JPH10168097A - Glucide-protein conjugate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject new conjugate, comprising a glucide-protein conjugate prepared by thermally reacting a glucide containing an acidic saccharide having carboxyl group as a constituent saccharide with a protein in an aqueous system and useful as a modifier, etc., for coffee whiteners, sponge cakes, etc. SOLUTION: This new glucide-protein, comprises a mixed and heated substance of a glucide containing an acidic saccharide having carboxyl group as a constituent saccharide with a protein, has new functions different from those of the individual glucicle and protein before the reaction and is useful for various applications such as a modifier, etc., for coffee whiteners, sponge cakes, etc. The glucide-protein conjugate is obtained by carrying out the thermal reaction of the glucide containing an acidic saccharide having carboxyl group such as uronic acid or a carboxylic acid etherified saccharide as a constituent saccharide with a glucide such as pectin, alginic acid, gum arabic, gellan gum or carboxymethyl cellulose with the protein such as a soybean protein, a wheat protein, a casein, an ovalalbumin or a gelatin in an aqueous system at >=100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbohydrate-protein complex produced by reacting a carbohydrate containing a carboxyl group-containing acidic sugar as a constituent sugar with a protein in water, and a method for producing the same.

[0002]

2. Description of the Related Art As a chemical reaction generally used for forming a complex between a carbohydrate and a protein, an aminocarbonyl reaction for bonding a carbonyl group in a carbohydrate with an amino group in a protein is known. It has been applied to coloring, flavoring and flavoring of foods such as miso and soy sauce, or development of new functional materials as disclosed in JP-A-3-215498.

[0003]

With respect to the aminocarbonyl reaction, various studies have been made on the reaction conditions and the like. However, the reaction is disadvantageous in the color, fragrance,
The taste may be added, the reaction takes time,
There was a problem that the desired product could not be obtained easily in a short time, such as difficulty in controlling the reaction, and it was not always satisfactory.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above points and found that a saccharide containing an acidic saccharide having a carboxyl group as a constituent saccharide and a protein were mixed in water at 100 ° C. or higher. , A finding that a carbohydrate-protein complex (containing an acidic sugar) is easily produced by a very simple method. The present invention has been completed based on such findings.

That is, the present invention provides a carbohydrate-protein complex comprising a heated mixture of a carbohydrate containing a carboxyl group-containing acidic sugar and a protein, and a carbohydrate-protein containing a carboxyl group-containing acid sugar and a protein. In water to mix
A method for producing a carbohydrate-protein complex, wherein a heating reaction at 0 ° C. or more is carried out.

According to the present invention, examples of acidic sugars having a carboxyl group include uronic acids such as galacturonic acid, glucuronic acid and mannuronic acid, and carboxylic acid etherified sugars such as carboxymethyl etherified glucose. Examples of carbohydrates containing these as constituent sugars include pectin, alginic acid, natural polysaccharides such as gum arabic, fermented polysaccharides such as gellan gum, carboxymethylcellulose, synthetic polysaccharides such as propylene glycol alginate, pectin degradation products, and alginic acid degradation. And acidic oligosaccharides such as a product.

The carboxyl group may be in a state where an alcohol such as methyl alcohol is ester-bonded, but is preferably present in a free or salt state. The content of the acidic saccharide in the saccharide is preferably as high as possible, but is preferably at least 10% by weight, more preferably at least 20% by weight, further preferably at least 30% by weight.

On the other hand, proteins include plant-derived proteins such as soybean protein, corn protein, wheat protein and pea protein, as well as animal proteins such as casein, ovalbumin, whey protein, gelatin, actin, myosin and silk protein. Protein may be used, polypeptide,
Any proteins such as peptides and amino acids can be used.

Heating of carbohydrates and proteins is carried out in an aqueous system for 100 hours.
It is necessary to raise the temperature to at least ℃. In general, it may be heated under pressure in a dissolved or dispersed state in water, in a wet state, or in a paste state. Heating temperature is 10
If the temperature is lower than 0 ° C., it takes a long time, and the complex between the acidic sugar-containing saccharide and the protein is not satisfactorily formed, so that it is difficult to obtain the desired complex.

[0010] Carbohydrates and proteins containing an acidic sugar having a carboxyl group as constituent sugars may be in either a water-soluble state or a water-insoluble state. When it is insoluble in water, it is more efficient to perform complexation at the same time as extraction.

To obtain a complex of an acidic sugar-containing saccharide and a protein, a suitable ratio of the two is as follows.
0: 1 to 1: 100, preferably 50: 1 to 1:50,
More preferably, it is 10: 1 to 1:10.

As described above, the complex is produced by mixing a carbohydrate containing an acidic sugar having a carboxyl group as a constituent sugar and a protein in an aqueous system and then heating the mixture to 100 ° C. or higher. An example is as follows.

First, the raw material is suspended in an aqueous solution or water, and the pH may be any pH, but is preferably adjusted to pH 2 to 11, more preferably pH 4 to 9,
After heat treatment at a temperature of 00 ° C. or higher, the water-soluble fraction is separated and then dried as it is, or after neutralization, for example, dialysis treatment, activated carbon treatment, resin adsorption treatment or ethanol precipitation treatment, thereby performing inorganic salts, By drying after removing and purifying the hydrophobic substance or the low-molecular substance, a target carbohydrate-protein complex containing acidic sugar can be obtained.

The formation of the complex can be easily confirmed by analyzing the reaction product by high performance liquid chromatography using gel filtration. That is, when the reaction product obtained by heating the mixture of acidic sugar and protein was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption (OD 280 nm) was observed at a higher molecular weight position than when only acidic sugar or protein was thermally decomposed. As a result, it can be easily confirmed that the acidic sugar and the protein are complexed.

The acidic sugar-containing saccharide-protein complex of the present invention has a novel function different from individual acidic sugar-containing saccharides and proteins before the reaction. For example, emulsifying power, emulsifying stabilizing ability, physical property improving ability of flour products, dispersion stabilizing ability, which are not found in individual saccharides or proteins before the reaction,
Functions such as foaming power, bubble stabilizing ability, and water retaining ability are exhibited by forming the complex.

[0016]

The embodiments of the present invention will be described below with reference to examples, but these are only examples, and the spirit of the present invention is not limited to these examples. In addition, in an example, all parts and% mean a weight basis.

Example 1 500 g of low methoxy pectin (LM-pectin) and 100 g of soybean protein were dissolved in 5400 g of warm water, the pH was adjusted to 6.0, and the mixture was heated at 105 ° C. for 2 hours and LM-pectin and soybean protein were dissolved. To produce a mixed heated product. After heating, cool to room temperature and centrifuge (10000G x 30 minutes)
The supernatant was dried to collect the solid. When this solid was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption was observed at a higher molecular weight position than when only the raw material, low methoxy pectin and soybean protein were thermally decomposed, and this solid was analyzed for both. It was confirmed to be a complex. This solid was converted into a 10% aqueous solution, soybean oil equivalent to the mixture was added, and the mixture was mixed with a homomixer at 1000%.
When emulsification was performed at 0 rpm, the emulsified particle size was 0.5
An emulsion having a good μ was obtained, which proved that a carbohydrate-protein complex was formed.

Further, 5 parts of this saccharide-protein complex was added to 75 parts of water, and 0.1 parts of commercially available milk flavor was added thereto.
20 parts of refined coconut oil, to which 300 parts were added, was preliminarily emulsified with a homomixer at 70 ° C., and then 300 ml with a high-pressure homogenizer.
This emulsification was performed at kgf / cm2 to prepare a coffee whitener. This coffee whitener exhibited a stable emulsified state, and no emulsification destruction such as aggregation and oil separation was observed even after storage for one month.

Further, when the coffee whitener was added to regular coffee (80 ° C., pH 5.3) containing 5% of sugar, emulsification such as feathering did not occur.
It had heat resistance and acid resistance. Further, the coffee whitener was added to regular coffee adjusted to pH 6.8 with baking soda, and retort sterilization was performed at 121 ° C. for 15 minutes. However, emulsification destruction such as oil separation did not occur and the coffee whitener had retort resistance. there were.

Comparative Example 1 500 g of LM-pectin and 100 g of soybean protein were dissolved in 5400 g of warm water, the pH was adjusted to 6.0, and the mixture was heated at 80 ° C. for 2 hours. After heating, the mixture was cooled to room temperature, centrifuged (10000 G × 30 minutes), and the supernatant was dried to collect a mixed heated product of LM-pectin and soybean protein. Emulsification was performed in the same manner as in Example 1 using this mixed heated product,
The emulsified particle diameter was only 5.3 μm, and the oil was separated when the prepared emulsion was left for a while.

Comparative Example 2 500 g of LM-pectin was dissolved in 4500 g of warm water.
The pH was adjusted to 6.0 and heated at 120 ° C. for 30 minutes.
After heating, the mixture was cooled to room temperature and centrifuged (10000 G × 3).
(0 min), the supernatant was dried to recover the heated LM-pectin. An emulsification treatment was performed in the same manner as in Example 1 using this heated product, but no emulsification was performed.

Comparative Example 3 100 g of soybean protein was dissolved in 900 g of warm water, the pH was adjusted to 6.0, and the mixture was heated at 120 ° C. for 30 minutes. After heating, the mixture was cooled to room temperature and centrifuged (10000 G × 30).
), And the supernatant was dried to recover the soybean protein heated product. Emulsification was performed in the same manner as in Example 1 using this heated material, but the emulsified particle size was only up to 4.2 μm, and
When the prepared emulsion was left for a while, oil separated.

Comparative Example 4 500 g of LM-pectin and 100 g of soybean protein were separately dissolved in water to prepare 10% solutions, and then both solutions were adjusted to pH 6.0 and heated at 120 ° C. for 30 minutes. . After heating, cool to room temperature and centrifuge (10000 g
The supernatant was dried to recover each of the heated LM-pectin and the heated soybean protein. After mixing these heated materials, an emulsification treatment was carried out in the same manner as in Example 1, but the emulsified particle size was only up to 3.0 μm. Further, when the prepared emulsified material was left for a while, oil was separated.

Example 2 After dissolving 500 g of high methoxy pectin (HM-pectin) and 100 g of soy protein in 5400 g of warm water, the pH was adjusted to 6.0, and the mixture was heated at 120 ° C. for 30 minutes to obtain HM-pectin and soy protein. Was formed. After heating, the mixture was cooled to room temperature and centrifuged (10,000 g × 30).
Min) and the supernatant was dried to collect a solid. When this solid was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption was observed at a higher molecular weight position than when only the raw material, high methoxy pectin and soybean protein were thermally decomposed, and this solid was found It was confirmed to be a complex. Further, when the emulsification treatment was performed using this solid product in the same manner as in Example 1, a good emulsion having an emulsified particle diameter of 0.6 μm was obtained, and a saccharide-protein complex was formed. Was able to substantiate.

Using this composite, a sponge cake was prepared on a trial basis with the following composition, and changes in texture and storage were examined. For comparison, a sponge cake with no complex added was also experimentally produced as a control.

Sponge cake formulation (parts by weight) 重量 Example 2 ────────────────────────────────── Whole egg 100 100 Sugar 100 100 Soft flour 100 100 Water 35 35 Emulsified fat 15 15 Baking powder 22 Carbohydrate-protein complex 1-───────────────────────────────────

[0027] As a result, the sponge cake of Example 2 had a smoother texture and was more crispy than that of Comparative Example 5, and had a very good texture. Further, the sponge cake was stored in a closed container at 20 ° C. for 7 days and the change in hardness was measured. As a result, as shown below, the increase in hardness was suppressed in the sponge cake of Example 2 and aging was observed. The prevention effect was seen.

Changes in storage ─────────────────────────────────── Storage days * Hardness (g / cm2 ) ** Water content ────────────────────────────────── Example 2 0 45.2 35.4 7 80.5 30.8 Control 0 48.1 35.5 7 122.0 30.2 ─────────────────────────────────── * Storage days (days) are samples Days stored at 20 ° C. in closed containers. ** Hardness (g / cm2) is measured by using a rheometer (manufactured by Fudo Kogyo Co., Ltd.) using a 40 mm diameter plunger at a table speed of 50 mm / min. Value measured in.

Example 3 After dissolving or dispersing 500 g of sodium alginate and 100 g of soybean protein in 11400 g of warm water, the pH was adjusted to 6.0.
And heated at 120 ° C. for 30 minutes to form a mixed heated product of sodium alginate and soy protein. After heating, the mixture was cooled to room temperature and centrifuged (10,000 g × 30).
Min) and the supernatant was dried to recover a solid. When this solid was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials sodium alginate and soybean protein were thermally decomposed, and this solid was combined with both. I confirmed my body. When an emulsification treatment was performed using this solid product in the same manner as in Example 1, a good emulsion having an emulsified particle size of 0.7 μm was obtained, and the formation of a carbohydrate-protein complex was substantiated.

Example 4 500 g of LM-pectin and 50 g of soybean protein were added to warm water 4
After dissolving in 950 g, the pH was adjusted to 4.0, and the mixture was heated at 120 ° C. for 30 minutes to form a mixed heated product of LM-pectin and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. The solid was analyzed by high performance liquid chromatography using gel filtration. As a result, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials LM pectin and soybean protein were thermally decomposed. I confirmed my body. Further, when an emulsification treatment was carried out in the same manner as in Example 1 using this solid product, the emulsified particle size was 0.1 mm.
A good emulsion of 6μ was obtained, supporting the formation of a carbohydrate-protein complex.

Example 5 500 g of LM-pectin and 500 g of soybean protein were dissolved in 9000 g of warm water, the pH was adjusted to 9.0, and the temperature was adjusted to 120 ° C.
For 30 minutes to form a mixed heated product of LM-pectin and soy protein. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. The solid was analyzed by high performance liquid chromatography using gel filtration. As a result, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials LM pectin and soybean protein were thermally decomposed. I confirmed my body. When emulsification treatment was performed using this solid product in the same manner as in Example 1, a good emulsion having an emulsified particle size of 0.4 μm was obtained, and the formation of a carbohydrate-protein complex was substantiated. .

Example 6 500 g of LM-pectin and 100 g of casein were added to warm water 5
After dissolving in 400 g, the pH was adjusted to 6.0 and the mixture was heated at 120 ° C. for 30 minutes to form a mixed heated product of LM-pectin and casein. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. The solid was analyzed by high performance liquid chromatography using gel filtration. As a result, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials LM pectin and casein were thermally decomposed. Was confirmed. When an emulsification treatment was performed using this solid product in the same manner as in Example 1, the emulsified particle diameter was 0.8.
A good emulsion of μ was obtained, and the formation of a carbohydrate-protein complex was substantiated.

Example 7 After 500 g of LM-pectin and 100 g of wheat protein were dissolved in 5400 g of warm water, the pH was adjusted to 6.0, and 150 ° C.
For 2 minutes to form a mixed heat of LM-pectin and wheat protein. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. The solid was analyzed by high performance liquid chromatography using gel filtration. As a result, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials LM pectin and wheat protein were thermally decomposed. I confirmed my body. Further, when an emulsification treatment was carried out in the same manner as in Example 1 using this solid product, the emulsified particle size was 0.1 mm.
A good emulsion of 5μ was obtained, supporting the formation of a carbohydrate-protein complex.

Example 8 1000 g of Satsuma mandarin peel and 100 g of soybean protein were suspended in 4900 g of hot water, and the pH was adjusted to 4.0.
The mixture was heated at 30 ° C. for 30 minutes to simultaneously carry out extraction of pectin and mixing and heating with soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. When this solid was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption was observed at a higher molecular weight position than when only the raw materials of Satsuma mandarin peel and soybean protein were thermally decomposed. Was confirmed to be a complex. Further, when an emulsification treatment was performed using this solid product in the same manner as in Example 1, a good emulsion having an emulsified particle diameter of 0.4 μm was obtained, and the formation of a carbohydrate-protein complex was substantiated. .

Example 9 1000 g of beet lees and 100 g of soy protein were mixed with hot water 49
After suspending in 100 g, the pH was adjusted to 5.0, and
By heating for 0 minutes, extraction of beet pectin and mixing and heating with soybean protein were simultaneously performed. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to recover a solid. When this solid was analyzed by high performance liquid chromatography using gel filtration, ultraviolet absorption was observed at a higher molecular weight position than when only the raw material, beet meal and soybean protein were thermally decomposed, and this solid was a composite of the two. I confirmed my body. Further, when an emulsification treatment was carried out in the same manner as in Example 1 using this solid product, a good emulsion having an emulsified particle size of 0.5 μm was obtained, and the formation of a carbohydrate-protein complex was substantiated. .

Comparative Example 5 Dextrin (D) which is a carbohydrate containing no acidic sugar as a constituent sugar
E = 5) 500 g of soybean protein and 500 g of hot water
After dissolving in 0 g, the pH was adjusted to 6.0 and heated at 105 ° C. for 2 hours. After heating, cool to room temperature and centrifuge (10
(000 g × 30 minutes), and the supernatant was dried to recover a mixed heated substance of dextrin and soybean protein. An emulsification treatment was performed in the same manner as in Example 1 using this heated product, but no emulsification was performed.

Comparative Example 6 500 g of arabinogalactan and 100 g of soybean protein, which are carbohydrates containing no acidic sugar, were dissolved in 5400 g of warm water, the pH was adjusted to 6.0, and the mixture was heated at 120 ° C. for 30 minutes. . After heating, cool to room temperature and centrifuge (1000
(0 g × 30 minutes), and the supernatant was dried to collect a mixture of arabinogalactan and soybean protein. An emulsification treatment was carried out in the same manner as in Example 1 using this mixed heated product, but no emulsification was performed.

Comparative Example 7 500 g of λ-carrageenan, which is a carbohydrate containing a carboxyl group-containing acidic sugar having a sulfuric acid group, and 100 g of soybean protein were dissolved in 5400 g of warm water, and the pH was adjusted to 6.0. And heated at 120 ° C. for 30 minutes. After heating, the mixture was cooled to room temperature and centrifuged (10,000 g × 30).
), And the supernatant was dried to recover a mixed heated product of λ-carrageenan and soybean protein. An emulsification treatment was carried out in the same manner as in Example 1 using this mixed heated product, but no emulsification was performed.

Comparative Example 8 1000 g of Satsuma mandarin peel was suspended in 5000 g of hot water.
The pH was adjusted to 4.0 and pectin was extracted by heating at 120 ° C. for 30 minutes. After heating, the mixture was cooled to room temperature, centrifuged (10000 g × 30 minutes), and the supernatant was dried to collect the heat-extracted pectin. Using this pectin, emulsification was performed in the same manner as in Example 1, but no emulsification was performed.

COMPARATIVE EXAMPLE 9 1000 g of Satsuma mandarin peel and 100 g of soybean protein were suspended in 4900 g of hot water, the pH was adjusted to 4.0, and the suspension was adjusted to 80 ° C.
For 2 hours to perform pectin extraction and mixed heating with soybean protein. After heating, cool to room temperature and centrifuge (1
(0000 g × 30 minutes), and the supernatant was dried to collect a mixed heated substance of pectin and soybean protein. An emulsification treatment was carried out in the same manner as in Example 1 using this mixed heated product, but no emulsification was performed.

[0041]

As described above, after mixing a saccharide containing an acidic saccharide having a carboxyl group as a constituent saccharide and a protein, the mixture is heated at 100 ° C. or higher in an aqueous system to obtain a saccharide-protein containing an acidic saccharide. The complex could be obtained easily. Such a complex has a novel function different from individual carbohydrates and proteins before the reaction, and can be used for various uses such as a coffee whitener and a sponge cake modifier.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A23L 1/19 A23L 1/19 (72) Inventor Yuichi Maeda 4-3 Kinokudai, Kiniwadai, Taniwahara-mura, Tsukuba-gun, Ibaraki Prefecture Tsukuba Fuji Oil Co., Ltd. R & D center

Claims (6)

[Claims] 1. A carbohydrate-protein complex comprising a mixture of a carbohydrate and a protein containing an acidic sugar having a carboxyl group as a constituent sugar and a protein. 2. The carbohydrate-protein complex according to claim 1, wherein the acidic sugar having a carboxyl group is uronic acid. 3. The saccharide-protein conjugate according to claim 1, wherein the acidic saccharide having a carboxyl group is a carboxylic acid etherified saccharide. 4. A process for producing a carbohydrate-protein complex, wherein a carbohydrate containing an acidic sugar having a carboxyl group and a protein are subjected to a heating reaction at 100 ° C. or higher in an aqueous system. 5. The method according to claim 4, wherein the heating reaction between the saccharide containing the acidic saccharide having a carboxyl group as a constituent saccharide and the protein is performed simultaneously with the extraction of the saccharide. 6. The method according to claim 4, wherein the heating reaction between the protein and a saccharide containing an acidic saccharide having a carboxyl group as a constituent saccharide is performed simultaneously with the extraction of the protein.