JP2731882B2 - Gelling agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an apiin (apii).
n) or a novel gelling agent containing a gelling substance containing apiin as a main component, and a gel food containing the gelling agent. More specifically, the present invention relates to parsley (Pe).
a novel gelling agent containing apiin, a kind of flavonoid compound obtained as an active ingredient, extracted and purified from T. troselinum sativ-um), and containing the component, and particularly thermoreversible under low and high temperature conditions The present invention relates to a novel gelling agent having excellent gel-forming properties and various gel foods containing the gelling agent.

[0002]

BACKGROUND OF THE INVENTION Apiin itself, which is the main component of the gelling agent of the present invention, is a kind of flavonoid compound previously known as apigenin-7-apioglucoside. Approximately 3% is contained in parsley leaves and seeds, and in the aerial part of the ape, and its properties are colorless needles, which are hardly soluble in cold water and cold alcohol, and easily soluble in hot water and hot alcohol. When hydrolyzed with a dilute mineral acid, it is decomposed into apigenin, apiose, and glucose, one molecule each, and 1%
When hydrolyzed with sulfuric acid, the knowledge that apiose is first decomposed to produce glucose apigenin as a glycoside, and that ordinary recrystallization results in a glue-like mass and difficult crystallization. Have been obtained.

[0003] As described above, although the general physicochemical properties of apiin are known to some extent, the field of application thereof has not been clarified so far as far as the present inventors know. It is not at present.

[0004]

However, the present inventors have been conducting research on the components and physical properties of the extract of parsley granules, and have found that certain components of parsley granules have a thermoreversible gel formation. Have the ability to
As a result of proceeding with the identification of the component and conducting a similar study on raw parsley, it was found that a certain extract fraction obtained from an extract of raw parsley also had a gel-forming ability.

Therefore, the present inventors have eagerly aimed at isolating and identifying a component having gel-forming ability obtained from the above-mentioned parsley granules and raw parsley extract, and elucidating the chemical structure thereof. As a result of repeated studies, specific extraction and purified fractions obtained from raw parsley leaves and seeds have gel-forming ability, and specific extraction and purified fractions extracted and purified from the parsley It has been found that the solution has a strong gel-forming ability under cooling conditions, and that the gel is thermoreversible. The present inventors focused on these points, extracted a substance having a gel-forming ability from the solution, purified, analyzed its chemical structure, and confirmed that it was unexpectedly consistent with the apiin. It turned out to be. However, there has been no report that apiin has a gelling property, and such a matter is a novel finding found by the present inventors.

[0006] Based on such knowledge, the present inventors have:
Various experiments were carried out using purified gelled substances extracted from raw parsley and purified.The gelled substances formed relatively strong gels in acidic and alkaline regions. , To form a stronger gel by coexisting metal ions such as calcium, the gel-forming ability, particularly, that a strong gel is formed in an alcohol solution, further, to produce various gel foods and the like The present invention has been found to have various properties such as being useful as a main component of the gelling agent, and has completed the present invention.

That is, an object of the present invention is to provide a novel gelling agent having thermoreversible gel forming properties. Further, the present invention provides a simple means for extracting apiin useful as a main component of the gelling agent from parsley, in high yield, a specific means for purification treatment, and apiin or apiin obtained by the means. It is an object of the present invention to provide a novel gelling agent containing a gelling substance as a main component.

Another object of the present invention is to provide a novel gelling agent capable of forming a stronger gel by coexisting a specific metal ion. Still another object of the present invention is to provide various gelled foods containing the novel gelling agent.

[0009]

The structure of the present invention for achieving the above object comprises the following technical means (1) to (6).

(1) A gelling agent containing apiin or a gelling substance containing apiin as a main component.

(2) The gelling agent according to (1), wherein the apiin or the gelling substance containing apiin is extracted from parsley.

(3) a step of subjecting apiin or a gelling substance containing apiin to heat treatment of parsley in hot water, and then subjecting the supernatant obtained by centrifugation to butanol extraction; The gelling agent according to the above (1), wherein the gelling agent is extracted from parsley and purified by the steps of evaporating to dryness, dissolving in methanol, and then purifying.

(4) The gelling agent according to the above (1), wherein apiin or a gelling substance containing apiin is a main component, and a metal ion or a salt containing a metal ion is allowed to coexist.

(5) The gelling agent according to the above (4), wherein the metal ion is calcium.

(6) A gel food comprising the apiin or a gelling substance containing apiin as a main component and the gelling agent according to the above (1).

Next, the configuration of the present invention will be described in detail. The apiin used as a main component of the gelling agent of the present invention is an apigenin-7-apioglucoside compound, and its structure is represented by the following formula (I), in which apiose, glucose, apigenin And a structural unit consisting of

[0017]

Embedded image

As the apiin or the gelling substance containing apiin used in the present invention, a substance extracted and purified from parsley is preferably used, but is not limited thereto. It may be of material origin or synthesized. And, in the case of a material obtained from a natural material such as parsley, a completely purified product, that is, a gelling substance containing apiin purified to a certain level as well as apiin itself,
Alternatively, a crudely purified product mainly containing the component in a fraction of an extract of a natural material such as parsley can be used as appropriate.

The gelling agent of the present invention contains such an apiin material as a main component. In addition, it is possible to co-exist with appropriate secondary materials required as a gelling agent. Various materials such as coloring agents, seasonings, other gel-forming substances, fragrances, sour agents, bulking agents, pH adjusters, preservatives, nutrients, and food additives can be added as needed. is there.

As the form of the gelling agent of the present invention containing such various materials, any form such as a solution, a powder, a granule, and a capsule can be used. It can be processed into a suitable form.

The apiin as a main component of the gelling agent of the present invention can be obtained as a hot water extract by heating raw parsley in hot water, and centrifuging the parsley heated with hot water. After the supernatant obtained by separation is subjected to an extraction treatment with an alcohol such as butanol to obtain an alcohol extract such as butanol, the alcohol layer such as butanol is evaporated to dryness, and then an alcohol such as methanol is added. It is produced by dissolving and then purifying to a single peak by chromatography.

As described above, as the solvent, butanol is excellent in solubility and is particularly preferably used. However, other alcohols and the like can be used as appropriate, and are not limited thereto. . And pH at the time of butanol extraction
The condition is preferably in the range of pH 3 to 9, particularly around pH 4, as the pH of the boiling liquid.

Next, the butanol extract was evaporated to dryness to form an aqueous solution.
It is adsorbed through a sep pak (Waters) or the like, and dissolved and eluted with an alcohol solution such as methanol. 60% as the alcohol solution to be dissolved
The above methanol solution is preferred. After elution with the methanol solution, purification is performed using medium pressure chromatography (MPLC) to obtain a purified gelled substance.

Purification by medium pressure chromatography (MPLC) can be repeated two or three times until a single peak is obtained, depending on the degree of purification.
The MPLC is, for example, C-18 as a column.
(Manufactured by Yamazen Corporation) and the like, and 30 to 80% methanol (gradient) are preferably used as the solvent, but the solvent is not limited thereto. And about the gelation fraction obtained by MPLC, for example, by HPLC,
Confirm the purity of the purified product.

As described above, the purification treatment by chromatography is preferably used, but the treatment means is not limited to this. For example, ion exchange, gel filtration,
Other general purification treatment means such as adsorption and ultrafiltration can be used in appropriate combination.

The apiin or the gel substance containing apiin thus purified is hardly soluble in water.
It has the property of dissolving well in an alcohol solution and forming a strong gel in an alcohol solution, and particularly has a strong gel-forming ability in an ethanol solution. Gelation depends on temperature conditions, and does not gel at high temperatures and hardly gels at room temperature, but gels under cooling conditions of 5 ° C or less, and the gelation is thermoreversible. .

The gel-forming ability is affected by metal ions, for example, NaCl, KCl, C
When a salt such as aCl _{2 is} added, the gel strength is increased as compared with the case where no salt is added. In particular, calcium ions have a large effect on the enhancement of the gel strength. The gel strength varies depending on the pH conditions, and the gel strength tends to be strong on the acidic side, but the gel strength tends to be strong even near pH 7.

The above-mentioned gelled substance having such properties is useful as a gelling agent for various gel-like compositions, and in particular, is derived from natural materials. It is useful as a gelling agent. The gelling agent of the present invention is particularly useful as a gelling agent for various alcohol-containing foods because it has a strong gel-forming ability particularly in an alcohol solution.By blending the gelling agent, for example, various alcoholic beverages, Cocktails, bonbon confections, various alcohol-containing foods mixed with alcoholic beverages, and the like can be easily processed into gelled foods.

The above-mentioned gelling substance is well dissolved under a heating condition of, for example, 75 ° C. or lower than the boiling point of ethanol and becomes a solution, but is thermoreversible which forms a gel when cooled again. By utilizing such properties, it is possible to process a normal liquid food into a product that can be enjoyed as a gelled food.

As described above, the gelling agent of the present invention is useful not only to gel various liquid foods but also to form a strong gel in the case of a solution containing high ethanol. For example, it is possible to easily produce a product that can be expected to have various effects such as improvement of preservability of the contents of packaged food for refrigeration by gelled ethanol and humidity adjustment by moisture retention.

Further, the gelling agent is used to fix the cooked processed food to a level that prevents the food from being shaken in the container when the packaged processed food is transported refrigerated at about 0 ° C. due to its gelling action. It is also useful as a fixing agent for
For example, by adding the gelling agent of the present invention dissolved in a diluted ethanol solution to cooked processed foods such as stews, curries, soups, and boiled foods, the contents of the foods can be effectively fixed, and the foods can be found during refrigerated transportation. The variation phenomenon of the contents can be prevented.

As described above, the gelling agent of the present invention is particularly useful for the production of various gelled foods, but the field of application is not limited to gelled foods, and can be used for health drinks, pharmaceuticals,
It can also be used as a gelling agent for producing other gel-like compositions such as cosmetics, medium base materials, analytical carriers, and the like. It can also be used as a gel product having a bactericidal action of the present invention, and the field of use is not particularly limited.

Hereinafter, an experimental example of the gelling substance of the present invention will be shown, and its unique effect will be verified.

1. Purification of gelled substance 5 g of parsley powder obtained by drying raw parsley with hot air and pulverizing it
Was extracted by boiling with 180 ml of hot water. Then, at 25 ° C,
The supernatant obtained by centrifugation at 7,000 rpm for 5 minutes was adjusted to pH 4, filtered, the filtrate was extracted with n-butanol, and then the butanol layer was evaporated to dryness. The sample was converted to an aqueous solution.
It was adsorbed through -18 sep pak (Waters).

Next, 70% methanol was flowed into this,
The mixture was eluted and purified using medium pressure chromatography (MPLC) to obtain a gelled fraction. The confirmation of the gelation fraction was performed by subjecting each peak of MPLC to TLC. The TLC uses silica gel as a plate, isopropanol, acetone, 1M lactic acid (4: 4: 2) as a developing solvent, and aniline, diphenylamine, acetone, 85% phosphoric acid (0.5 ml, 0.
5 g, 25 ml, 3.75 ml). The gelled material was found to correspond to a spot with an Rf value of 0.9 in TLC.

The peaks obtained by the above-mentioned MPLC were collected and subjected to MPLC again.
As a result of confirming the purity, a single peak at 210 nm was obtained. It should be noted that gelation in these operation processes was confirmed by completely evaporating the solvent, adding H ₂ O to the dried sample, and adding 5 mL of boiling water.
Immersion for 10 minutes, ice cooling for 10 minutes, and confirmation of gelation. In this way, about 20 mg of a purified product was obtained from 5 g of dried parsley.

2. Identification of gelling substance 1. As a result of performing mass spectrometry using the parsley gelling substance of the purified product obtained in the above as a sample, the molecular weight of the parsley gelling substance was 564. Next, UV absorption spectrum measurement was performed using a Hitachi spectrophotometer U-2000 in a measurement range of 200 to 400 nm, and IR absorption spectrum measurement was performed using a Hitachi infrared spectrophotometer 270-30. Then, in the measurement range of 4,000 to 400 cm ^-1 , as a result of performing each,
It was confirmed that the absorption pattern of the parsley gelling substance coincided with the absorption pattern of commercially available apiin.

Next, the NMR analysis was performed using JEOL EX-40.
As a result of using Type 0 and measuring ¹³ C and DEPT as measurement items, it was confirmed that the peak pattern in the chart of the parsley gelling substance coincided with that of commercially available apiin.
Furthermore, as a result of identification of the parsley gelling substance and the decomposed product of the parsley gelling substance by HPLC, each of them showed a pattern corresponding to that of commercially available apiin.

FIG. 1 shows the HPLC patterns of the parsley gelling substance and apiin. In addition, as shown in FIG. 2, the HPLC pattern of a sample in which both were mixed at a ratio of 1: 1 showed one peak.

Further, the decomposition product of the parsley gelling substance was identified by HPLC by comparison with a commercially available product, and it was confirmed that apigenin and glucose were contained. Apigenin and glucose were part of the chemical structure of the parsley gelling substance. It was confirmed that it constituted. From the above results, it was determined that the parsley gelling substance was consistent with apiin.

3. Gel properties of parsley gelling substance (1) Ethanol concentration and gel strength In order to adjust the concentration of the purified product of the parsley gelling substance prepared in the above to 0.2% and 0.4%, the sample was weighed into a test tube, and ethanol solutions having an ethanol concentration of 0% to 60% were added to each tube. After adding 2 ml and dissolving at 75 ° C,
The mixture was further heated for 15 minutes, and 1 ml was dispensed into the measurement container. This was left in a refrigerator at 5 ° C. for 30 minutes to form a gel. Immediately, as a result of measuring the gel strength with a rheometer,
For example, when the concentration of the purified product was 0.2%, it was found that the gel strength was highest at an ethanol concentration of 40%. Table 1 shows the results of verifying the relationship between the ethanol concentration and the gel strength when the purified product concentration was 0.2% and 0.4%.

[0042]

[Table 1]

(2) Purified product concentration and gel strength In order to adjust the concentration of the purified product to 0.2% to 1.2%,
The sample was weighed into a test tube, and 1.2 ml of a 40% ethanol solution was added. Next, a gel was formed in the same manner as in the above (1), and the gel strength of each sample was measured. As a result, the gel strength tended to increase as the concentration of the purified product increased. Then, the concentration of the purified product was 1.
It was found that up to 0%, there was an almost proportional relationship. 40%
Table 2 shows the results of verifying the relationship between the concentration of the purified product and the gel strength in the case of the ethanol solution.

[0044]

[Table 2]

(3) Influence of pH The concentration of the purified product was adjusted to 0.2% and 0.4%, and a 40% ethanol solution of pH 3 to 9 was prepared in a test tube. The purified product is weighed and each p
1.2 ml of H solution was added. Next, a gel was formed in the same manner as in the above (1), and the gel strength of each sample was measured. As a result, at the concentration of the purified product of 0.2% and 0.4%, the gel strength was highest at pH 3. The gel strength was strong on the acidic side, and the gel strength became weaker as the pH approached neutrality, but in the case of a 40% ethanol solution, it tended to become strong again at around pH 7. Table 3 shows the results obtained regarding the relationship between pH and gel strength in the case of a 40% ethanol solution.

[0046]

[Table 3]

(4) Influence of salt and sugar The purified product and various additives are weighed into a test tube such that the concentration of the purified product is 0.2% and 0.4%.
A sample was prepared by adding 1.2 ml of a 40% ethanol solution. Among the additives, salts include NaCl, KC
1, MgCl ₂ .6H ₂ O, CaCl ₂ .2H ₂ O
In addition, glucose and saccharose (sucrose) were used as sugars, respectively, and the added amounts were each １ ／ of the purified product amount. However, the final concentration of the salt was adjusted to the concentration as a metal ion.

Next, a gel was formed in the same manner as in the above (1), and the gel strength of each sample was measured. As a result, when NaCl, KCl, and CaCl ₂ were added, the gel strength was higher than when no NaCl, KCl, or CaCl ₂ was added. It turned out to be the strength of. 4
Table 4 shows the results of verification of the relationship between salt and sugar and gel strength in the case of a 0% ethanol solution.

[0049]

[Table 4]

[0050]

Next, the present invention will be specifically described based on examples.

Example 1 Production of gelling agent Raw parsley was dried with hot air, and the resulting parsley powder was boiled and extracted with hot water for 30 minutes, and then centrifuged at 25 ° C., 7, The supernatant obtained after 5 minutes at 000 rpm was filtered and the pH was adjusted to 4, followed by a butanol extraction treatment. Then, the butanol layer was evaporated to dryness to obtain an aqueous solution.
The mixture was adsorbed through an 8 sep pak (Waters), and 70% methanol was flowed through the adsorbent to obtain a 70% methanol solution. Subsequently, the purification process by chromatography was repeated using MPLC until a single peak was obtained in the same manner as in the experimental example, thereby obtaining a purified product of the parsley gelling substance.

The concentration of the purified gelled substance is 0.4%
And dissolved in 40% ethanol to adjust the pH to 4.0.
Then, a gelling agent having a gel-forming ability was produced under cooling by allowing CaCl ₂ to coexist at 0.2%. The obtained gelling agent is 0 ° C (ice-cooled), 5 ° C (refrigerator)
Had a strong gel-forming ability under the following conditions.

Example 2 Production of gel-like confectionery A purified product of the gelling substance obtained in Example 1 was blended at a concentration of 0.4%, and sugar, an acidulant, a flavor, and a natural pigment were further added, A wine-containing confectionery material based on a properly blended wine is prepared, and the confectionery material adjusted to pH 4.0 is filled in a cup-shaped container, and left under ice-cooling conditions of 0 ° C. for 30 minutes to obtain a gel-like wine confectionery. Was manufactured. Flavor,
A gel food having good texture and texture was obtained.

Example 3 Preparation of Gel Cocktail The purified gelled substance obtained in Example 1 was dissolved in a whiskey-based cocktail to a concentration of 0.4%, and lemon juice was added. The mixture adjusted to be acidic was immediately allowed to stand under ice-cooling conditions of 0 ° C. to produce a gel-immobilized cocktail. The resulting gel cocktail has a flavor,
The aroma was that of a normal cocktail, a new type of gel-like product with a unique texture.

Example 4 Production of Storage Cold Storage Food The purified gelled substance obtained in Example 1 was dissolved in a 50% ethanol solution to a concentration of 0.4%, and the pH was adjusted to 4.0. The prepared product was blended in a refrigerated bag-packed fresh noodle pack prepared by a conventional method, and after sealing, immediately refrigerated under ice-cooling conditions of 0 ° C. or lower. The resulting product had good flavor and high preservability due to the bactericidal action and moisturizing action of the gelled ethanol solution.

[0056]

The gelling agent of the present invention is mainly composed of apiin or a gelling substance containing apiin having high solubility in an alcohol solution, and is particularly useful as a gelling agent for an alcohol-containing composition. Things. In addition, the gelling substance has a thermoreversible gel forming ability, and can be widely applied as a gelling agent for foods and the like by utilizing the specific gelling property. Furthermore, the gelling agent of the present invention is mainly composed of a natural product obtained by extracting and purifying from the natural material parsley, and is a gelling agent for producing various gel foods. And has the advantage of being safe and suitable for use.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows the peak patterns of the parsley gelling substance and apiin by HPLC, wherein the upper row shows apiin,
The lower part shows a parsley gelling substance.

FIG. 2 shows an HPLC peak pattern of a sample in which a parsley gelling substance and apiin are mixed at a ratio of 1: 1.

Claims (6)

(57) [Claims] A gelling agent comprising apiin or a gelling substance containing apiin as a main component. 2. The gelling agent according to claim 1, wherein the apiin or the gelling substance containing apiin is extracted from parsley. 3. A process in which apiin or a gelling substance containing apiin is subjected to a heat treatment of parsley in hot water, and then a supernatant obtained by centrifugation is subjected to an extraction treatment with butanol. The gelling agent according to claim 1, wherein the gelling agent has been extracted from parsley and purified by the steps of evaporating to dryness, dissolving in methanol, and then purifying. 4. The gelling agent according to claim 1, wherein apiin or a gelling substance containing apiin is used as a main component, and a metal ion or a salt containing a metal ion is allowed to coexist. 5. The gelling agent according to claim 4, wherein the metal ion is calcium. 6. A gel food comprising the apiin or a gelling substance containing apiin as a main component and the gelling agent according to claim 1.