JP4822272B2 - How to improve the fragrance of food or medicine - Google Patents

Description

  The present invention relates to a method for improving the aroma of a food or pharmaceutical product. More particularly, the present invention relates to a method for effectively imparting or enhancing a fragrance or sweet scent, or a fragrance or sweet scent and a baked color to food or medicine.

  The “scent” and “baked color” of the food have a great influence on the deliciousness of the food. Among them, the aroma components generated when the food is heated for processing, storage, cooking, etc. “Color” is the main cause of the unique flavor of the food. The aroma and baked color generated by heating food are caused by an aminocarbonyl reaction (sometimes referred to as Maillard reaction) between sugars and amino acids or proteins in the food. For example, the characteristic aroma and roast color generated when roasting barley and coffee beans are representative.

Many studies for enhancing the taste of food using aminocarbonyl reaction have been conducted. For example, Patent Document 1 discloses a method for enhancing the flavor by devising the production process of barley tea. No. 2 reports a method for producing tofu with a rich scent of soybeans by adding sugar to the production process followed by heat treatment. Further, Patent Document 3 discloses a method for efficiently applying a preferred baked color to foods during microwave heating. As described above, a method for enhancing a specific scent of a specific food or imparting a preferable scent or baking color has already been reported.
Further, the present inventors have reported in Patent Document 4 that a Maillard reaction-modified protein with improved gel properties can be obtained by Maillard reaction between the sugar and protein using D-psicose which is a rare sugar. .

JP 2006-42742 A JP 2005-6505 A Japanese Patent Laid-Open No. 8-131092 JP 2004-269359 A

  However, there has been no report on a method that can efficiently impart or enhance a preferred aroma, sweet scent, and / or a preferred baking color that leads to the deliciousness of many foods that are more versatile.

The inventors of the present invention have now studied the aroma components generated by the aminocarbonyl reaction using rare sugars and the characteristics of the baked color. Therefore, the present inventors analyzed aroma components generated by aminocarbonyl reaction using rare sugars, and aimed to use and improve rare sugars in perfumes such as foods and pharmaceuticals.
That is, the object of the present invention is to effectively impart or enhance a preferred fragrance component that leads to the deliciousness of food or pharmaceutical product among the fragrance components generated during heat treatment in food or pharmaceutical product to the food or pharmaceutical product. It is possible to provide a method capable of efficiently imparting or enhancing a preferable baked color as necessary.

  As a result of intensive studies to solve the above problems, the present inventors have found that D-psicose, which is one of the rare sugars, is compared with D-fructose by aminocarbonyl reaction by heating between amino acids and proteins. It is found that pyrazines and furanones that are known to give a favorable flavor to foods and pharmaceuticals are produced more clearly, and D-psicose can be used as a partner sugar for aminocarbonyl reactions with amino acids and proteins. The present inventors have found that this is a method for efficiently imparting or enhancing a food or medicine with a preferable aroma component that leads to the deliciousness of food and ease of incorporation of medicines.

  Furthermore, the present inventors have also found that the aminocarbonyl reaction using D-psicose further proceeds more efficiently than D-fructose (fructose), and it is possible to attach a baked color more quickly and easily. The present invention has completed a method capable of efficiently imparting or enhancing a fragrance or sweet scent to foods or pharmaceuticals, and efficiently imparting or enhancing a preferred baking color as needed.

The present invention consists of pyrazines and / or furanones that are produced more by aminocarbonyl reaction using D-psicose and L-phenylalanine than aminocarbonyl reaction using glucose or fructose and L-phenylalanine. Incorporating L-phenylalanine into a food or medicine having a functional characteristic that there is no increase in calories based on the psicose modified by aminocarbonyl reaction using psicose and L-phenylalanine , containing an aroma component, or The gist is a method for improving the fragrance of a food or medicine characterized by being produced during the production of the medicine.

The method for improving the fragrance of the food or medicine of the present invention is a heated fragrance component that is generated by adding or adding D-psicose and L-phenylalanine before the heating step. by keeping to or added added D- psicose and L- phenylalanine, an amino carbonyl reaction with D- psicose and L- phenylalanine, it compared with aminocarbonyl reaction with glucose or fructose and L- phenylalanine L which has a functional characteristic that there is no increase in calories based on the psicose modified by aminocarbonyl reaction using psicose and L-phenylalanine , which contains a fragrance component consisting of pyrazines and / or furanones, which is produced more -Phenylarani The blending a food or pharmaceutical, or be generated during the manufacture of food or pharmaceutical and gist a method characterized.

The heating step is a step with heat treatment performed during the production of food or pharmaceutical, and the method for improving the fragrance of the food or pharmaceutical of the present invention, D-psicose before the step with heat treatment performed during the production of food or pharmaceutical and by previously added to or added L- phenylalanine, D- by psicose and L- phenylalanine aminocarbonyl reactions with, resulting more than compared to the aminocarbonyl reaction with glucose or fructose and L- phenylalanine , containing aroma component consisting of pyrazines and / or furanones, psicose and L- phenylalanine food L- phenylalanine has the functional property that there is no increase in calories based on modified the psicose by aminocarbonyl reaction with Others can be incorporated into pharmaceutical or be generated during the manufacture of food or pharmaceutical and gist a method characterized.

The method for improving the aroma of the food or pharmaceutical product of the present invention is a step involving a heat treatment in which a heating step is performed when a flavor is formed in advance by forming a fragrance by the reaction of D-psicose and L-phenylalanine . D -psicose is added or added prior to the step involving the heat treatment performed when producing a flavor for food or pharmaceuticals by forming a fragrance by the reaction of D-psicose and L-phenylalanine. And psicose containing an aromatic component composed of pyrazines and / or furanones, which is produced by aminocarbonyl reaction using L-phenylalanine and glucose or fructose and aminocarbonyl reaction using L-phenylalanine more than that. And L And characterized in that to produce L- phenylalanine has the functional property that there is no calories increased based on modified the psicose by aminocarbonyl reaction with phenylalanine be incorporated into food or pharmaceuticals, or food or during the manufacture of a medicament This is the gist of the method.

  Rare sugars are defined as “monosaccharides and their derivatives that rarely exist in nature”, and their chemical synthesis is difficult, so there has been little research on substitutes for commonly used sugars. However, the present inventors have developed a method for mass-producing D-psicose from D-fructose (fructose) using D-tagatose-3-epimerase to enable industrial utilization of D-psicose. D-psicose is a non-caloric sugar that has a weaker sweetness than sucrose and is very soluble in water. In recent years, foods have been required to be low in calories as well as delicious with increasing diet-oriented, and non-calorie has become an important point in using the functions of sugar. Psicose is a highly useful sugar.

  ADVANTAGE OF THE INVENTION According to this invention, in a foodstuff or a pharmaceutical, it is possible to effectively impart or enhance a preferred aroma component that leads to the deliciousness of a food or a pharmaceutical product among the aroma components generated when heat-treated. If necessary, a preferable baked color can be efficiently imparted or enhanced.

  By adding or pre-adding D-psicose before the heating process of the target food or drug, it is possible to generate a large amount of preferable aroma components that lead to the deliciousness of the food or drug during the heating process, Since a preferable baked color can be efficiently imparted or enhanced as needed, it is possible to provide a delicious food or a pharmaceutical product that has been imparted or enhanced with a savory or sweet fragrance, and a desired baked color as necessary. It has the effect of being able to.

Considering the mechanism by which we perceive odors, odor molecules enter the nasal cavity with the flow of air and stimulate special sensory receptor cells (olfactory cells). Then, an electrical signal (impulse) is generated from it, enters the olfactory bulb, which is a part of the brain through the olfactory nerve, and is sent through the piriform leaves and the amygdaloid nucleus to the higher central part of the brain, where it is the first smell sense. Occur.
In the case of odor, the sensation of smell is low because the trigeminal nerve distributed in the nostril as an auxiliary nerve, the glossopharyngeal nerve distributed in the pharynx, and the vagus nerve distributed in the larynx are also stimulated by the odor substance. Is a complex sensation caused by the excitement of these nerves.
As can be seen, in order for an odor sensation to occur, it is necessary for the odor molecule to reach the nasal odor receiving cells and provide stimulation. Therefore, some physicochemical conditions are required for fragrant substances. The generally accepted conditions for scented substances are as follows.
1) The molecular weight is 300 or less and it is volatile 2) It has both water-soluble and oil-soluble properties 3) It has functional groups and unsaturated bonds in the molecule

  The origins of aroma components in foods are diverse, but from the viewpoint of their production mechanisms, 1) those that are biosynthesized through the normal metabolic processes of living organisms (food ingredients), 2) tissues of fresh food, cell cutting, grinding It can be broadly classified into those produced by biodegradation caused by crushing, and 3) produced by chemical reactions caused by processing, cooking, and the like. However, there are a wide variety of food ingredients, and there are few cases where a single ingredient is used, and many are used in a mixed state of plant and animal ingredients. “Freshness” is an important quality factor in vegetable foods, especially vegetables and fruits, and many of the aroma components that characterize “freshness” are produced by enzymatic oxidation of lipids. In addition, non-enzymatic changes in lipids in animal and plant foods are an important problem encountered in the processing, storage and distribution stages, and in particular, volatile carbonyl compounds produced by non-enzymatic lipid oxidation reactions are important. Heating aroma is an important aroma that is formed during food processing. The formation of aroma by the reaction of sugar and amino acid has been known for a long time, and now the reaction is widely applied to the production of food flavors. The study shown in the examples was aimed at examining the generation of these heated aroma components and their aroma characteristics.

When heated for the purpose of processing, storing and cooking foods, it produces a unique aroma depending on its ingredients and processing conditions. In general, this type of scent is an aroma that gives a food-specific flavor and is called a heated aroma. The main precursors are sugars, amino acids and proteins. Even when these are heated alone, various volatile substances are generated by the thermal decomposition, but the most characteristic is aroma generation by the aminocarbonyl reaction between sugar and amino acid or protein. The reaction formula is simply shown in FIG. The carbonyl group of the sugar and the amino group of the amino acid undergo dehydration and condensation to form a substance called a Schiff base. When the nitrogen atom of this Schiff base is protonated, the electron affinity of the carbon atom is remarkably increased, which occurs following enolization of the nitrogen glycoside in the amino reaction with the sugar, the Amadori rearrangement (Hines rearrangement), and more. It is known that it becomes a driving force for elimination of a hydroxyl group and the like from the β-position.
The aroma produced by such an aminocarbonyl reaction is roughly divided into three stages.
The first step is the production of gaseous substances at room temperature and the production of substances by sugar cyclization. Production of volatile substances such as carbon dioxide, ammonia and hydrogen sulfide, and sugar cyclization by dehydration, furans such as furfural and HMF, furanones such as sotron, 4H-pyran-4-ones such as maltol and DDMP And so on.
The second stage is the production of aldehydes by Strecker decomposition. Strecker degradation occurs with α-dicarbonyl (glyoxal, methylglyoxal, glucosone, 3-deoxyglucosone, etc.) and α-amino acid generated during the reaction, and the α-amino acid is decarboxylated to produce an aldehyde with one less carbon number. Generate.
The third stage is the formation of a heterocyclic compound. Amino reductone produced by Strecker decomposition of α-dicarbonyl compounds is condensed and cyclized, and many are heterocyclic compounds having nitrogen or sulfur atoms. This includes pyrazine, pyrrole, pyridine and thiazole derivatives, which are important as roasting aroma components for foods and the like. Table 1 shows the aromas produced by the reaction between glucose and amino acids.

D-psicose is a sugar that is currently mass-produced among rare sugars. Psicose is one of the hexoses having a ketone group among monosaccharides. This psicose is known to have D-form and L-form as optical isomers. Here, since D-psicose is a known substance but rarely exists in nature, it is defined as “rare sugar” according to the definition of the International Society of Rare Sugars. D-psicose is a D-form of psicose classified as ketose and is a hexose (C6H12O6). Such D-psicose may be obtained by any means including those extracted from the natural world and those synthesized by chemical or biosynthesis methods. Relatively easily, for example, it may be prepared by a technique using epimerase (for example, see JP-A-61-225776). The obtained D-psicose solution can be purified by a method such as deproteinization, decolorization, desalting, etc., if necessary, and concentrated to collect a syrup-like D-psicose product. A fraction with a purity of 99% or more can be easily obtained by fractionation and purification. Such D-psicose can be used as a monosaccharide as it is, and is also expected to be used as various derivatives as required.
Regarding a derivative of D-psicose, a compound obtained by converting a molecular structure from a certain starting compound by a chemical reaction is referred to as a derivative of the starting compound. Derivatives of hexose containing D-psicose include sugar alcohols (when monosaccharides are reduced, aldehyde groups and ketone groups become alcohol groups and polyhydric alcohols with the same number of carbon atoms) and uronic acids (monosaccharides) This is an oxidized version of the alcohol group. Naturally, D-glucuronic acid, galacturonic acid, and mannuronic acid are known. Amino sugar (the OH group of the sugar molecule is replaced with NH2 group, glucosamine, chondrosamine, coordination Are common), but are not limited thereto.

D-psicose can be used in the form of a mixture with D-fructose. The complex crystalline saccharide containing D-psicose and D-fructose, which has already been developed, will be described with respect to the mixture of D-psicose (see JP-A-2001-11090).
In order to produce such a mixed carbohydrate, it is advantageous to prepare a mixture of D-psicose and D-fructose by allowing D-ketohexose 3-epimerase to act on D-fructose to undergo an epimerization reaction. it can. The proportions of D-psicose and D-fructose in the prepared sugar are usually about 20-25% and about 80-75%, respectively, per solid. If necessary, it is also optional to produce a mixed carbohydrate of this proportion of D-psicose and D-fructose by allowing D-ketohexose 3-epimerase to act on D-psicose. It is also possible to produce a mixture of D-psicose and D-fructose by epimerizing D-fructose using an inorganic and / or organic catalyst. In that case, since the purity of D-psicose is usually low, D-psicose is removed by adding D-psicose or removing D-fructose by solvent fractionation, membrane separation, column fractionation, yeast treatment, enzyme treatment, etc. It is also possible to increase the purity of. Of course, a mixture of D-psicose and D-fructose may be prepared by simply blending D-psicose and D-fructose in an arbitrary ratio.
A sugar solution containing D-psicose and D-fructose is used to produce a complex crystalline carbohydrate containing D-psicose and D-fructose, which is collected and contains D-psicose and D-fructose. A complex crystalline saccharide may be produced, and the production method thereof is a saccharide containing D-psicose and D-fructose, preferably a composition ratio of D-psicose and D-fructose of about 1: 2 to 1. : 4 high concentration solution, preferably an aqueous solution having a solid concentration of 70 to 98% (w / w), for example, in an auxiliary crystal can, and a complex containing D-psicose and D-fructose as seed crystals An appropriate amount, preferably about 0.01 to 10%, of a crystalline saccharide may be contained, mixed and assisted crystallization to form a mass kit, which may be powdered and collected. At this time, a hydrophilic organic solvent such as ethanol may be added to a sugar solution containing D-psicose and D-fructose to promote the production of a complex crystalline carbohydrate containing D-psicose and D-fructose.

With regard to D-psicose alone or a mixture of D-fructose and D-psicose, it has become possible to develop foods / sweeteners or pharmaceuticals that use aroma components generated by the aminocarbonyl reaction or impart a baked color with aroma. That is, as foods or pharmaceuticals, there are foods containing sweeteners, sugar-coated tablets, etc., but compositions containing D-psicose and / or derivatives thereof and / or mixtures thereof, It can be used as an edible material that imparts a baked color together with an aroma component or aroma.
For example, a case where D-psicose is used as a sweetener will be described. D-psicose crystals, syrup, complex of D-psicose and D-fructose When using crystalline saccharide as a sweetener, for example, flour, glucose, maltose, isomerized sugar, sucrose, trehalose, honey, Other sweetness such as maple sugar, sorbitol, xylitol, lactitol, maltitol, dihydrochalcone, stevioside, α-glycosyl stevioside, rakanka sweet, glycyrrhizin, L-aspartyl-L-phenylalanine methyl ester, saccharin, glycine, alanine etc. It may be used by mixing with an appropriate amount of one kind or two or more kinds of ingredients, and can also be used by mixing with a bulking agent such as dextrin, starch, lactose and the like. It is also optional that the form is used as it is or mixed with a bulking agent, excipient, binder or the like, if necessary, and formed into granules, spheres, tablets, rods, plates, cubes or the like. D-psicose sweetness is refined and refreshing, without the discomfort associated with bitterness and astringency like saccharin, but rather similar to the sweetness of fructose. The sweetness is about 70% of sucrose. The sweetness of D-psicose and complex crystalline saccharides containing D-psicose and D-fructose harmonizes well with other tastes of various substances such as acidity, salt to taste, astringency, umami, and bitterness. It can be advantageously used for sweetening and taste improvement of ordinary foods and beverages, and for quality improvement.

  In the present invention, when sugars such as reducing sugars are used in foods that are subjected to heat treatment in the production process and / or foods that are heat-treated during cooking, the sugars that are usually used are replaced. By using D-psicose in addition to its sugar, it produces an aroma component that gives a favorable flavor, and exhibits the inventive function of efficiently imparting or enhancing a desired baked color to food as needed Can be made. Furthermore, when using it, take into consideration the characteristics of the food used, the level of flavor that you want to give, the level of baked color, and when using other sugars, the amount of sugar used, etc. The mode of use and the like may be examined within the scope of studies usually conducted in the course of food development, and there are no particular items to be noted when using D-psicose.

Similarly, when sugar is used in normal food, especially when sugar is used in food for flavoring or baking using aminocarbonyl reaction by heat treatment, in place of sugar normally used for the purpose, or The present invention can be easily carried out by using D-psicose in addition to the sugar.
For example, D-psicose is used on the surface of microwave foods such as gratin, doria, pizza, baked potatoes, grilled rice balls, sweet potatoes, cakes, etc. Furthermore, by adding sugars such as sucrose, glucose, fructose, maltose, xylose, galactose, arabinose, ribose, etc., it is possible to further enhance the preferred roast color that occurs when food is heated in a microwave oven, and its fragrance The scent can also be enhanced.
In this case, the method of applying D-psicose to the surface of the microwave food is not limited, but usually D-psicose is added with sugars such as sucrose, glucose and fructose as necessary, and margarine and the like are added to the aqueous solution of amino acids. Emulsified oils and fats are added to form a paste-like mixture, which is then applied, kneaded, sprinkled or sprinkled and processed into a microwave-cooked food. The amino acid is at least one selected from protein hydrolysates obtained by hydrolyzing proteins such as glycine, alanine, phenyl, arginine, lysine or gelatin, egg white, soybean or wheat with acid or enzyme. It can be easily obtained as a raw material or industrial raw material. The emulsified fat is not limited as long as it is an emulsified fat that is usually used as a food material.

The amount of D-psicose used may be selected on the basis of what kind of food is to be obtained as described above. For example, when an amino acid is present as the partner of the aminocarbonyl reaction, D-psicose alone In this case, the amount of amino acid may be about 0.1 to 3 times, more preferably about 0.2 to 2 times the weight of amino acid. In any case, the lower limit and upper limit of the amount used consider the degree of fragrance and baked color obtained, and the upper limit of the amount used is not only the invention function that the fragrance is too strong and the baked color is attached, but also the food form It may be determined in consideration of the degree of sweetness indicated by D-psicose.
For example, when D-psicose is used together with emulsified oils and fats, the amount of emulsified oils and fats is not limited, but usually 5 to 20 times (by weight) is used with respect to D-psicose or a mixed sugar or amino acid with other sugars. . Moreover, when using emulsified fats and oils, D-psicose or mixed sugars with other sugars and amino acids, the amount of mixed sugars with D-psicose or other sugars is not limited, but usually 0.5 to amino acids. Use ~ 3 times (weight).
In addition to the above foods, it can be widely applied to, for example, pilaf, fried rice, spaghetti, croquettes, mentakatsu, shumai, spring rolls, piroshki or bread, and the cooking method is not limited. The obtained processed food is heated and cooked in a microwave oven. The cooking time varies depending on the state of the processed food (room temperature, refrigerated, frozen), the type / amount, the aroma or taste of the baked color, the performance of the microwave oven, etc., but usually it may be about 30 seconds to 15 minutes.

The above has basically described the food for which the heat treatment is performed in the production process and / or the food for which the heat treatment is performed during cooking. However, in the present invention, the heated aroma as an important aroma formed during the processing of the food. Can be applied to the production of food or pharmaceutical flavors. In addition, an aroma can be formed in advance by the reaction of sugar and amino acid, and it can be used as a food or pharmaceutical flavor. Therefore, the method for improving the fragrance of a food or a pharmaceutical using an aroma component generated by the aminocarbonyl reaction using D-psicose of the present invention performs the heat treatment during food production and / or cooking. It can be used as a sweetener used in foods, or as a flavor for foods or pharmaceuticals subjected to heat treatment.
Various foods that can be applied are, for example, soy sauce, powdered soy sauce, miso, powdered miso, moromi, horsetail, fried potato, mayonnaise, dressing, vinegar, three cups of vinegar, powdered sushi vinegar, Chinese food, tentsuyu, noodle soup, sauce , Ketchup, grilled meat sauce, curry roux, stew element, soup element, dashi element, compound seasoning, mirin, new mirin, table sugar, coffee sugar, etc. (Flavor) It can be advantageously used as an improving agent, a quality improving agent and the like.
In addition, for example, various Japanese sweets such as rice crackers, hail, rice cakes, rice cakes, buns, eels, eels, sheepskin, water sheep rice cakes, brocade balls, jellies, castellas, rice cakes, bread, biscuits, crackers, cookies, pies, puddings , Butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy and other Western confectionery, ice cream, sorbet and other ice confectionery, fruit syrup pickles, ice syrup and other syrups, flower Paste such as paste, peanut paste, fruit paste, fruit such as jam, marmalade, syrup pickles, confectionery, processed foods of vegetables, breads, noodles, cooked foods such as cooked rice, artificial meat, Fukujin pickled, lettuce pickled , Senzuke, Rakkyo pickles, etc. Pickles, pickled vegetables such as Chinese cabbage pickles, ham, sausage and other livestock products, fish ham, fish sausages, fish products such as seaweed, chikuwa, tempura, sea urchin, squid salted, Variety of delicacies such as vinegared kombu, sakisume, blowfish mirin, paste, wild vegetables, sushi, small fish, shellfish made with shellfish, stewed beans, potato salad, side dish foods such as kombu rolls, dairy products, fish meat , Animal meat, fruit, vegetable bottling, canned food, synthetic liquor, fruit liquor, western liquor, liqueur and other liquors, coffee, cocoa, juice, carbonated beverages, lactic acid beverages, lactic acid bacteria beverages and other soft drinks, pudding mix, hot cakes Premix powders such as mixes, instant juices, instant coffee, instant juice powders, instant soups such as instant soups, and other sweeteners, as well as a taste improvement Agent, can be advantageously used as such as quality-improving agent.
Compositions containing D-psicose and / or its derivatives and / or mixtures thereof are less sweet, such as ramen, noodles, udon, and potatoes made from flour and starch, as well as mashed potatoes, salads and croquettes. Can be used for foods that do not require it. Moreover, it is made from wheat flour, starch or rice flour as the main raw material, and can be used for the same purpose in confectionery and breads which do not require much sweetness. Thus, it can be seen that the composition in which the D-psicose and / or derivative thereof and / or mixture thereof according to the present invention is blended has a very wide range of use amount.

Moreover, sugar-coated tablets can be mentioned as examples in which an aroma is formed in advance by the reaction of sugar and amino acid and used as a food or pharmaceutical flavor. Sugar-coated tablets are widely used as pharmaceuticals and foods such as solid preparations because they are covered with a sugar coating layer on the surface so that they are easy to take and have good appearance, and also have a moisture-proof effect. . For the manufacture of sugar-coated tablets, in general, the process of applying a sucrose solution to the tablets and drying is repeated to finish the formation of the sugar-coated layer, the shape of the tablets is adjusted to an ellipse, wax is applied, and glazing is applied to the sugar-coated tablets It is what.
In general, sucrose solutions for sugar coating are prepared by adding gelatin, gum arabic, polyvinylpyrrolidone or the like as a binder to sucrose as a base to increase the strength of the sugar coating layer of the sugar-coated tablet. Further, powders such as talc, calcium sulfate, calcium phosphate, and precipitated calcium carbonate are added as necessary. The present invention can be easily carried out by forming a fragrance in advance by the reaction of D-psicose and an amino acid in place of or in addition to the sugar used for the sugar-coated tablet and using it as a flavor. Drugs, especially those with a strong odor that are difficult to swallow and those that are bitter and hard to swallow, have been improved with sugar-coated tablets, but there are still some that are difficult to swallow, so the aminocarbonyl reaction using D-psicose of the present invention The sugar-coated tablet containing the aromatic component generated by the above can provide a sugar-coated tablet that is easier to drink.
There are many other medicines that are difficult to drink, as is well known. Since barium has a unique odor and taste, it is already easy to drink with some additives, but it could be improved further. It is also possible to use the aromatic component generated by the aminocarbonyl reaction using D-psicose of the present invention in order to give an aroma and sweetness to those which are difficult to drink with such liquid drugs and diagnostic aids. . Some medicines are in powder form, and similarly, the addition of aroma components generated by the aminocarbonyl reaction using D-psicose of the present invention may make it easier to drink.

  Details of the present invention will be described using test examples and the like. The present invention is not limited to these test examples.

In the aminocarbonyl reaction shown in FIG. 1, the present inventors focused on rare sugars, particularly D-type ketohexose (D-psicose, D-sorbose, D-tagatose). Its structural formula is shown in FIG. Rare sugars are monosaccharides that exist only in trace amounts in nature compared to “natural monosaccharides” that exist in large quantities in nature among monosaccharides. There are about 7 types of natural monosaccharides, such as glucose and fructose, and about 50 types of rare sugars. Rare sugars are not only applied to the human body, such as pharmaceuticals, functional foods, and cosmetics, but also other animals, insects, microorganisms, etc. In addition to its application to plants, it is also attracting attention for its application as industrial materials.
Therefore, the present inventors analyzed aroma components generated by aminocarbonyl reaction using rare sugars, and aimed to use and improve rare sugars in perfumes such as foods and pharmaceuticals.

[experimental method]
(Preparation of heated aroma used for sensory test)
D-fructose and D-psicose 300mg (1.66mmol) are put in separate test tubes (inner diameter 0.8mm x height 120mm), and equimolar 20 amino acids (made by Wako Pure Chemical Industries, special grade) Added each. At this time, a sample containing only a sugar to which no amino acid was added was prepared as a control. To each of these, 6.0 ml of 0.2 M phosphate buffer (pH 7.0) was added, and each was well shaken to dissolve well. Aluminum heater (THERMO ALUMI BATH ALB-220, manufactured by Iwaki Glass Co., Ltd.) React at 100 ° C for 1 hour, observe the color, then micropipette each 1.5ml into brown bottles warmed with aluminum heater (60 ° C) And immediately covered the lid. After all the transfer from the test tube to the brown bottle, it was used for sensory test.

<Selection of sensory evaluation language (see Tables 2 and 3)>
The sensory test was performed by three panelists (one male, two females, average age 28 years). The amino acids used were 20 commonly known amino acids, including those reacted with only sugars without any other amino acids, and a total of 42 samples for each fructose and psicose were presented to the panel in two days.
The panelists were asked to express their odors in a wide range, and they collected words that were common among the panelists. The room temperature was kept at 27 ° C and the sample bottle temperature at 60 ° C.

<Implementation of a sensory test to fill in a score (see Figs. 3 and 4)>
About L-phenylalanine which shows a characteristic odor by the reaction with sugar, it reacted with fructose or psicose, and in order to have you smell the difference of both smells finely, I had you smell two smells at the same time. The sensory test was conducted using 13 panelists (8 men, 5 women, average age 26 years). The panelists were asked to rate each of the odor words they decided on, based on a five-point scale: 0 (no smell at all), 1 (somewhat smell), 2 (slightly smell), 3 (smells), and 4 (smells clearly). The room temperature was kept at 27 ° C and the sample bottle temperature at 60 ° C.

<About statistical processing>
The obtained scores were tested for significance by Wilcoxon's sign rank test. The idea of Wilcoxon's sign rank test is basically the same as the test of the difference between population means when there is a correspondence. This method can check whether or not there is a difference between two corresponding groups even if the data is rank data or the population distribution is unknown.

<GC, GC / MS analysis>
D-fructose and D-psicose (1.80 g (0.01 mol)) were placed in separate 200 ml round bottom flasks, and 1.65 g (0.01 mol) of L-phenylalanine was added. To this was added 40 ml of 0.2M phosphate buffer (pH 7.0), and the mixture was well shaken to dissolve well. Then, a ball-in cooler was attached, and the mixture was reacted for 1 hour with a mantle heater (100 ° C.). 30 ml of this reaction solution was liquid-liquid extracted with 20 ml of dichloromethane for 5 hours, and then dried over anhydrous sodium sulfate. It moved to the self-made concentration tube, 0.02 microliters of toluene was added as an internal standard substance, and it concentrated under nitrogen stream (flow rate 30 ml / min) for 6 hours. This concentrate was analyzed by GC and GC / MS under the following conditions. In addition, the retention index was automatically calculated from the retention time obtained by GC by the program of the data processor. The calculation formula is also shown below.

GC
Device: Hewlett Packard 5890A
Data processor: Shimadzu Chromatopack C-R6A
Column: FS-WCOT capillary column
： DB-WAX (60m × 0.25mmφ)
Column temperature: 35 ℃ → 200 ℃ (2 ℃ / min)
Purge: 0.5 min ON
Split ratio: 87: 1
Carrier gas: N ₂ (flow rate 0.52ml / min)
Sample vaporization temperature: 230 ° C
Sample detector temperature: 230 ° C
Detector: Hydrogen flame ionization detector (FID detector)

GC / MS
Equipment: JEOL JMS―SX102AQQHybrid Mass Spectrometer
Data processing equipment: JEOL JMS-DA5000
Column: FS-WCOT capillary column
： DB-WAX (60m × 0.25mmφ)
Column temperature: 35 ℃ → 200 ℃ (2 ℃ / min)
Purge: 0.5 min ON
Split ratio: 91: 1
Carrier gas: He (flow rate 0.44ml / min)
Sample vaporization temperature: 230 ° C
Ionization method: EI
Ionization voltage: 70eV

Retention index formula

<Measurement of browning degree by ultraviolet and visible spectroscopy>
D-fructose and 300 mg (1.66 mmol) of D-psicose were placed in separate test tubes (inner diameter 0.8 mm × height 120 mm), and equimolar L-phenylalanine 276 mg (1.66 mmol) was added. To this, 6.0 ml of 0.2M phosphate buffer (pH 7.0) was added, and it was well dissolved by shaking lightly. The reaction was performed at 100 ° C. with an aluminum heater (THERMO ALUMI BATH ALB-220, manufactured by Iwaki Glass Co., Ltd.), 100 μl was taken every 10 minutes, diluted, and the absorbance was measured under the following conditions. A total of 10 measurements were taken up to 100 minutes.

UV / VIS
Equipment: JASCO V-520SR UV-VIS spectrophotometer
Cell: Square quartz cell (optical path length 0.1cm x width 1.0cm)
Solvent: 0.2M phosphate buffer
Wavelength: 200nm ~ 600nm

<Measurement of reactivity by NMR spectroscopy>
D-fructose and D-psicose 60 mg are weighed into separate 10 ml eggplant-shaped flasks, and 1 drop of Sodium 3- (trimethylsilyl) propionate-d ₄ (heavy aqueous solution 5000 ppm) is added as a standard substance, and dissolved in 0.6 ml heavy water. The sample was immediately transferred to an NMR tube, and a ¹³ C-NMR signal was measured under the following conditions. Then, every few seconds, fructose was measured 3 times and psicose was measured 4 times, and the change in structure after dissolving in water was examined. The first measurement took about 4 minutes.
NMR
Equipment: JEOL JNM-A400 nuclear magnetic resonance equipment
Solvent: Heavy water Standard substance: Sodium 3- (trimethylsilyl) propionate-d ₄
Frequency: 400MHz

<GC-Sniffing analysis>
D-fructose and 7.20 g (0.04 mol) of D-psicose were placed in separate 500 ml round bottom flasks, and 6.60 g (0.04 mol) of L-phenylalanine was added. 160 ml of 0.2M phosphate buffer (pH 7.0) was added to this, and it was dissolved by shaking lightly. Then, a ball-in cooler was attached, and the mixture was reacted with a mantle heater (100 ° C.) for 1 hour. 150 ml of this reaction solution was subjected to liquid-liquid extraction with 100 ml of dichloromethane for 8 hours, and then dried over anhydrous sodium sulfate. This was filtered through a funnel, transferred to a 100 ml eggplant type flask, and concentrated to about 10 ml with an evaporator. The sample was transferred to a self-made concentration tube, concentrated for 6 hours under a nitrogen stream (flow rate 30 ml / min), and subjected to GC-Sniffing analysis under the following conditions.
GC-Sniffing attached a Sniffing-Port (not shown) to the column outlet and sniffed the smell that came out through the TCD detector. For smelling sniffing, I was tired from olfactory sensation, so I did not keep sniffing for more than 15 minutes. Moreover, since the component flowing out from the column was in a dry state, water vapor was bubbled into the Sniffing-Port, and the component eluted from the GC column was smelled together with the water vapor.
GC-Sniffing conditions
Device: Hewlett Packard 5890A
Data processor: Shimadzu Chromatopack C-R6A
Column: FS-WCOT Megabore capillary column
： DB-WAX (60m × 0.53mmφ)
Column temperature: 35 ° C to 200 ° C (2 ° C / min)
Carrier gas: He (flow rate 2.31ml / min)
Sample vaporization temperature: 230 ° C
Sample detector temperature: 230 ° C
Detector: Thermal conductivity detector (TCD detector)

[Results and discussion]
<Selection of odor terms>
Fructose and psicose are listed in Table 2 (Evaluation of odor produced by aminocarbonyl reaction with D-fructose and observation of color) and Table 3 (Evaluation of odor produced by aminocarbonyl reaction with D-psicose and observation of color). The color change in the aminocarbonyl reaction used and the evaluation of odor obtained by sensory test are summarized. Things that are similar in terms are roughly summarized. From Tables 2 and 3, it can be seen that the aminocarbonyl reaction using psicose is generally darker than that using fructose. From this, it is considered that in the reaction for 1 hour, the browning reaction proceeds faster in the case of psicose than in the case of fructose. In the case of fructose, there are many fragrant odor expressions in the smell, but in the case of psicose, a language related to burnt odor was frequently used. Moreover, when the two tables were compared, the odor expression produced by the reaction with L-lysine, L-histidine, L-proline, and L-arginine was significantly different between fructose and psicose. However, in this sensory test, they were evaluated on different days, so it is quite possible that there is not much difference in the odor expression that was expressed in different words. Also, since the smell was entered freely, the words fell apart, and it was difficult to compare the two with the same smell. Based on Tables 2 and 3, discussions were made by three panelists in our laboratory, and the odor terms were matched to suppress variations in evaluation in later sensory tests.

<Selection of scent expression to give a score>
Before conducting a sensory test with 13 panelists, we will conduct a sensory test with three panelists (1 male, 2 females, average age 28 years old) and discuss the two odors in detail. The words are "sweet, sour, bitter, fragrant (preferably smell), burnt odor (unfavorable smell), cheese odor, flowery (rose-like, violet-like), sulfur odor (perm-like, hot spring Odor), cracker odor, and coffee odor. At this time, similar words and abstract words were omitted, and specific words were selected as much as possible.

<GC, GC / MS analysis results>
A chromatogram obtained by GC of fructose is shown in FIG. The identified components, their retention index values and quantitative results are summarized in Table 4 (volatile components generated by the reaction of D-fructose and L-phenylalanine). The absolute amount was divided by the weight of the reacted sugar from the relative value of the weight of toluene, which is an internal standard substance, and expressed in parts per million. A total of 27 compounds could be identified. The identification of the volatile components produced by the reaction of D-glucose and L-phenylalanine has been reported in the paper, and the identification was performed with some reference. The compounds identified in Table 5 (volatile components produced by the reaction of D-psicose and L-phenylalanine) are summarized by functional group, and their odor characteristics are also extracted from the literature. Among them, there were 8 nitrogen-containing compounds, 6 alcohols, 4 esters and ketones. Looking at the odor characteristics in Table 6, the characteristic flower odors revealed from the results of sensory tests are thought to be mainly derived from 2-ethyl-1-hexanol and phenylacetaldehyde, and the sweet odor is pyrazine. It is thought to be derived from 2,6 dimethylpyrazine, furfuryl alcohol and benzothiazole. The honey odor is known to be derived from phenylacetic acid, but it could not be identified in this experiment. This is considered to be because phenylacetic acid was not strongly adsorbed on the column because phenylacetic acid was highly polar and the column used for GC this time was also highly polar.

As for fructose, the chromatogram obtained by GC as well as fructose is shown in FIG. 7, and the identified components, their retention index values and quantitative results are shown in Table 6 (volatile components produced by the reaction of D-psicose and L-phenylalanine). Summarized. The compounds identified in Table 7 (volatile components produced by the reaction between D-psicose and L-phenylalanine and odor characteristics) are summarized by functional group, and the odor characteristics are also extracted from the literature. The number of identifications was 37, and the main compounds were 10 nitrogen-containing compounds, 7 alcohols, 5 esters, 4 ketones and lactones, and more were identified than the reaction products with fructose. Similar to fructose, the characteristic odors of flowers revealed from the results of sensory tests in the odor characteristics of Table 7 are mainly from 2-ethyl-1-hexanol, furfuryl acetate, phenylacetaldehyde, etc. The sweet odor is thought to originate from pyrazine, 2,6-dimethylpyrazine, furfuryl alcohol, benzothiazole, cycloten, dihydro-2-methyl-3 (2H) -furanone, dihydro-3 (2H) -furanone, furaneol, etc. It is thought that it originates from. In addition, honey odor is known to be derived from phenylacetic acid, but phenylacetic acid was not detected in the case of psicose. Furthermore, it is known that the soy sauce odor characterized by organoleptic tests is derived from furanones, and that psicose produces more furanones than fructose. It is thought that this is the cause that was felt.
FIG. 7 shows the difference in absolute amount for each component obtained by the reaction of fructose and psicose with phenylalanine. The types of ingredients are almost the same, but the amount of psicose is generally larger. In sensory tests, psicose gave higher overall scores for sweetness, flowery aroma, etc. than fructose, but psicose produced more volatile components even in absolute amounts, and many volatile components by reaction It was thought that the smell became stronger.

<Measurement result of browning degree>
The results of ultraviolet / visible analysis are shown in FIGS. This plots the degree of browning of fructose and psicose over time at 320 nm and 400 nm, respectively.

  The degree of browning was expressed as the absorbance per 1 cm optical path multiplied by the dilution rate. The slope of the linear regression line is also shown. For both fructose and psicose, the degree of browning has increased over time. Psicose has a 1.85 times greater slope than fructose at a wavelength of 320 nm, and psicose has a 1.57 times greater slope at 400 nm. This indicates that psicose has a faster browning reaction.

<Reactivity measurement results>
The results of NMR analysis are shown in FIGS. This is the structural change over time,
Fructose was calculated from the signal derived from C-2, and psicose was calculated from the signal derived from C-5. The assignment of ¹³ C-NMR signals for fructose and psicose was performed with reference to the literature. 10 and 11, it can be seen that the structure of the psicose changes more drastically than the fructose, and the switching between the ring-opening type and the ring-closing type is faster. Since the aminocarbonyl reaction occurs when the ring is opened, it is considered that psicose having a faster structure change is more likely to react.

<GC-Sniffing analysis results>
The Sniffing results of the reaction product of fructose and phenylalanine are shown in Table 8 (GC-Sniffing analysis of the reaction product of D-fructose and L-phenylalanine). The peak numbers in the table correspond to the peak numbers in the chromatogram in FIG. Similarly, psicose Sniffing results are shown in Table 9 (GC-Sniffing analysis of reaction products of D-psicose and L-phenylalanine). The peak numbers in the table correspond to the peak numbers in FIG. Among the scents I felt, focusing on the sweet scent, there were characteristic scents such as 2,6-dimethylpyrazine, which is sweet and has an almond scent, cycloten which has a maple odor, and furaneol which has a scent of jam. Comparing Table 9 and Table 10, fructose has a sweet odor at 12 locations, but psicose has a sweet odor at 16 locations, and the overall strength of psicose exceeds that. Yes. In addition, pyrazines that are fragrant and have a chocolate smell in Table 10 (characteristic aroma components produced by the reaction of D-fructose and D-psicose with L-phenylalanine) and furanones that exhibit maple and caramel odors The absolute amounts of characteristic sweet ingredients are summarized in a table. It can be seen from Table 10 that psicose produces a greater amount of absolute overall. From these results, it was found that psicose produces more characteristic sweet aroma components than fructose in the reaction using phenylalanine.

  Utilization and improvement of rare sugars in foods, pharmaceuticals, and other flavorings can efficiently impart or enhance the preferred fragrance, sweet scent and / or preferred baked color that lead to its deliciousness in many foods that are more versatile. In addition, liquid and powder medicines and diagnostic aids that are difficult to take may be given aroma and sweetness to make them easier to drink.

The initial reaction of aminocarbonyl reaction is shown. The pyranose structure of α-D-ketohexose is shown. The result of the sensory test by the reaction product of D-fructose and L-phenylalanine is shown. The result of the sensory test by the reaction product of D-psicose and L-phenylalanine is shown. The gas chromatogram of the reaction product of D-fructose and L-phenylalanine is shown. The gas chromatogram of the reaction product of D-psicose and L-phenylalanine is shown. Note: Peak numbers in Table 6 and corresponding columns: DB-WAX (60 m × 0.25 mmφ), oven temperature: 35 ° C. → 200 ° C. (2 ° C./min) The volatile component produced | generated by reaction of D-fructose and D-psicose and L-phenylalanine is shown. The difference in the reaction speed of D-fructose and D-psicose is shown. The difference in the reaction speed of D-fructose and D-psicose is shown. The change of the structure in time of D-fructose dissolved in water is shown. Note: The proportion of molecules present was calculated from the C ¹³ -NMR signal derived from C-2. Use solvent or heavy water. The change of the structure in time of D-psicose dissolved in water is shown. Note: The proportion of molecules present was calculated from the C ¹³ -NMR signal derived from C-5. Use solvent or heavy water.

Claims (4)

Contains an aromatic component composed of pyrazines and / or furanones, which is produced by aminocarbonyl reaction using D-psicose and L-phenylalanine more than aminocarbonyl reaction using glucose or fructose and L-phenylalanine. Incorporating L-phenylalanine having a functional property of no increase in calories based on the psicose modified by aminocarbonyl reaction using psicose and L -phenylalanine into food or pharmaceuticals, or at the time of manufacturing foods or pharmaceuticals A method for improving the fragrance of a food or pharmaceutical product characterized by being produced. The method for improving the aroma of food or medicine according to claim 1, wherein the aroma component is a heated aroma component generated by adding or adding D-psicose and L-phenylalanine before the heating step. The method for improving the fragrance of a food or pharmaceutical product according to claim 2 , wherein the heating step is a step involving a heat treatment performed during the production of the food or pharmaceutical product. The method for improving the fragrance of a food or pharmaceutical product according to claim 2 , wherein the heating step is a step involving a heat treatment performed when a flavor is formed in advance by forming a fragrance by reaction of D-psicose and L-phenylalanine .