JP3860025B2 - Method for water-solubilizing muscle protein by treatment with reducing sugar under low relative humidity and water-soluble sugar-added muscle protein - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to food processing fields such as fishery processing industry and meat processing industry, further to health foods, and further to the fields of textile and material industries.
[0002]
[Prior art]
Fish meat and livestock meat are used as various processed foods such as kneaded products and sausages. This utilizes functional properties such as gel-forming ability, emulsifying ability, and water retention ability of proteins in fish and livestock meat.
Protein components extracted from fish meat are not yet fully utilized in food. In addition, gelatin, which is a protein mainly contained in bones, has been used as a stew or jelly since ancient times, but since the amino acid composition of gelatin is extremely unique, it has many significance as a luxury product, Its use was limited.
[0003]
[Problems to be solved by the invention]
Muscle proteins have functional properties such as gel-forming ability, emulsifying ability, water retention ability, etc., but muscle proteins are prone to degeneration and have difficulty in maintaining functional properties. Furthermore, a large amount of processing residue is generated in fish meat, but this effective use has also been desired.
On the other hand, it has also been desired to develop a liquid high protein-containing food so that elderly people and sick people whose chewing function has declined can easily take proteins with high nutritional value.
[0004]
However, conventionally, as a technique for solubilizing fish meat, there is a hydrolysis method using a proteolytic enzyme or an acid, but there is a drawback that a bitter peptide is generated when the molecular weight is insufficient. In addition, various processing characteristics of protein molecules are lost due to hydrolysis due to hydrolysis.
[0005]
The present inventors have already tried to add a sugar to a muscle protein by Maillard reaction to maintain the functional characteristics and to stabilize the protein function. It has already been found and reported to be soluble at concentrations (Journal of Agricultural and Food chemistry 1997, Vol. 45, No. 9, pp. 3419-3422, and Journal of Agricultural and Food Chemistry Vo. 48, No. 1 , pp.17-21).
[0006]
The Maillard reaction is a reaction between a reducing sugar and an α-amino group or an ε-amino group of an amino acid, starting with the formation of a Schiff base, through a transfer reaction, and an initial reaction until a relatively colorless amalide compound is generated, Furthermore, it can be classified into intermediate and final reactions that cause complex polymerization reactions and produce brown polymers (melainodin). The initial reaction occurs under relatively mild conditions, and progresses to the middle and final reactions as the temperature increases and the time increases. The initial reaction depends on the water content of the reaction system, and the relative humidity is 65 to 65. 70% is the maximum. It is said that the intermediate and final reactions are promoted by the coexistence of catalysts such as oxygen and metal (Chemical Review No.43 Food and Chemistry, The Chemical Society of Japan, Society Publishing Center, February 28, 1984 issue 107) ~ 109 pages).
As for muscle protein, sugar is added to protein by Maillard reaction between a reactive lysine residue in fish meat protein and the reducing end of sugar. The myosin molecule, which is the main component of muscle protein, has a molecular structure called a rod, and the rod site is insoluble in water. In particular, myosin molecules are insoluble in water because they aggregate and form filaments under low ionic strength. However, when the sugar is bound to the rod portion, this filament-forming ability is lost and the hydrophilicity of the site is further increased, so that the myosin molecule becomes water-soluble, and as a result, the entire muscle is dissolved even under physiological conditions.
[0007]
Conventionally, the addition of sugar to fish protein has been performed in the following steps.
That is, the back muscle of fish meat is cut into small pieces, washed with 50 mM NaCl three times, homogenized, filtered, and centrifuged several times at 5000 g-15 minutes to obtain a fish myofibrillar protein fraction (Mf). Was precipitated, and suspended and recovered homogeneously in 50 mM NaCl. Myosin is obtained by purifying Mf thus obtained by the ammonium sulfate fractionation method.
[0008]
When the obtained Mf and myosin are modified with glucose or ribose, Mf or myosin is suspended in 50 mM NaCl containing 0.1 to 0.6 M glucose or ribose, freeze-dried, and the freeze-dried product is dried at constant temperature and humidity. The protein is sugar-modified by maintaining at 30-50 ° C. and 65% relative humidity.
When modifying with an alginate oligosaccharide, Mf or myosin is suspended in a 50 mM NaCl-0.3 to 0.6 M sorbitol solution, the oligosaccharide is mixed and lyophilized, and the protein-sugar mixture is heated to 30 to 40 ° C. and relative humidity 65 % To retain and modify.
[0009]
However, myosin, which is the main component of muscle protein, has a larger and more complex structure than milk protein, plasma protein, plant protein and the like that have been studied so far, and is thermally unstable. Therefore, if the relative humidity is maintained at 65 to 70%, the Maillard reaction proceeds and the soot is bound, so that it is denatured due to the thermal motion of water molecules present in the surroundings, and the degree of water solubilization is low. I understood. In fact, the protein modified in this way is 0.1M NaCl, the degree of water solubilization is only 55 to 64%, and it cannot be said that the yield is high for industrial use. Met. In particular, for use in the food industry and the like, the salt content in foods is usually lower than the physiological saline concentration, and it has been desired to make water soluble under low ionic strength.
[0010]
[Means for Solving the Problems]
The present inventors have changed the conditions of the Maillard reaction of fish protein by changing the conditions such as using various sugars under high temperature and high humidity of 30 to 50 ° C. and 65% relative humidity, which were conventionally considered optimal. I have continued research. However, accidentally, the Maillard reaction treatment was performed under low relative humidity due to the malfunction of the experimental apparatus, and unexpectedly, the water solubility under low ionic strength increased.
Therefore, a salmon muscle suspension containing 0.6 M sorbitol was prepared, and an alginate oligosaccharide equivalent to the amount of myofibrillar protein was dissolved in the suspension, followed by dehydration to obtain a water content of 8.4%. This was kept in various humidity atmospheres (relative humidity 5-80%) and kept at 50 ° C. for 8 hours to react protein and sugar. As a result, when the relative humidity was 35% or less, the water content of the sample was further reduced (3% or less) and stabilized, but when the relative humidity exceeded 40%, environmental moisture was absorbed in the reaction process. For example, when the relative humidity was 50% and 65%, the sample moisture after 8 hours reached 11.1% and 20.7%, respectively. Then, when this protein was dissolved in 0.1M NaCl and its solubility was measured, it was found that there was a significant relationship between the relative humidity during the reaction and the effect of modifying the solubility. That is, as shown in FIG. 1 and FIG. 2, it has been found that high solubility can be imparted when the reaction is carried out under the condition that the relative humidity is 35% or less and the water content of the fish protein sample in the reaction process is 6% or less. It is.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a water-soluble protein having sufficient solubility is produced even under low ionic strength by adding a sugar to muscle protein under the condition of suppressing relative humidity.
In the present invention, various meats are minced, muscle protein is extracted, or mixed as it is with reducing sugars , dehydrated, and kept in the range of 30 to 70 ° C. at a relative humidity of 35% or less, By maintaining the water content within 0.25-6%, meat or muscle protein is water-soluble even at low ionic strength.
[0011]
Examples of the muscle protein that can be used in the present invention include muscle proteins of all living organisms such as fish meat, livestock meat, shellfish, and squid. Furthermore, the meat as referred to in the present invention means a meat containing muscle protein and a meat selected from mollusk or crustacean muscle, fish meat, or livestock meat. By mincing these meats, it is possible to make them water-soluble as they are without the need to extract and purify muscle proteins. Shredding means cutting the meat by various means, and includes, for example, homogenization processing and minced meat processing, preferably to the extent that it passes through a mesh of 5 mm, more preferably 3 mm or less. It is desirable to chop up to minced or mince.
[0012]
Reducing sugars that can be used in the present invention include monosaccharides (glucose, ribose, etc.), oligosaccharides having an average polymerization degree of 20 or less and those having a reducing end, for example, reducing properties such as alginic acid oligosaccharides and chitosan oligosaccharides. Examples include oligosaccharides.
Examples of the protein denaturation inhibitor in the present invention include glucose and sorbitol. These protein denaturation inhibitors such as sorbitol are particularly effective when the reducing sugar to be added has a small protein denaturation effect such as an alginate oligosaccharide.
[0013]
The mixing ratio of protein and sugar in the present invention is desirably in the range of muscle protein: saccharide = 1: 0.1 to 1:10, and further, mollusk or crustacean muscle, fish meat, or livestock meat and sugar. It is desirable that the mixing ratio of the muscle protein and sugar contained in the same range.
[0014]
Meat selected from muscle protein or minced mollusc or crustacean muscle, fish, or livestock meat is subjected to dehydration after mixing with sugar. The dehydration treatment can be performed by various means, for example, heat treatment under a low humidity of 10% relative humidity, freeze drying, spray drying, reduced pressure drying, or a combination thereof. . In addition, the water content can be adjusted to 0.25 to 6.0% suitable for the Maillard reaction by dehydration, but the relative humidity is 35% or less even if the water content at the end of the dehydration process exceeds 6.0%. And by keeping at 30-70 ° C., the water content can also be in the range of 0.25-6.0%.
[0015]
The water-soluble muscle protein of the present invention can be used not only as an emulsifier for food addition due to its excellent emulsifiability, but also because it is water-soluble, it can be very easily added to and mixed with other foods. Fish meat can be homogeneously mixed in the livestock meat food (or in agricultural food) to produce processed food. Furthermore, for example, as a functional protein supply for medical use, a) liquid food (for patients with reduced swallowing function, baby food), b) high protein sports drink, c) vitamin A, D, Fat-soluble vitamins such as E and highly unsaturated fatty acids can be added to these foods.
[0016]
The glycosylated muscle protein produced by the method of the present invention and water-soluble under low ionic strength is not denatured from the conventional glycosylated muscle protein under high humidity, and the muscle protein This is a novel structure that is structurally different in that it has the property that the degree of aggregation of the main component myosin molecule is small and, as a result, it is difficult to aggregate by heating (FIG. 3).
Further, the method of the present invention will be described in detail by way of examples.
[0017]
【Example】
[Example 1] Glucose (18.5 g) equal to the amount of myofibrillar protein (18.5% wet weight) was mixed with 100 g of scallop and scallop scallops, and then dehydrated by pressurization and freeze-drying. The water content was 0.7%. When this was kept at 50 ° C. and 30% relative humidity for 12 hours, 60% of lysine residues in scallop myofibrillar protein bound to glucose. The solubility of this glucose-modified protein in 0.1M NaC1 was 89%, and water-solubilization of scallop shells was achieved. In addition, it was confirmed by SDS-polyacrylamide gel electrophoresis analysis that no protein degradation occurred during this series of treatments.
[Example 2] Salmon muscles and alginic acid oligosaccharide salmon muscles were chopped with a meat chopper until they passed through a 2 mm sieve <J1S-8811>. After mixing 100g of this fish meat with the same amount of myofibrillar protein (15% wet weight) and alginate oligosaccharide (15g) and sorbitol (14.1g), it was dehydrated by freeze-drying to increase the water content. 0.9%. Subsequently, when kept at 60 ° C. for 4 hours, the alginate oligosaccharide molecule reacted with a lysine residue in salmon muscle to form a protein-alginate oligosaccharide complex (hereinafter referred to as Meat-AO). By controlling the reaction relative humidity during the production of Meat-AO to 35% or less, the solubility of Meat-AO in 0.05M-0.1M NaC1 was 88-93%, and the water-solubilization of salmon muscle could be achieved. In addition, it was confirmed by SDS-polyacrylamide gel electrophoresis analysis that no protein degradation occurred during this series of treatments.
[0018]
[Example 3] Beef thigh meat and glucose or alginic acid oligosaccharide cow thigh meat was kept at 4 ° C for 7 days after slaughtering, then trimmed the clamped tissue to ground meat (chopper mesh size: 3 mm), 5 Washed 3 times with double volume of physiological saline (myofibrillar protein concentration was 9.5%). Glucose and alginate oligosaccharides were mixed 1: 1 and 1: 0.1 in a weight ratio of the washed meat to the myofibrillar protein contained therein. When the alginate oligosaccharide was added, sorbitol having a weight equivalent to 6% of the meat (final concentration of about 0.3 M) was further mixed. These meat-sugar mixtures were then freeze-dried to a moisture content of 0.7% and then held at 50 ° C. and a relative humidity of 5% for 12 hours to obtain glucose-modified muscle (Meat-G) or alginate oligosaccharide-modified muscle (Meat -AO). Although normal muscle protein does not dissolve in physiological saline, the solubility of Meat-G and Meat-AO in 0.05M NaC1 was 79% and 85%, and water solubility of beef was achieved. In addition, it was confirmed by SDS-polyacrylamide gel electrophoresis analysis that no protein degradation occurred during this series of treatments.
[0019]
[Example 4] Salmon muscle and alginate oligosaccharide Fish meat (salmon) minced in the same manner as in Example 2 was suspended in a 0.6 M sorbitol solution (myofibrillar protein concentration 1%). After adding an alginate oligosaccharide equivalent to myofibrillar protein, the water content was dehydrated to 8.4% by freeze-drying.
(I) When reacted at 50 ° C. under 5% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process is 1.6%, and the solubility in 0.1M NaCl is 93%. Solubilized.
(Ii) When reacted at 50 ° C. under 35% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process is 5.4%, and the solubility in 0.1M NaCl is 93%. Solubilized.
[0020]
[Example 5] Salmon muscle and alginate oligosaccharide Fish meat (salmon) minced in the same manner as in Example 2 was suspended in a 0.3 M sorbitol solution (myofibrillar protein concentration 1%). After adding an alginate oligosaccharide equivalent to myofibrillar protein, the water content was dehydrated to 4.9% by lyophilization.
(I) When the reaction was carried out at 50 ° C. and 5% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process was 0.8%, and the solubility in 0.1M NaCl was 89%. Solubilized.
(Ii) When reacted at 50 ° C. under 35% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process is 3.0%, and the solubility in 0.1M NaCl is 88%. Solubilized.
[0021]
[Comparative Example 1]
Fish meat (salmon) minced in the same manner as in Example 2 was suspended in a 0.6 M sorbitol solution (myofibrillar protein concentration 1%). After adding an alginate oligosaccharide equivalent to myofibrillar protein, the water content was dehydrated to 8.4% by freeze-drying.
(I) When the reaction was performed at 50 ° C. and 55% relative humidity for 8 hours, the water content of the protein-sugar complex during the reaction was 11.1%, and the solubility in 0.1M NaCl was 73%.
(Ii) When the reaction was carried out at 50 ° C. and 65% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process was 20.7%, and the solubility in 0.1M NaCl was 61%. .
[0022]
[Comparative Example 2]
Fish meat (salmon) minced in the same manner as in Example 2 was suspended in a 0.3 M sorbitol solution (myofibrillar protein concentration 1%). After adding an alginate oligosaccharide equivalent to myofibrillar protein, the water content was dehydrated to 4.9% by lyophilization.
(I) When the reaction was performed at 50 ° C. and 55% relative humidity for 8 hours, the water content of the protein-sugar complex in the reaction process was 9.3%, and the solubility in 0.1M NaCl was 70%. .
(Ii) When the reaction was carried out at 50 ° C. and 65% relative humidity for 8 hours, the water content of the protein-sugar complex during the reaction was 14.7%, and the solubility in 0.1M NaCl was 55%.
[0023]
【The invention's effect】
According to the present invention, even under low ionic strength, various muscle proteins such as fish meat and livestock meat were successfully water-solubilized even under low ionic strength.
The water-soluble protein of the present invention can be easily added to and mixed with fish and livestock meat and various foods to expand food processing applications, and is also useful for protein supplementation for the elderly with reduced chewing function. In addition, it is also possible to produce various molded products such as spinning and sheeting by once water-solubilizing and then drying. Since such a molded article is composed of protein and is easily decomposed by microorganisms even after disposal, it is excellent in environmental conservation.
[Brief description of the drawings]
FIG. 1 shows the effect of water during the sugar modification reaction on the solubility of alginate oligosaccharide-modified salmon myofibril protein.
White circle: The salmon muscle samples shown in Example 4 and Comparative Example 1 were kept at 60 ° C. for 4 hours under various humidity.
Black circle: Salmon muscle samples shown in Example 4 and Comparative Example 1 were kept at 50 ° C. for 8 hours under various humidity conditions.
[Fig. 2] Effect of relative humidity on the water solubilization of muscle proteins during the reaction with sugar. The experimental conditions are the same as in FIG.
FIG. 3 shows thermal aggregation properties of carp myofibril protein modified with alginate oligosaccharide.
The protein modified with alginate oligosaccharide was dissolved in 0.16 M and 0.5 M NaCl (pH 6.7), heated at various temperatures for 3 hours, and the solubility was measured. It can be seen that the unmodified protein is heat-denatured to aggregate and easily insolubilized.

Claims (9)

Minced meat selected from mollusk or crustacean muscle, fish meat or livestock meat (sawmill, the same shall apply hereinafter) , mixed with reducing sugars, dehydrated, and in an environment of 30-70 ° C with a relative humidity of 35% or less The water content is reduced to 0.25 to 6.0% and the water content is maintained in the environment.   After mixing muscle protein from mollusk or crustacean muscle, fish meat, or livestock meat with reducing sugars, dehydrated to a moisture content of 0.25-6.0% in an environment of 30-70 ° C. at a relative humidity of 35% or less, A method for water-solubilizing muscle protein by maintaining the water content in an environment. The method according to claim 1 or 2 , wherein the reducing saccharide is a reducing monosaccharide or a reducing oligosaccharide. The method according to any one of claims 1 to 3 , wherein the reducing saccharide is any one of glucose, ribose, chitosan oligosaccharide, and alginic acid oligosaccharide.   Minced meat selected from mollusk or crustacean muscle, fish meat, or livestock meat, mixed with reducing sugars, dehydrated, water content 0.25-6.0% in an environment with a relative humidity of 35% or less and 30-70 ° C Meat that has been water-solubilized by holding so that it becomes. 6. The water-soluble meat according to claim 5 , wherein the reducing saccharide is a reducing monosaccharide or a reducing oligosaccharide. 6. The water-soluble meat according to claim 5 , wherein the reducing saccharide is any one of glucose, ribose, chitosan oligosaccharide, or alginic acid oligosaccharide. The method according to any one of claims 1 to 4 , wherein the reducing saccharide and the protein denaturation inhibitor are mixed and then dehydrated. Meat solubilized by the method according to claim 8 .

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