JP2904855B2 - Aminocarbonyl reaction accelerator for food and aminocarbonyl reaction acceleration method - Google Patents

Description

Description: BACKGROUND OF THE INVENTION <Technical Field> The present invention relates to an improvement in a method for coloring food by a browning reaction. More specifically, the present invention relates to an aminocarbonyl reaction accelerator for food and an aminocarbonyl reaction acceleration method. In other words, the present invention relates to a method for producing a browned food.

It has long been known that various foods turn brown when they are processed or stored, and among them, for non-enzymatic browning, the substrates are amino compounds and carbonyl compounds in the food. From some sources, this browning reaction is called the aminocarbonyl reaction, and the Browning reaction found in foods is called the Maillard reaction in the name of a researcher who has clarified that it is due to the reaction of these reaction substrates. ing. In the present specification, the terms “browning reaction” and “aminocarbonyl reaction” are appropriately used, but the meanings are the same.

This browning can be caused by amino acids,
Amino compounds such as proteins, as well as reducing sugars and fatty acids, and carbonyl compounds such as ascorbic acid or their precursors are included, so if such coloring is not desired, it will be a major problem in food quality control,
On the other hand, there are foods that actively utilize this browning. For example, baked confectionery, bread, chikuwa, fried Satsuma and the like.

In the case of foods that are willing to utilize the browning reaction, not only rely on the amino and carbonyl compounds that are the substrates of the reaction to be derived from the food, but also actively add these substrates to the food. It is also being done.

In the case of foods that actively utilize the browning reaction, coloring is to enhance the palatability by adding a so-called baked color, and it is necessary to finish the baked color easily and beautifully. In addition, since this reaction is promoted by heating, it goes without saying that the heating for browning is preferably performed at a low temperature or in a short time.

<Prior art> From the above viewpoints, means for promoting browning include (a) using a large amount of a substrate for the reaction, (b) using a substrate that is easy to react, and (c) accelerating the reaction. It is possible to add a substance.

However, the means (a) is not preferable from the viewpoint of changing the taste and physical properties of the food and leading to an increase in cost. As means (b), for example, it is known to use a pentose such as xylose or ribose as a carbonyl compound or a precursor thereof,
Popular xylose is expensive. As a means of (c), it is conceivable to add metal ions such as iron and copper which are known to have a browning reaction accelerating action. Although approved for use as a toughening agent for fortification, it is not suitable as an accelerator for browning reactions.

[Summary of the Invention]

<Summary> The present invention aims to provide a solution to the above points, and aims to achieve this purpose by using a specific reaction accelerator.

That is, the aminocarbonyl reaction accelerator for food according to the present invention is characterized by using a nucleic acid-related substance composed of (deoxy) ribonucleic acid or a hydrolyzate thereof or a phosphate ester of sugar as an active ingredient.

Further, the aminocarbonyl reaction accelerating method according to the present invention comprises:
In a method of producing a colored food by causing an aminocarbonyl reaction in a food, the aminocarbonyl reaction is effectively carried out by using a nucleic acid-related substance comprising (deoxy) ribonucleic acid or a hydrolyzate thereof, or a phosphate ester of a sugar. Promoting the aminocarbonyl reaction by performing the reaction in the presence of an aminocarbonyl reaction accelerator as a component (wherein the nucleic acid-related substance is inosine-5'-monophosphate or guanosine-5'-monophosphate, When adding it to food, the amount of the nucleic acid-related substance to be added should be 0.1% in the food to be subjected to aminocarbonyl reaction.
% By weight or more).

<Effect> According to the present invention, a reaction between an amino compound and a carbonyl compound, that is, a browning reaction is remarkably promoted. Therefore, when the reaction substrate is added, the amount can be reduced, and the heating conditions can be relaxed with respect to temperature and / or time.

One of the reaction accelerators used in the present invention is ribonucleic acid or deoxyribonucleic acid or a hydrolyzate thereof or a specific amine compound of a nucleoside or nucleotide, so that it is generally inexpensive, but is particularly effective as a reaction accelerator. Uridine-5'-monophosphate (5'-
UMP) and cytidine-5'-monophosphate (5'-CMP)
Is a by-product of producing inosine-5'-monophosphate (5'-IMP) and guanosine-5'-monophosphate (5'-GMP), which are useful as nucleic acid seasonings, by hydrolyzing ribonucleic acid. Therefore, it can be said that it is particularly inexpensive and easily available.

[Specific description of the invention]

<Browning Reaction in Food> The present invention is directed to a method of causing a browning reaction, which is a reaction between an amino compound and a carbonyl compound, to occur in food to color the food, and to promote the browning reaction. This is an improvement of this method.

Therefore, the browning itself of the food as an object to be improved is essentially the same as the conventionally known one.

Therefore, the target foods include, for example, the following.

(A) Fish paste products: Chikuwa, kamaboko, grilled plate, etc.

(B) Breads: bread, sweet bread, French bread, and others.

(C) In addition, cookies, potato chips, rice crackers, oysters, soy sauce, coffee, and other foods that are baked or burnt using a browning reaction that does not depend on an enzyme reaction.

When these foods do not contain a sufficient amount of amino compounds and carbonyl compounds as themselves or as precursors thereof as a substrate for the intended browning reaction,
One or both of these substrates can also be added to the food. In this case, the addition can be selectively made to the surface of these excipients, in addition to the addition to fish pickles in the case of seafood paste products and flour dough in the case of breads.

Examples of the amino compound and the carbonyl compound or the precursor thereof to be added include, for example, amino acids such as glycine, alanine, valine, threonine, sodium glutamate, reducing sugars such as glucose, fructose, mannose, xylose, and ribose; fatty acids such as oleic acid; Examples include linoleic acid, linolenic acid, ascorbic acid, and others.

<Promotion of browning reaction> (1) Definition of "added" The present invention provides a browning of a food known per se as described above in the presence of an added nucleic acid-related substance or the like to produce a food. It is intended to promote the browning reaction.

Here, “added” means eliminating the promotion of browning that may be caused by a nucleic acid-related substance inherently contained in food. There is no limitation on the mode of addition as long as the nucleic acid-related substance and the like are intentionally added. Therefore, if there is an appropriate precursor compound for the intended nucleic acid-related substance, etc., it is added to the food in that form, and by subsequent processing, "in situ"
Changing to the desired compound is also one of the "added" embodiments referred to in the present invention.

In addition, when the term “added” is used, the addition of the reaction accelerator is not limited to the case where the reaction accelerator is substantially uniformly present in the food by performing this for fish meat and meat dough. Is applied only to the surface of the shaped body of the pickpocket or the dough, or is preferentially applied. In addition, even when the reaction accelerator is uniformly present inside the food, if the heating conditions are different between the inside of the food and the surface, for example, when the surface is heated to a higher temperature, only the surface is browned. It goes without saying that a change reaction can occur. In the present invention,
This is the reason why “in food” is specified without specifying the site of browning.

The nucleic acid-related substance added as a reaction accelerator in the present invention may be 5′-IMP or 5′-GMP, but it is known that these are added to foods as nucleic acid seasonings (foods). Is added so as to be present inside). Therefore, in the case of adding these two types of nucleotides to the interior of food, the amount of addition is limited in the present invention in order to avoid conflict with known examples (details will be described later).

(2) Browning Reaction Accelerator One of the browning reaction accelerators according to the present invention is a nucleic acid-related substance composed of (deoxy) ribonucleic acid or a hydrolyzate thereof. Here, “(deoxy) ribonucleic acid” means both ribonucleic acid and deoxyribonucleic acid. The term "hydrolyzate" means that the degree of polymerization of the polymer (deoxy) ribonucleic acid is significantly reduced by hydrolysis.

Thus, one example of a hydrolyzate is a nucleotide or nucleoside that is a constituent unit or “monomer” of these polymers, and another example is a polymer of these dimers or more.

Natural (deoxy) ribonucleic acid is obtained by polymerizing a unit nucleoside through a phosphate ester bond between 3'-5 'hydroxyl groups. In the present invention, a unit nucleotide effective as a reaction accelerator is the nucleoside of the nucleoside. 2'-, 3 '
Any of-, and 5 '(for ribose) or 3'- and 5'- (for deoxyribose) may be phosphorylated.

The nucleotides of the present invention also include those in which at least one of a plurality of hydroxyl groups of the nucleoside is phosphorylated, and those in which the phosphorylation of a given hydroxyl group is more than monophosphorylation. Things.

Since the nucleotide used as a reaction promoter in the present invention is not limited to 5'-phosphate, "(deoxy) ribonucleic acid" used as a reaction promoter in the present invention is a polymer of such a nucleotide. Accordingly, it is intended to include those having a bonding mode other than the 3'-5 'bonding. Therefore, the "nucleic acid-related substance" in the present invention can also be defined as "a nucleoside or a nucleotide or a polymer of a dimer or more of a nucleotide".

Another one of the browning accelerators according to the present invention is a phosphoric acid ester of sugar. The phosphate ester of the sugar of the present invention,
This includes those in which at least one of a plurality of hydroxyl groups of the saccharide is phosphorylated, and those in which the phosphorylation of a given hydroxyl group is more than monophosphorylation. The types of saccharides include monosaccharides to polysaccharides (monosaccharides and oligosaccharides are preferred).

Still another one of the browning reaction accelerators according to the present invention is:
It is a specific one of the bases constituting the nucleoside or nucleotide, ie, cytosine.

Representative examples of these reaction accelerators are as follows.

(A) ribonucleic acid (B) deoxyribonucleic acid (C) adenosine-2'-monophosphate (2'-AMP),
Adenosine-3'-monophosphate, adenosine-5'-monophosphate, cytidine-2'-monophosphate (2'-CM
P), cytidine-3'-monophosphate, cytidine-5'-
Monophosphate, inosine-2'-monophosphate (2'-IM
P), inosine-3'-monophosphate, inosine-5'-
Monophosphate, guanosine-2'-monophosphate (2'-GM
P), guanosine-3'-monophosphate, guanosine-
5'-monophosphate, thymidine-5'-monophosphate (5 '
-TMP), uridine-2'-monophosphate (2'-UMP),
Uridine-3'-monophosphate, uridine-5'-monophosphate, deoxyadenosine-5'-monophosphate (5'-
dAMP), deoxycytidine-5'-monophosphate (5'-
dCMP), deoxyguanosine-5'-monophosphate (5 '
-DGMP), deoxyuridine-5'-monophosphate (5 '
-DUMP) and at least one member selected from the group consisting of deoxyinosine-5'-monophosphate (5'-dIMP).
At least one riboside selected from the group consisting of cytidine, deoxycytidine, deoxyinosine and deoxyadenosine (E) cytosine (F) glucose-1-phosphate (G-1-P) , Glucose-6-phosphate (G-6-P), fructose-1-
Phosphoric acid (F-1-P), fructose-6-phosphate (F
-6-P), fructose-1,6-diphosphate (F-1,6-
DP), ribose-5-phosphate (R-5-P), galactose-1-phosphate (Gla-1-P).

These can be used together within each group and / or between groups. For example, non-regiospecific hydrolysis of a ribonucleic acid will produce a mixture of various 5'-nucleotides, and such a mixture can be used in the present invention. Insufficiently performing such hydrolysis will produce mixtures of nucleotide polymers of various degrees of polymerization (or even mixtures with unit nucleotides), but the present invention also uses such mixtures. be able to. Considering that the method for producing nucleotides is typically based on the hydrolysis of (deoxy) ribonucleic acid, a mixture comprising nucleic acid-related substances in the form of a mixture as described above is one of the preferred reaction accelerators. Can be. As nucleotides, 5′-UMP and 5′-CMP
Are particularly preferred.

The nucleic acid-related substances as described above are known per se, and can be obtained from known raw materials by a known method. For example, (deoxy) ribonucleic acids include those derived from animals or plants, and can be obtained from the animals and plants. Representative (deoxy) ribonucleic acids are yeast (especially brewer's yeast, baker's yeast, torula yeast, etc.) RNA and salmon milt DNA. In the case of yeast RNA, for example, yeast fungi The body can be obtained by washing the body with water, extracting with hot saline, removing the cells, and adding an acid to the extract to precipitate it ("nucleic acid fermentation",
1976, Amino acid / nucleic acid roundtable, edited by Kodansha, pp. 67-68). Extraction using alkali instead of salt
-37354 and JP-B-51-37355). In order to increase the purity of ribonucleic acid, for example, a method of treating cells with a mineral acid before extraction (JP-B-52-18200), A method of treating a ribonucleic acid extract with a protease (Japanese Patent Publication No. 42-1783)
No. 6) and a method of treating with sodium polyacrylate (Japanese Patent Publication No. 56-46837). The production of nucleotides or oligomers thereof by hydrolysis of (deoxy) ribonucleic acid is described in, for example, "Nucleic Acids-Biology, Chemistry and Physics" (1963, Shozo Osawa et al., Hirokawa Shoten), p.
55 to 55 or the like.

Nucleobases such as cytosine can be obtained by hydrolysis of nucleic acids or corresponding nucleosides or nucleotides.

These nucleotides, nucleosides, nucleobases and the like can also be produced by a fermentation method.

Esters of sugars such as glucose-1-phosphate can be obtained by extraction from animals and plants containing them. Alternatively, the sugar may be chemically phosphorylated.

In the present invention, it goes without saying that these nucleic acid-related substances and sugar phosphates may be used in the form of salts. Accordingly, in the present invention, for example, "(deoxy)
The term "ribonucleic acid" is intended to include its salts such as alkali metal salts, alkaline earth metal salts, ammonium salts and the like.

(3) Browning treatment Except for using the browning reaction accelerator as described above, the browning reaction promotion according to the present invention can be carried out by a method which is not essentially different from the conventional browning treatment.

The reaction accelerator may be added so as to be substantially uniformly present inside the food (for example, kneaded by adding it to fish meat or meat dough), or a shaped product of fish meat or meat dough May be applied to the surface. As described above, an amino compound and / or a carbonyl compound which is a substrate for the browning reaction may be added. In this case, the reaction may be performed by mixing with a reaction promoting substance.

The amount of the nucleic acid-related substance or the like as the reaction promoting substance may be at any suitable level. Since these reaction promoting actions are generally strong, a small amount of addition is generally sufficient. However, a relatively large amount can be added from the viewpoint of reducing the amount of the browning reaction substrate to be added or relaxing heating conditions. When the reaction accelerator is substantially uniformly present in the food, the amount added is 0.05% in the food.
It is usually about 2% by weight, preferably 0.1-1% by weight (based on the finished weight of the food).

When the nucleic acid-related substance or the like as the reaction accelerator is 5'-IMP or 5'-GMP, it may not be operable to distinguish it from the case where it is added as a nucleic acid seasoning.
Therefore, when 5'-IMP or 5'-GMP is added so as to be substantially uniformly present inside the food for differentiation from known examples, when added as such as a seasoning, Is added in an amount larger than the upper limit of 0.09% by weight, that is, 0.1% by weight or more, particularly 0.2% by weight or more.

In any browning treatment of any food, raw materials such as fish pickles, salt, sugar, flour, seasonings, etc. may be the same as usual, except for the addition of nucleic acid-related substances, etc. Just as it is. However, when adding nucleotides, the addition should be done in the latter half as much as possible in order to reduce the influence of phosphatase (having dephosphorylation activity) activity, and the temperature of the addition should be low. Is desirable. In addition, since the color is more easily formed in the baking process than usual, it is necessary to pay attention to the heating temperature and the heating time (the coloring is achieved at a lower temperature and a shorter time than the usual method).

In the present invention, "browning treatment" does not necessarily mean a treatment for browning alone. Because browning is promoted by heating, heating a food for cooking or the like usually results in browning.

<Experimental Example> The following experimental example is for specifically explaining the present invention.

 The reagents and the like used in the experiment are as follows.

(A) Ribonucleic acid: Tokyo Chemical Industry Co., Ltd. Ribonucleic acid (derived from yeast) (b) Deoxyribonucleic acid sodium salt: SIGMA CHEMICAL
Co.TYPE III (c) 5'-UMP: SIGMA CHEMICAL Co. or Yamasa Shoyu Co., Ltd. (d) 5'-TMP: SIGMA CHEMICAL Co. (e) Other nucleic acid-based substances: Yamasa Shoyu Co., Ltd. ) Other reagents: Wako Pure Chemical Industries, Ltd. The nucleotide and sugar phosphates used in Reference Examples and Examples used sodium salts.

Reference Example 1 2.4% glucose solution, 2.4% glycine solution or a solution containing 2.4% each of glucose and glycine, and 0.1% uridine-5'-monophosphate (5'-UMP) in these solutions
Autoclave treatment (121 ℃,
15 minutes), the absorbance of the solution before and after the reaction was measured at OD 430 nm, and the increase in the absorbance is shown in Table 1.

Addition of 5'-UMP to a solution containing glucose and glycine promoted browning significantly.

Reference Example 2 2.4% glucose solution, 2.4% glycine solution or a solution containing 2.4% each of glucose and glycine, and a solution prepared by dissolving glucose-6-phosphate (G-6-P) in these solutions to a concentration of 0.1%. Is autoclaved (121 ° C, 1
5 minutes), the absorbance of the solution before and after the reaction was measured at 0D430 nm, and the increase in the absorbance is shown in Table 2.

When G-6-P was added to the solution containing glucose and glycine, browning was remarkably promoted.

Reference Example 3 A nucleic acid-related substance or a phosphoric acid ester of sugar shown in Table 3 was added to a solution containing glucose and glycine at 2.4% each in an amount of 0.1%.
% And autoclaved (121 ° C, 1
5 minutes), the absorbance of the solution before and after the reaction was measured at 0D430 nm, and the increase in the absorbance is shown in Table 3.

Reference Example 4 5'-UMP was added to a solution containing glucose and glycine at 2.4% each.
Was dissolved to the concentration shown in Table 4 (g / 100 cc of solution) and subjected to autoclaving (121 ° C., 15 minutes). The absorbance of the solution before and after the reaction was measured at OD430 nm, and the increase in the absorbance was measured. The results are shown in Table 4.

The browning reaction was promoted even by a small concentration of 5% -UMP as low as 0.01%.

Reference Example 5 0.5% of various sugars shown in Table 5 were added to a 2.4% glycine solution.
And 5'-UMP
Was subjected to an autoclave treatment (121 ° C., 15 minutes), and the absorbance of the solution before and after the reaction was changed to O.
The increase in absorbance measured at D430 nm is shown in Table 5.

The addition of 5'-UMP to the sugar used as the substrate for the aminocarbonyl reaction accelerated the reaction.

Reference Example 6 A solution containing 1.2% each of xylose and glycine and a solution in which 5'-UMP was dissolved to 0.1% in these solutions were heated in a water bath, and the absorbance of the solution was measured with time at OD430 nm. The change in the absorbance is shown in Table 6.

By the addition of 5'-UMP, the browning reaction proceeded remarkably in a short heating time.

Example 1 In the production of baked kamaboko, scallop cod-free salted surimi
1000 g, salt 27 g, sugar 30 g, potato starch 70 g, sodium glutamate 7 g, mirin 30 g, and egg white 60 g were thoroughly rubbed, and 200 g of each of the substances shown in Table 7 was added in predetermined amounts and mixed well again. Put these in a mold and use a steamer for 10
Heated for minutes. After further cooling, the product was heated in an oven toaster for 7 minutes to obtain a product. The color of the resulting baked kamaboko was evaluated by 10 judges.

Example 2 In the production of baked kamaboko, scallop cod-free salted surimi
1000 g, salt 27 g, sugar 30 g, potato starch 70 g, sodium glutamate 7 g, mirin 30 g, and egg white 60 g were thoroughly rubbed, and 200 g of each of the substances shown in Table 8 was added in predetermined amounts and mixed well again. Put these in a mold and use a steamer for 10
Heated for minutes. After further cooling, the product was heated in an oven toaster for 7 minutes to obtain a product. The color of the resulting baked kamaboko was evaluated by 10 judges. Table 8 shows the results.

The most favorable of the three types was evaluated as one point.

The product to which G-6-P or R-5-P was added exhibited a preferable burning color as compared with the product to which these were not added. However, those to which R-5-P was added were colored orange after heating with a steamer.

Example 3 In the production of grilled kamaboko, scallop cod-free salted surimi
1000 g, salt 27 g, sugar 30 g, potato starch 70 g, sodium glutamate 7 g, mirin 30 g, and egg white 60 g were sufficiently rubbed, put into a mold, and heated with a steamer for 10 minutes. After cooling, cut into appropriate sizes, apply 0.5 ml of the solution shown in FIG. 9 per 100 cm ^{3 and} heat with an oven toaster for 8 minutes.
The product. The color of the resulting baked kamaboko was evaluated by 10 judges. Table 9 shows the results.

The most favorable one of the four types was evaluated as one point.

0.4% 5'-UMP and 5% glucose mixed solution or 1
The one coated with the 5% -UMP solution showed a preferable baking color as compared with the one coated with another solution.

Example 4 In the manufacture of cookies, 400 g of flour, 12 salt-free butters
0 g, 160 g of sugar, 2 g of baking powder, 2 g of salt, and 2 eggs were mixed, and a predetermined amount of each substance shown in Table 10 was added to 100 g of the mixture, followed by mixing again. These were heated in an oven toaster for 4 minutes to obtain products. The color of the resulting cookies was evaluated by 10 judges. Table 10 shows the results.

The most favorable one of the four types was evaluated as one point.

The product to which 5'-UMP and glucose were mixed and added and the product to which 5'-UMP was added exhibited a more preferable baking color than the other products.

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Claims (6)

(57) [Claims] 1. An aminocarbonyl reaction accelerator for food, comprising a nucleic acid-related substance comprising (deoxy) ribonucleic acid or a hydrolyzate thereof or a phosphate ester of sugar as an active ingredient. 2. The aminocarbonyl reaction accelerator for foods according to claim 1, wherein the active ingredient is uridine-5'-monophosphate or cytidine-5'-monophosphate. 3. The aminocarbonyl reaction accelerator for food according to claim 1, wherein the active ingredient is cytosine. 4. A method for producing a colored food by causing an aminocarbonyl reaction in a food to produce a colored food, wherein the aminocarbonyl reaction is carried out by adding an added (deoxy) ribonucleic acid or a nucleic acid-related substance comprising a hydrolyzate thereof or a sugar. To promote the aminocarbonyl reaction by performing the reaction in the presence of an aminocarbonyl reaction accelerator containing a phosphoric acid ester as an active ingredient (if the nucleic acid-related substance is inosine-5'-
When monophosphoric acid or guanosine-5'-monophosphate is added to food, the amount of the nucleic acid-related substance to be added is such that the content in the food to be subjected to the aminocarbonyl reaction becomes 0.1% by weight or more. ).
Aminocarbonyl reaction promoting method. 5. The aminocarbonyl reaction accelerator according to claim 4, wherein the active ingredient is uridine-5'-monophosphate or cytidine-5'-monophosphate. 6. The method for accelerating an aminocarbonyl reaction according to claim 4, wherein the active ingredient is cytosine.