstevia sweetener. This sweetener had a sweetness of 50, but was non-reducing similarly to sucrose, and had water activity and osmotic pressure similar to sucrose.

[0032]Example 8 Addition example 1 to food and drink (to jam
Utilization) 60 g of cut strawberry, sweetener 1 prepared in Example 6
40 g, 0.7 g of pectin and 0.4 g of citric acid
The mixture was heated and boiled down to a sugar concentration of 65% to obtain a product.
Unprecedented di
It was jam. Example 9 Addition Example 2 to Foods and Drinks (Utilization for Pastry) 100 g of raw candy, 50 g of sucrose, sweetness prepared in Example 6
Mix 50g of agent, 0.6g of salt and 50g of water and heat
And kneaded to a moisture of 30% to obtain a product. Less sweetness
A light-colored, glossy paste that takes advantage of the flavor of the ingredients
Met.

Example 10 Examples of Addition to Chemicals (Usage to Dentifrice) 50 g of calcium phosphate dihydrate, 10 g of glycerin,
A product was prepared by mixing 13 g of the sweetener prepared in Example 7, 2.5 g of sodium lauryl sulfate, 1.5 g of spearmint oil, 1.0 g of tragacanth gum and 22 g of water.
The product had no irritating sweetness and had a soft mint flavor.

Reference Example 1 Production of β-DFA by Condensation of Fructose 150 g of fructose was dissolved in 40 g of water, and 0.6 ml of a 10% citric acid solution was added. While stirring this with a mixer, heat it with an electric heater, and evaporate
The reaction was performed at 140 ° C. for 20 minutes. The reaction product was diluted with water to a sugar concentration of about 50%, adjusted to pH 2 with hydrochloric acid, and then treated in a boiling water bath for 30 minutes to decompose condensates other than DFA (difructose dianhydride). This is N
a-type strongly acidic cation exchange resin (UBK manufactured by Mitsubishi Chemical Corporation)
-530, resin amount 11.8 L).
35 g of an A-containing (5%) fraction was obtained as a solid content. Then, this solution was concentrated to a concentration of 50%, and a column for reverse phase chromatography (YMC manufactured by YMC)
-Pack ODS-AQ, 10 x 100 cm x 2)
, And the solution was passed through at a flow rate of 250 ml / min using demineralized water as a mobile phase, fractionated and fractionated. 2 g of syrup) were obtained. The specific rotation and C-NMR chemical shift of the obtained β-DFA were as follows. Specific rotation [α]: -80 C-NMR chemical shift: 100.7 (C-2),
(81.6, 79.4, 74.9) (C-3, C-4,
C-5), (63.7, 62.6) (C-1, C-6)

[0035]

The sweetener or sugar content enhancer of the present invention is non-caloric or almost zero in calories, is non-reducing, has excellent stability, has high solubility in water, has low sweetness, Β, a carbohydrate with no laxative effect
-Since DFA is used as an active ingredient, it is useful as a non-caloric sweetener, as a sugar content increasing agent, and as a stable sweetener that hardly causes diarrhea. Such a sweetener or a sugar content-increasing agent can be used for imparting sweetness to a food or drink or a drug or for increasing the sugar content.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Tetsuya Yatake 2-20-2 Hinode, Funabashi-shi, Chiba Pref.

Claims (4)

[Claims] 1. Di-β-D-fructofuranose 1,2
': A sweetener or a sugar content-increasing agent containing 2,1' dianhydride (hereinafter referred to as β-DFA in the claims) as an active ingredient. 2. Use of β-DFA for imparting sweetness to foods or drinks or medicines or increasing the sugar content. 3. A food or drink having a sweet taste or an increased sugar content by containing β-DFA. 4. A drug imparted with sweetness or increased sugar content by containing β-DFA.