JPH03160963A - Noncrystalline honey and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title honey easy to handle with no crystal separated during storage by acting an enzyme on a honey solution to decrease the glucose content in the honey. CONSTITUTION:A solution prepared by diluting honey by a factor of normally 2-1000 (esp. 2-100) with water or an appropriate solvent is incorporated with an enzyme or subjected to an immobilized enzyme to initiate a reaction. For said enzyme, in the case of glucose oxidase, one classified as Aspergillus sp. is normally used; in the case of catalase, one stemmed from animal or plant or microorganisms is used. The enzymatic reaction should be made at 30-50 deg.C in the case of glucose oxidase or catalase, or 60-80 deg.C in the case of glucose isomerase. After reaction, the reaction fluid is put to ion exchange chromatography to remove both the proteins and enzymes contained in the honey. Thereby, the glucose content in the honey can be reduced and the objective noncrystalline honey with any Brix degree and to be used as a sour sweetener can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to amorphous honey and a method for producing the same.

[Conventional technology] Honey is mainly made by bees decomposing sugar (sucrose) obtained from various plants into glucose and fructose using the secreted enzyme invertase, and there are other components as well. contains small amounts of minerals, organic acids, oligosaccharides, proteins, etc. In recent years, the consumption of honey has increased rapidly as people's health consciousness has increased, and its use as a link agent has increased in particular.

In addition, honey is mainly composed of sugar, and when used in drinks, acidulants are added separately as well as sweeteners such as sugar, fructose, glucose, latinose, and maltose coupling sugar. Honey has both sourness and sweetness, and there is no processed honey product that can be used alone. Citric acid is a typical organic acid that is widely used as an acidulant due to its price and taste, and malic acid and tartaric acid are also used to some extent. However, although glucono delta lactone and D-curconic acid have the excellent characteristic of having a mellow sour taste, they are only used as leavening agents and in tofu production in the food field, and are expensive and expensive compared to other organic acids. Not used.

[Problems to be solved by the invention] As mentioned above, the consumption of honey is increasing, but crystals are formed over time during the honey manufacturing process, processing process, or during the storage of so-called table honey used at home by general consumers. There is a problem in that when crystals are precipitated, they are difficult to handle unless the crystals are dissolved by heat.

Crystal precipitation is caused by glucose, which is the main ingredient in honey. The glucose content of honey varies depending on the type of plant that bees collect.For example, honey obtained from acacia is difficult to crystallize, but crystal precipitation cannot be avoided over a long period of time, and honey derived from other plants does not crystallize easily. In this case, crystal precipitation is always observed. The occurrence of crystallization has traditionally been regarded as one indicator of pure honey, but this is because counterfeit (impure) honey mixed with isomerized sugar, starch syrup, sugar, etc. is on the market, and honey containing The low amount is caused by crystallization or non-occurrence.

Furthermore, there is a deep-rooted belief that honey is genuine (pure) when it crystallizes, and to date, no improvements or ideas have been made to address the problems caused by crystallization, and urgent improvements are awaited.

Furthermore, although honey is a raw food, it does not easily spoil. However, honey is a supersaturated solution of sugar, and the excess sugar tends to crystallize into a saturated solution. Partially crystallized honey has a high moisture content in the non-crystalline portion, making it easier to ferment. If the water content exceeds 19%, it will ferment sooner or later, producing foam and turning into acetic acid through alcohol.

Such changes occur very slowly after crystallization begins, resulting in a lack of stability over time.

The present invention has been made in view of the above problems, and includes:
The purpose is to provide amorphous honey that does not precipitate crystals during storage and is easy to handle, and a method for producing the same.

[Means and effects for solving the problem] The inventor of the present application is
We investigated the problem of honey crystallization and search for ingredients that have both sour and sweet tastes. By decomposing honey with enzymes, it is possible to obtain honey that does not produce any crystals, and if the main components are fructose, glucono delta lactone, and D-gluconic acid, it has both sour and sweet taste. Based on the idea that it would be possible to prepare a sour sweetener, the present invention was completed after repeated research.

Then, amorphous honey was obtained by lowering the amount of glucose in the honey by applying an enzyme to the honey solution. When glucose oxidase is used as an enzyme alone or in combination with catalase, glucose is converted to glucono delta lactone and D-gluconic acid, resulting in amorphous honey that can be used as a sour sweetener with acidity. .

Furthermore, when glucose isomerase is used as an enzyme, glucose is converted to fructose, resulting in amorphous honey that has almost the same sweetness as crystalline honey.

When we analyzed the moisture, fructose, glucose, and acidity in honey, we found the results shown in the following table (the data is the average value of the analysis results for each of 20 honeys from different production areas).

As a result, honey contains 31-36% glucose and 40-46% fructose, and like acacia, it has a low glucose content (glucose)/(
Those with a lower water content ratio than others tended to have delayed crystal precipitation.

The quality standards for honey are as follows.

Moisture: 23% or less, direct reducing sugar: 65% or more,
Glucose: less than 50% of direct reducing sugar, sucrose...
5% or less, ash content...0.4% or less, IMF (5-hydroxymethylfurfural)...5nlg/l00
g or less, acidity...47n1 or less of IN-sodium hydroxide per 100g, starch dextrin reaction...(
one).

The inventors of the present application have investigated the conversion of glucono delta lactone and D-gluconic acid or the conversion of glucose to fructose within an acceptable range that satisfies the quality standards for glucose. To produce amorphous honey by converting glucose into fructose, the ice melting rate (hydrolysis rate) of glucose should be up to 30%, and the glucose should be converted into glucono delta lactone and D-gluconic acid to produce sour sweetness. When producing amorphous honey as a raw material, it is preferable to set the ice melting rate to 20 to 80%.

Honey has a high Brix degree, so it is difficult for enzymes to act on it as it is. Therefore, honey is diluted with water or a suitable solvent, and the pH is adjusted to 5 to 8 using a basic substance. However, even if the pH is not adjusted, raising the reaction temperature or
Equivalent results can be obtained by increasing the amount of enzyme or increasing the reaction time.

Usually 2 to 1000 times more honey, preferably 2 to 100 times more
The reaction is initiated by adding the enzyme or allowing the immobilized enzyme to act on the diluted solution. The origin of enzymes
It can be used regardless of its purity, and may also be the bacterial cells themselves obtained by culturing microorganisms.

As the glucose oxidase (EC]..1.3.4), those of the genus Aspercillus are generally used, but other enzymes or microbial cells of the genus Streptomyces, Pseudomonas, Gluconobacter, and Acetobacter can also be used. used. The catalase used is of animal, plant, or microbial origin. Aspergillus niger
lus niger) is preferable in terms of its ability to efficiently produce both glucose oxidase and catalase and its action. Furthermore, if vilanose oxidase (E C 1.1.3.10) obtained from Basidiomycetes is used, the following will occur: glucose + 02 → glucozone + H 2 0 2 glucozone + H 2 → fructose 8, and fructose can be obtained from glucose.

Glucose isomerase (EC5.3.1.9) derived from the genus Streptomyces is generally used.

This enzyme is commercially available in an immobilized form, and may be used. Enzyme immobilization is done using alginic acid, agarose,
This can be achieved by general methods such as entrapping, adsorption, or direct covalent bonding of fluorine to polysaccharides such as chitosan, styrene resins, nylon, polyacrylamide, etc. Enzyme immobilization makes it possible to carry out the reaction continuously, increasing the reaction efficiency, enabling repeated use of the enzyme, and simplifying the operation of removing the enzyme from the reaction solution. It's advantageous. A packed bed type is used as the column of the reactor, but the liquid may be passed in either a downward flow or an upward flow. For example, when using immobilized glucose oxidase, the space velocity (SV) is usually 2 to IO, and the reaction temperature is 40 to 5.
When operated continuously at 0°C, the half-life of glucose is 3 months (
40°C), it can be said to be sufficiently stable and has high utility value from a cost standpoint.

9 Enzyme reaction is glucose oxidase, catalase 30
~50°C, 60-80°C for glucose isomerase
Do it with The conversion rate of glucose can be determined by collecting the reaction solution and measuring its conductivity, using high-performance liquid chromatography, or measuring the absorbance at a specific wavelength. It is confirmed by measuring the residual amount of acid or glucose or fructose. Alternatively, the amount of gluconic acid may be measured using a gluconic acid measurement kit [manufactured by Boehringer Mannheim Yamanouchi Co., Ltd.].

When glucose oxidase is used, the hydrolysis reaction of glucose is reversible, so glucono delta-lactone or D
-The reaction rate decreases significantly with the accumulation of gluconic acid. The reaction is promoted by coexisting catalase in the reaction system or by trapping the produced glucono delta lactone or D-gluconic acid with an ion exchange resin column.
If the ice melting rate is up to 30%, there is little need to coexist with catalase. Further, regarding glucose isomerase, there is no particular problem as it is sufficient to isomerize the amount of glucose in the honey to 25 to 30% of the amount of glucose in the honey.

The amount of enzyme added may be 1 to 5%, preferably 2 to 4%, based on the substrate. It goes without saying that any desired ice melting rate or isomerization rate can be obtained by adjusting the reaction conditions.

After the reaction, proteins and enzymes contained in honey are removed by filtering the reaction solution with a membrane filter, or subjecting it to ion exchange chromatography, hydrophobic chromatography, or the like. Although protein can be removed by heat treatment, good quality products cannot be obtained because 5-hydroxymethylfurfural (HMF) is produced by decomposition of residual fructose and glucose during heat treatment. By adding an appropriate filter aid to the solution after removing enzymes and proteins, filtering, and concentrating the filtration filter as necessary, amorphous honey with various degrees of Brix and amorphous honey as an acidic sweetener can be obtained. Honey is prepared.

11 Since the amorphous honey thus obtained has a small amount of glucose, it does not crystallize even after long-term storage, making it easy to handle and can be used in a wide range of fields.

In addition, amorphous honey containing a large amount of glucono-delta-lactone and D-gluconic acid has a low pH due to glucono-delta-lactone or D-gluconic acid, and is difficult to spoil and can be stored in a branched form. More preferably, D-gluconic acid is a substance that is difficult to crystallize, resulting in a product with appropriate viscosity. Also, if you want to powderize the product, add excipients such as starch, dextrin, lactose, sodium carboxymethyl cellulose, natural polysaccharides, etc.
Powder can be easily obtained by spray drying or freeze drying.

In addition, glucono delta lactone and D-gluconic acid are different from other organic acids in the acid family because they have a mellow sourness and are excellent in taste. Taking advantage of the taste of glucono delta lactone and D-gluconic acid, it is not only used at the table, but also in Kiyohara drinking water, various juices, lactic acid bacteria drinks, frozen fruits (ice cream, sherbet), and processed foods (chewing gum, celery). candy,
It can be used in all applications in which glucono delta-lactone or D-gluconic acid is used, such as jam, ketchup, sauce, mayonnaise, etc.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 1 kg of honey (clover, produced in Argentina, Brix degree 78) was weighed, 50 N of water was added thereto, and the pH was adjusted to 6.0 with 1'N sodium monohydroxide solution. Next, 20 g of glucose oxidase [Hiderase (trade name), manufactured by Amano Pharmaceutical Co., Ltd.] was added and 4
The reaction was allowed to take place at 0°C for 1 hour.

Thereafter, 50 g of activated carbon (powder) was added and stirred to filter diatomaceous earth. The filtrate was concentrated using an evaporator to obtain amorphous honey with a Brix degree of 78. The glucose in the honey solution before reaction was 6.6 g/n and the amount of D-gluconic acid was very small, but after the reaction, the amount of D-gluconic acid that had survived in the honey solution before concentration was 1. .33
It was 4g #.

Test Example 1 The amorphous honey obtained in Example 1 and the honey before enzyme treatment were stored at various temperatures for one month and changes over time were observed. The results are shown in the table below.

(The more + means more crystal precipitation, and 1 means no crystal precipitation.) As is clear from the table, no crystals were precipitated in the amorphous honey obtained in the examples.

Example 2 10 g of glucose oxidase [GOD Grade I, manufactured by Boehringer Mannheim Yamanouchi Co., Ltd.] and Katara 14 grade [Type I, manufactured by Boehringer Mannheim Yamanouchi Co., Ltd.] were added to a 0.2% sodium alginate solution.
Co., Ltd.] was dissolved and added dropwise to a 1% calcium chloride solution to enclose the enzyme in calcium alginate to prepare an immobilized enzyme. Separately, weigh out 1 kg of honey (astragalus, made in China, Brix degree 75), add 100 ml of water, mix well, and adjust the pH to 7 with IN sodium hydroxide solution.
．． It was set to 0. 100 g of the above-mentioned immobilized enzyme was added to this solution, and the mixture was reacted at 40° C. for 1 hour with stirring. The reaction limb was filtered to remove the immobilized enzyme, and then the protein in the solution was removed by a membrane filter. This product was concentrated using an evaporator to obtain amorphous honey with a Brix degree of 78. The glucose in the honey solution before treatment was 3.5 g #, but after the reaction, the amount of curcos in the honey solution before concentration was 2.6 g #. That is,
28% of glucose was hydrolyzed.

Example 3 To 20 cc of chitosan beads (Chito Pearl 3010 (trade name) manufactured by Fujibo Co., Ltd.) was added 100 cc of 5% talcose Oki 15 Cidase and stirred for 2 hours.

After washing with water, a 2.5% glutaraldehyde solution was added at a ratio of Chitopal resin of 1:1, and after further shaking for 2 hours, suction filtration was performed. The absorbance of the filtrate at 280 nm is 0.
．． The immobilized enzyme was prepared by washing with 50 times as much water as the amount of resin until the amount became 1 or less. A column was filled with 30 g of this immobilized glucose oxidase. Special Chimitsu (Orange, Mexican, Brix degree 77) 500
g was weighed, 51 g of water was added and mixed well to prepare a honey solution. This honey solution was poured into the column, and
It was operated continuously for 1 hour at 0°C. Next, 20 g of octyl agarose was added to this treated solution, which was quickly filtered to remove honey protein from the solution, and concentrated to a Brix degree of 80 using an evaporator. The glucose in the honey solution before treatment was 36 g/l, but after the reaction, the glucose before concentration was
Glucose in the honey solution was 30 g/V.

Example 4 Add 500 liters of water to 5 kg of honey (clover, produced in Argentina, Brix degree 75) and mix well.
Add IN sodium monohydroxide solution to this to adjust the pH to 8.
It was adjusted to 0. Glucose isomerase (manufactured by Novoindustri, derived from the genus Streptomyces) was added to this solution and reacted at 50° C. for 1 hour. The reaction solution was operated in the same manner as in Example 1 to obtain amorphous honey with a Brix degree of 79. The conversion rate of glucose to fructose was 16%.

Example 5 2 kg of honey (clover, produced in Argentina) and 2 kg of water
01 and the pH was adjusted to 7.0 with IN sodium monohydroxide solution.
Adjusted to 0. This solution was passed through a column filled with the immobilized enzyme of Example 3, and reacted at 40°C for 3 hours. During the reaction, the pH of the solution was kept at 7 with IN sodium hydroxide solution. Further, a DEAE (diethylaminoethylcellulose)-Sepharose column was connected in series to the bottom of the immobilized enzyme column to continuously adsorb D-gluconic acid produced in the reaction. After the reaction was completed, the column was washed with a sufficient amount of water, and the washing solution was mixed with the reaction solution, which was concentrated using an Evaporator. The analytical values of the obtained amorphous honey as a sour sweetener are shown below.

Fructose: 43.5%, Glucose: 5. 1%,
D-gluconic acid: 28%, water: 20% When the taste of this amorphous honey was confirmed, it was sweet and sour, but not a pungent sour taste, but a mellow taste. Furthermore, when this amorphous honey was diluted with water and sampled as a raw material for drinks, it was confirmed that it could be used without any problems.

[Effects of the Invention] As detailed above, according to the present invention, since the amount of glucose contained in honey is small, no crystals are precipitated even when stored for a long period of time, and unlike conventional honey manufacturing processes, honey In processing processes that use
It has become possible to easily use it for a long period of time without any effort. In addition, non-crystalline honey, which is produced by oxidizing glucose and contains a large amount of glucono delta-lactone and D-gluconic acid, has both sourness and sweetness, making it an excellent food with functions as an acidulant and a sweetener. Becomes the material.

Furthermore, it can be easily produced under mild reaction conditions by allowing an enzyme to act on a honey solution.

Claims (1)

[Claims] 1. Amorphous honey characterized by lowering the amount of glucose in the honey by allowing an enzyme to act on the honey solution. 2. A method for producing amorphous honey, which comprises lowering the amount of glucose in honey by allowing an enzyme to act on a honey solution. 3. A method for producing amorphous honey, which comprises reacting a honey solution with glucose oxidase alone or in combination with catalase. 4. A method for producing amorphous honey, which comprises allowing glucose isomerase to act on a honey solution. 5. The method for producing amorphous honey according to any one of claims 2 to 4, wherein the enzyme is an immobilized enzyme.