JP4488750B2 - L-arabinose-containing syrup - Google Patents

Description

  The present invention relates to an L-arabinose content syrup and compositions such as foods, cosmetics and pharmaceuticals containing the same.

  L-arabinose is a non-caloric carbohydrate that has a taste similar to sucrose and exhibits poor absorbability. In nature, it exists as a constituent sugar of polysaccharides such as arabinan and arabinoxylan in hemicellulose of higher plants. Moreover, it is contained in fermented foods such as miso and liquor, instant coffee, etc. although it is a trace amount in the state of monosaccharides.

  L-arabinose has an activity of inhibiting a hydrolase of a disaccharide such as sucrose (α-glucosidase inhibitory activity), and thus has an effect of suppressing an increase in blood glucose level when sucrose is ingested. (For example, refer nonpatent literature 1), and the utilization in the form of powder or syrup is anticipated as a raw material for functional foods, such as food for specified health.

As a method for producing such L-arabinose, a method obtained from a natural material is known. For example, acid hydrolysis or enzymatic decomposition of hemicellulose obtained by alkaline extraction from a plant containing L-arabinose as a constituent sugar of hemicellulose (see, for example, Patent Document 1), and L-arabinose constitutes hemicellulose. A crude sugar solution obtained by direct acid hydrolysis (for example, see Patent Document 2) or enzymatic degradation (for example, see Patent Documents 3 and 4) of a plant body contained as a sugar is desalted according to a conventional method. This is a method of processing such as purification. The form of L-arabinose thus obtained is an aqueous solution, powder, crystal, and also a mother liquor and a semi-crystallized slurry during crystallization, and the proportion of L-arabinose in the total carbohydrate is Usually, it is about 55 to 90%. Further, pure (95% or more) L-arabinose which has been subjected to a purification treatment is also known.
J. et al. Appl. Glucosci. , Vol. 46, no. 2, p. 159-165 (1999) Japanese Patent No. 3031534 JP-A-11-313700 JP 2001-286294 A JP 2002-95491 A

  When L-arabinose is used in the food field, the pharmaceutical field, or the like, it is desired to use a syrup (solution) for convenience of handling. However, storage in syrup is easy to spoil, and even if you try to increase the concentration to suppress it, L-arabinose has a relatively low solubility in water, so it exceeds the solubility (Brix sugar content of about 35-40%) The solution was extremely unstable at room temperature and easily precipitated L-arabinose hydrous crystals, resulting in the problem of losing the homogeneous fluidity that is a feature of syrup. In addition, if the storage temperature is set low in order to suppress spoilage, the syrup is likely to freeze, and in any case, there is a problem that serious problems are caused in tank storage, pump transportation, and the like.

  Further, the L-arabinose-containing product obtained by the above-mentioned method has a low Brix sugar content in a solution that does not crystallize in a room temperature environment, although the proportion of L-arabinose in the total carbohydrate is as low as 55 to 90%. There was also a problem that it was as low as 50% or less and still easily rot.

  On the other hand, α, α-trehalose, like L-arabinose, has a relatively low solubility in water, and has a low Brix sugar level in a solution that does not crystallize in a room temperature environment and is said to be easily spoiled. One. In the case of this saccharide, there is known a syrup that is hardly crystalline or amorphous in a range of compositions to which other saccharides are added (see, for example, JP 2000-325033 A). Due to the difference in properties between the two, it has been difficult to apply the composition range and types of carbohydrates to L-arabinose as they are.

  An object of the present invention is to provide a syrup containing L-arabinose which does not crystallize or decay during long-term storage at room temperature and does not freeze under storage at 0 ° C.

  As a result of intensive investigations to solve such problems, the present inventors have observed a phenomenon in which the Brix sugar content of a solution that does not cause crystallization increases slightly when the purity of L-arabinose is lowered. -The present inventors have found the fact that it is effective to adjust the ratio of arabinose and other carbohydrates and the Brix sugar content to a specific range, and have reached the present invention.

That is, the present invention is (1) a syrup containing L-arabinose, D-glucose, D-galactose and D-fructose , wherein the proportion of L-arabinose in the total carbohydrate is 16-49%, And the gist of the L-arabinose-containing syrup characterized by having a Brix sugar content of 55 to 75% .

  The gist of the present invention is the L-arabinose-containing syrup as described in (1), which does not freeze even when left in an environment of 0 ° C. for 1 week or longer.

  The gist of the present invention is the L-arabinose-containing syrup according to (1), wherein the L-arabinose hydrated crystals do not crystallize even when left in a 10 ° C. environment for 1 week or longer. .

  The gist of the present invention is the L-arabinose-containing syrup according to (1), which does not rot even if left in a 20 ° C. environment for 1 week or longer.

  Furthermore, the gist of the present invention is a composition containing any of the aforementioned L-arabinose-containing syrups, and preferably the composition is a food, cosmetic or pharmaceutical product.

  According to the present invention, crystallization and decay of L-arabinose hydrated crystals can be suppressed even when stored for a long time in a room temperature environment, and further freezing at 0 ° C. storage can be suppressed. Pumping and tank truck transportation are easy. Therefore, since the present invention can be advantageously used as a sweetener, a taste improver, a quality improver and the like for the production of various compositions such as foods, cosmetics, and pharmaceuticals, the present invention is applicable to related industries such as foods, cosmetics, and pharmaceuticals. The impact is significant.

  Hereinafter, the present invention will be described in detail.

  The production method of L-arabinose used in the present invention is not limited. It may be a commercially available pure L-arabinose having a purity of 95% or more, or may be an L-arabinose-containing product obtained from a plant as described above. Such an L-arabinose-containing material usually has a ratio of L-arabinose in the total carbohydrate of about 55 to 90%, and is effectively used in the present invention.

  The production method of D-glucose used in the present invention is not limited. Even with commercially available pure D-glucose, corn starch and potato starch are saccharified and hydrolyzed, followed by desalting and purification according to conventional methods, aqueous solutions, powders and crystals of D-glucose. Is also useful.

As the saccharide other than D-glucose used in the present invention, D -galactose and D-fructose which are saccharides that are readily soluble in water and can suppress crystallization of L-arabinose are necessary. is there. D-galactose and D-fructose are preferable in that the composition is adjusted and the properties of the aqueous solution (specific gravity, Brix sugar content, etc.) are similar to those of L-arabinose. The production method of D-galactose and D-fructose need not be specified in particular. In addition to using commercially available pure carbohydrates, any of aqueous solutions, powders, and crystals containing the carbohydrates obtained from plant raw materials can be used. Can be used.

The L-arabinose-containing syrup of the present invention is a syrup containing the above-mentioned L-arabinose, D-glucose, D-galactose and D-fructose , wherein the proportion of L-arabinose in the total carbohydrates contained in the syrup is It is necessary to be within a specific range and the brix sugar content of the syrup to be within a specific range.

  In the present invention, the amount of L-arabinose and other carbohydrates contained in the L-arabinose-containing syrup is diluted with the syrup as necessary, and then a high-performance liquid chromatograph system (column; Biorad ion exchange column, Minex HPX-87H, φ × 300 mm, column temperature; 60 ° C., mobile phase; 0.005 N sulfuric acid, flow rate; 0.6 mL / min, detection; differential refractive index).

  In the present invention, the proportion of L-arabinose in the total sugar contained in the syrup needs to be 16 to 49% by mass, preferably 30 to 45%, and more preferably 35 to 45%. %.

  Further, in the present invention, the Brix sugar content of syrup means a value at 20 ° C. obtained by a Brix sugar content meter (for example, manufactured by Atago, Digital Sugar Content Palette Series).

  In the present invention, the Brix sugar content of the syrup needs to be 55 to 75%, preferably 60 to 65%, and more preferably 60 to 63%.

  The L-arabinose-containing syrup of the present invention may contain proteins, lipids, sweeteners, bulking agents, antioxidants and the like in addition to L-arabinose and other carbohydrates.

  The above-mentioned L-arabinose-containing syrup having a specific L-arabinose ratio and having a specific Brix sugar content does not freeze even when left for 1 week or longer in an environment of 0 ° C., preferably −20 It will not freeze even if it is left in an environment of ° C for a week or more.

  In addition, the L-arabinose-containing syrup having the above-mentioned specific L-arabinose ratio and having a specific Brix sugar degree can crystallize L-arabinose hydrous crystals even when left in a 10 ° C. environment for one week or longer. Preferably, it does not crystallize L-arabinose hydrated crystals even if left in a 1 ° C. environment for 1 week or longer, and more preferably left in a −20 ° C. environment for 1 week or longer. However, L-arabinose hydrated crystals are not crystallized.

  Furthermore, the L-arabinose-containing syrup having the above-mentioned specific L-arabinose ratio and having a specific Brix sugar content does not rot even if left in a 20 ° C. environment for one week or longer.

  Next, the manufacturing method of the L-arabinose containing syrup of this invention is demonstrated.

  In order to produce the L-arabinose-containing syrup of the present invention, L-arabinose and other carbohydrates may be dissolved in water so as to exhibit a predetermined ratio of L-arabinose and a predetermined brix sugar content. The ratio of L-arabinose can be adjusted by adding L-arabinose or other saccharides, and the Brix sugar content can be adjusted by diluting with water or concentrating by reduced pressure.

  As specific examples of the production method, (1) a predetermined amount of L-arabinose is added to water and dissolved by heating, and then a predetermined amount of D-glucose and / or other carbohydrate is added and dissolved therein. 2) A predetermined amount of a high concentration solution prepared by heating and dissolving L-arabinose and a high concentration solution of D-glucose and / or other sugar prepared separately are mixed. (3) A predetermined amount of L-arabinose And other methods such as dissolving D-glucose and other carbohydrates and concentrating under reduced pressure until a predetermined Brix sugar content is obtained. (4) Various methods from plants containing L-arabinose as a constituent sugar of hemicellulose A method of adding D-glucose and / or other saccharides to the L-arabinose-containing composition obtained in step 1 and adjusting the composition to a predetermined composition range and Brix sugar content.

  In the method of (4), an L-arabinose-containing composition is obtained by using an enzyme having an activity of acting on a natural product containing arabinan, arabinoxylan or arabinogalactan to release L-arabinose, arabinan, arabinoxylan or A method of acting directly on a natural product may be mentioned after separating and extracting arabinan, arabinoxylan or arabinogalactan from a natural product containing arabinogalactan, or without separate extraction.

  Natural products containing arabinan, arabinoxylan or arabinogalactan include apples, beets, soybeans, corn, rice, wheat, etc., as well as orange fiber, tangerine juice candy, apple fiber, apple juice candy, beets By-products such as fiber, beet pulp, peanut ginger, rice bran, corn koji, soybean koji, corn fiber and peanut oil cake.

  Examples of the enzyme having an activity of acting on a natural product containing arabinan, arabinoxylan or arabinogalactan to release L-arabinose include arabinan degrading enzymes such as arabinase (arabanase) and arabinofuranosidase (Details) (See JP 2001-286294 A).

  Another composition of the present invention contains the above-described L-arabinose-containing syrup, and the L-arabinose-containing syrup is used as a sweetener, a taste improver, a quality improver, a stabilizer, an excipient, and the like. It can be advantageously used in various compositions such as foods and drinks, feeds, feeds, cosmetics, and pharmaceuticals.

  The addition amount of the L-arabinose-containing syrup contained in these compositions may be appropriately determined depending on the application, and may be generally 0.01 to 100%.

  Hereinafter, the present invention will be described specifically by way of examples.

  In the examples, L-arabinose and other saccharides were quantified by the above-described high performance liquid chromatograph system. Moreover, the Brix sugar content was measured by the above-mentioned Brix sugar content meter.

  The presence or absence of rot of the L-arabinose-containing syrup was evaluated by the number of viable bacteria in the sample. That is, 0.1 g of each sample was collected and diluted in 2 mL of physiological saline, 1 mL of which was mixed with SCD agar medium (manufactured by Nissui Pharmaceutical), cultured in a 37 ° C. constant temperature bath for 24 hours, and detected as a general bacterium Count colonies to obtain the number of general bacteria. The remaining 1 mL is mixed with Sabouraud agar medium (manufactured by Nissui Pharmaceutical) and cultured in a thermostatic bath at 25 ° C. for 5 to 7 days to count the detected fungal colonies. did.

Reference Example 1 [Measurement of solubility of L-arabinose in water]
First, the solubility of L-arabinose in water at room temperature was examined. In a glass beaker, 10 g of water and 20 g of L-arabinose (manufactured by Wako Pure Chemicals, special grade reagent) are put, and the temperature is kept at 10, 15, 20, 25, 30, 35 and 40 ° C. for 24 hours while stirring and mixing them. Subsequently, the mixture was filtered with a filter paper (No. 5C manufactured by Advantech) and diluted to a Brix sugar content of about 1%, and then L-arabinose and other carbohydrates in the filtrate were quantified. The specific gravity at 20 ° C. was measured with a balance. From these results, the L-arabinose solubility in 100 g of water at each temperature was determined. The results are shown in Table 1.

  From the results of Table 1, it can be seen that L-arabinose has a relatively low solubility in water and is a saccharide that is easily crystallized at room temperature.

Reference Example 2 [Preparation of L-arabinose-containing aqueous solution]
22.5 L of water was added to 4.5 kg of beet pulp (manufactured by Cargill Co., Ltd., 11% moisture), and heat treatment was performed at 100 ° C. for 3 hours. After the treatment, 22.5 L of water was further added and the mixture was allowed to cool to 45 ° C., and then Sumiteam PX (Nippon Kagaku pectinase, liquid, pectinase activity 5000 units / g, arabanase activity 80 units / g as an L-arabinose releasing enzyme. 67.5 g) was added to release L-arabinose. After the reaction, the slurry was squeezed and filtered using a filter cloth, and the resulting reaction solution was centrifuged to obtain 43 L of a crude sugar solution free from insolubles. This was concentrated to 10 L with a rotary evaporator, passed through an ultrafiltration membrane (SIP3013 manufactured by Asahi Kasei, molecular weight cut off 6000), and then a cation exchange column (PK216, H + type, φ135 × 280 mm, 4 L manufactured by Mitsubishi Chemical), anion Exchange column (Mitsubishi Chemical WA30, OH− type, φ135 × 490 mm, 7 L), mixed bed column (Mitsubishi Chemical PK216, H + type, 0.5 L, PA412, OH− type, 1 L, φ135 × 105 mm, total 1. 5L) was successively passed through for desalting. After adding 1Kg of powdered activated carbon (Carborafine manufactured by Takeda Pharmaceutical Co., Ltd.) to 40L of the obtained refined sugar solution and treating for 30 minutes while keeping the temperature at 60 ° C, the activated carbon is removed by diatomaceous earth filtration and further up to 2L with a rotary evaporator. Concentration and sterilization filtration were performed with a filter having a pore size of 0.45 μm to obtain 3.1 kg (brix sugar content 56.3%) of an aqueous solution containing 1.1 kg of L-arabinose.

  The resulting L-arabinose-containing aqueous solution has a Brix sugar content of 56.3%, and the proportion of L-arabinose in the total carbohydrate is 63.8% (others, D-glucose; 20.3%, D-galactose; 8.0%, D-fructose; 7.9%).

Test 1 [Storage test of aqueous solution containing L-arabinose (Comparative Example 1)]
20 g of the L-arabinose-containing aqueous solution obtained in Reference Example 2 was collected in a sample bottle and stored in a constant temperature environment of 0 ° C., 10 ° C., and 20 ° C., and stored on the first day, the third day, and the first week. Observation was performed to visually evaluate the presence or absence of freezing and the presence or absence of crystallization, and the presence or absence of decay was evaluated by the above-described method. The obtained results are shown in Table 2.

  As is clear from the results in Table 2, the samples were frozen by the third day when stored at 0 ° C. or lower. Further, in an environment of 20 ° C. or lower, crystallization was observed in all samples by the first week. Furthermore, rot (detection of fungal colonies) was observed in all samples by the first week under an environment of 10 ° C to 20 ° C. From the above results, it was found that long-term storage was difficult with the composition of saccharides such as the L-arabinose aqueous solution obtained in Reference Example 2 and the Brix sugar content.

Test 2 [Preparation of L-arabinose-containing syrup and storage test 2 (Example 1, Comparative Example 2)]
L-arabinose-containing aqueous solution obtained in Reference Example 2 (ratio of L-arabinose in the total sugars; 63.8%, (others, D-glucose; 20.3%, D-galactose; 8.0% , D-fructose; 7.9%), Brix sugar content; 56.3%) was concentrated with a rotary evaporator to adjust the Brix sugar content to 60% and 75% (Comparative Example 2). Moreover, as shown in Table 3, D-glucose, D-galactose, and D-fructose were added and dissolved as other carbohydrates to adjust the composition (Example 1). These were left to stand in a constant temperature environment of 0, 10, and 20 ° C. respectively for one week. Like Comparative Example 1, the presence or absence of freezing in an environment of 0 ° C., the presence or absence of crystallization in an environment of 20 ° C. or less, and 20 ° C. The presence or absence of corruption in the environment was evaluated. The results are shown in Table 3.

  As is clear from the results in Table 3, the L-arabinose-containing aqueous solution obtained in Reference Example 2 with an increased Brix sugar content (Comparative Example 2) does not cause the L-arabinose-containing syrup to freeze or spoil, Crystallization occurs easily in a room temperature environment, but in the case of adjusting the proportion of L-arabinose in the total carbohydrate by adding other carbohydrates (Example 1), crystallization of L-arabinose-containing syrup It became possible to suppress corruption and freezing.

Test 3 [Storage Test 3 of L-arabinose-containing syrup (Examples 2 to 5, Comparative Examples 3 and 4)]
L-arabinose-containing aqueous solution obtained in Reference Example 2 (ratio of L-arabinose in the total sugars; 63.8%, (others, D-glucose; 20.3%, D-galactose; 8.0% , D-fructose; 7.9%), Brix sugar content: 56.3%), D-glucose, D-galactose and D-fructose are added and dissolved as other carbohydrates, and L occupies the total sugar -Ratio of arabinose 50% (Comparative Example 3), 45% (Example 2), 41.2% (Example 3), 30% (Example 4), 20% (Example 5), 15% ( The composition shown in Table 4 was prepared by adjusting to Comparative Example 4) and concentrating with a rotary evaporator. This was left to stand in a constant temperature environment of 0, 10, and 20 ° C. for one week respectively, and as in Comparative Example 1, the presence or absence of freezing in an environment of 0 ° C., the presence or absence of crystallization in an environment of 20 ° C. or less, and 20 ° C. The presence or absence of corruption in the environment was evaluated. The results are shown in Table 4.

  As is apparent from the results in Table 4, the crystallization of L-arabinose-containing syrup was obtained in the case where the ratio of L-arabinose in the total carbohydrate was adjusted by adding other carbohydrates (Examples 2 to 5). It became possible to suppress corruption and freezing. When the ratio of L-arabinose in the total sugar is outside a certain range (Comparative Examples 3 and 4), the L-arabinose-containing syrup does not freeze or decay, but crystallization easily occurs at room temperature. It was.

Test 4 [Preservation test 4 of L-arabinose-containing syrup (Examples 6 to 8, Comparative Examples 5 to 7)]
L-arabinose-containing aqueous solution obtained in Reference Example 2 (ratio of L-arabinose in the total sugars; 63.8%, (others, D-glucose; 20.3%, D-galactose; 8.0% , D-fructose; 7.9%), Brix sugar content: 56.3%), D-glucose, D-galactose and D-fructose are added and dissolved as other carbohydrates, and L occupies the total sugar -The proportion of arabinose was adjusted to 41.2%. Water was added to this or concentrated with a rotary evaporator, and Brix sugar content was 50% (Comparative Example 5), 54% (Comparative Example 6), 60% (Example 6), 63% (Example 7), 75 % (Example 8) and 76.5% (Comparative Example 7), which were left in a constant temperature environment of 0, 10, and 20 ° C. for one week, respectively. The presence or absence of freezing at the bottom, the presence or absence of crystallization in an environment of 20 ° C. or lower, and the presence or absence of decay in an environment at 20 ° C. were evaluated. The results are shown in Table 5.

As is clear from the results in Table 5, when the Brix sugar content exceeds a certain range (Comparative Examples 5 to 7), crystallization and decay of L-arabinose-containing syrup occurs at room temperature and freezes at 0 ° C storage. It is apparent that it is not suitable as the L-arabinose-containing syrup of the present invention.

Claims (6)

A syrup containing L-arabinose, D-glucose, D-galactose and D-fructose , wherein the proportion of L-arabinose in the total carbohydrate is 16-49% and the brix sugar content is 55-75% An L-arabinose-containing syrup characterized by The L-arabinose-containing syrup according to claim 1, wherein the syrup does not freeze even when left in an environment of 0 ° C for 1 week or longer . The L-arabinose-containing syrup according to claim 1 , wherein the L-arabinose hydrated crystals do not crystallize even when left in a 10 ° C environment for 1 week or longer . The L-arabinose-containing syrup according to claim 1, wherein the syrup does not rot even if left in a 20 ° C environment for 1 week or longer . The composition containing the L-arabinose containing syrup of any one of Claims 1-4. The composition according to claim 5, wherein the composition is a food, cosmetic or pharmaceutical product.