RU2317299C2 - Associate containing trehalose and calcium chloride as crystalline monohydrate or anhydrous crystal - Google Patents

Abstract

FIELD: cosmetics, pharmacy.

SUBSTANCE: invention relates to associates containing trehalose and calcium chloride as a crystalline monohydrate comprising above said components and water in the molar ratio = 1:1:1, or as anhydrous crystal containing above said components in the molar ratio = 1:2. Indicated crystals of two species of associates of trehalose and calcium chloride can be used in different branches in production of foodstuffs, cosmetic agents and others.

EFFECT: valuable properties of compounds.

3 cl, 20 tbl, 15 dwg, 30 ex

Description

Technical field

The present invention relates to new associates of saccharides and compounds containing metal ions, and more particularly to associates of trehalose or maltitol and compounds containing metal ions.

Description of the Related Art

Compared to carbon, oxygen, hydrogen, nitrogen, etc. metal elements such as sodium, potassium, calcium, magnesium, iron, copper, zinc, nickel, etc., are not necessary in large quantities for living organisms. However, they are essential elements for maintaining normal biological functions. Such metal elements are usually introduced into living organisms in the form of compounds comprising ionized metal elements (compounds containing metal ions or metal ion compounds), such as salts, and perform corresponding functions in organisms.

Magnesium and calcium are known to be minerals involved in enzymatic reactions in human organisms and required in relatively large quantities. Magnesium and calcium deficiencies cause bone thinning due to osteoporosis and osteomalacia, because these metal elements are present in relatively large amounts in the bones of living organisms. Recently, magnesium deficiency has been recognized as the cause of diseases such as diabetes and hypertension.

Magnesium is an essential mineral for plants and is generally delivered to plants in the form of fertilizer with nitrogen, phosphorus and potassium in liquid or solid form and is used for their growth. It is known that a lack of magnesium causes a disease associated with its deficiency. Although, as described above, various metal elements are essential for living organisms, there is a case where compounds containing metal ions, such as salts, cause an unpleasant taste when administered orally, depending on the amount. Therefore, the problem of compounds containing metal ions in the food industry is recognized mainly because of the unpleasant taste of these compounds when administered orally, and various studies have been conducted to resolve this problem.

The authors of the present invention have extensively studied mainly the development and uses of new food materials, with particular emphasis on saccharides and saccharide-related substances. As part of the study, the authors of the present invention investigated compositions comprising saccharides and compounds containing metal ions (metal-ion compounds) to identify their new and effective uses in the food industry. In the study, the authors of the present invention found the fact that compounds containing metal ions, commonly used in the production, storage of food products or their raw materials, have adverse properties, such as dispersion in humid air due to hygroscopicity, restoring ability, oxidizing ability, low solubility in water, etc .; the inventors noted that, as usually assumed, adverse properties are inherent in compounds containing metal ions and cannot be improved; and that these problems were not recognized as problems to be resolved. The authors of the present invention believed that the development of preparations of compounds containing metal ions with improved adverse characteristics and their delivery would make a big contribution to the food industry.

The present invention solves a rather new problem that has arisen on the basis of the initial concept of the authors of the present invention by providing preparations comprising compounds containing metal ions or components of a mother salt solution, whose properties are inherent and unfavorable for industrial applications, such as dispersion in moist air due to hygroscopicity, restoring , oxidizing ability, low solubility in water, etc., are improved.

Description of the invention

Studies of the present invention have been started to solve the above problem, taking into account initial ideas about how to use saccharides. First, extensive research was conducted into the changes in the properties inherent in compounds containing metal ions, enabling them to coexist with saccharides in various combinations. As a result, it was revealed that two non-reducing saccharides, trehalose and maltitol, showed the functions of improving the solubility properties of compounds containing metal ions, in particular, increasing their solubility in water and suppressing their oxidation / reduction ability by allowing them to coexist with metal ion compounds, and that their functions markedly exceeded those of other saccharides. Then, to study the mechanism for the implementation of the above functions, a detailed analysis was carried out at the molecular level of the interaction between trehalose or maltitol and metal ion compounds. As a result, it was found that trehalose and maltitol formed associates with metal ion compounds and that the resulting associates showed the properties described above that are different from those of intact metal compounds. According to the results described above, it was found that the associates that can be obtained by allowing trehalose and maltitol to coexist with metal ion compounds showed many advantages for their use in the food industry, compared with conventional preparations of compounds containing metal ions. In the case of the components of the mother liquor, a specific example of such compounds containing metal ions are compounds including compounds of magnesium ions and / or compounds of calcium ions, which also formed associates and showed great advantages. The present invention has been made based on the initial representations of the present inventors described above. By reference, with respect to trehalose and salt associates, a crystalline associate constructed by trehalose and calcium bromide in a 1: 1 molar ratio was reported by William J. Cook et al. in Carbohydrate Research, Vol. 31, pp. 265-275 (1973). A crystalline associate was discovered during their research to elucidate the mechanism of plaque formation in the oral cavity. On the basis of their ideas, they did not suggest industrial methods of using the associate trehalose and calcium bromide or its crystalline form. Therefore, the present invention discloses associates of trehalose or maltitol and metal ion compounds, with the exception of calcium bromide, or components of the mother liquor, which can be used in various industries, such as food processing, preparation and use.

As described above, the present invention solves the above problem by providing trehalose or maltitol associates and or compounds containing metal ions or components of the mother liquor, and their preparation and use.

Brief Description of the Drawings

Figure 1 shows the x-ray diffraction of the crystalline associate of trehalose and calcium chloride (1: 1 molar ratio).

Figure 2 shows the x-ray diffraction pattern of the crystalline associate of trehalose and calcium chloride (molar ratio 1: 2).

Figure 3 shows the x-ray diffraction pattern of aqueous crystalline trehalose.

Figure 4 shows the x-ray diffraction pattern of crystalline calcium chloride dihydrate.

Figure 5 shows the absorption spectrum of infrared light by the associate trehalose and calcium chloride (molar ratio 1: 1).

Figure 6 shows the absorption spectrum of infrared light by the associate trehalose and calcium chloride (molar ratio 1: 2).

7 shows the absorption spectrum of infrared light by the associate of trehalose and magnesium chloride.

On Fig shows the absorption spectrum of infrared light by the associate of trehalose and strontium chloride.

Figure 9 shows the absorption spectrum of infrared light by the associate of trehalose and ferrous chloride.

Figure 10 shows the absorption spectrum of infrared light by the associate of trehalose and copper dichloride.

11 shows an infrared absorption spectrum of trehalose and nickel chloride associate.

12 shows an infrared absorption spectrum of an associate of trehalose and manganese chloride.

On Fig shows the absorption spectrum of infrared light by the associate of maltitol and calcium chloride.

On Fig shows the absorption spectrum of infrared light by the associate of maltitol and ferrous chloride.

On Fig shows the absorption spectrum of infrared light powder, including the associate of trehalose and a component of scale.

The best way of carrying out the invention

The present invention relates to associates of trehalose or maltitol and compounds containing metal ions (ion-metal compounds), with the exception of calcium bromide or components of uterine saline solutions, and to their preparation and use. Used in the present invention, the term "trehalose" means α, α-trehalose, a disaccharide in which two glucose molecules are linked together at their reducing groups via an α, α bond. Used in the present invention, the term "maltitol" means a sugar alcohol that can be obtained by reducing maltose, a disaccharide in which two glucose molecules are linked via an α-1,4-glucosidic bond. In the present invention, trehalose and maltitol are not limited by their purity and form (liquid, amorphous powder, hydrated crystalline powder, anhydrous crystalline powder, etc.) as long as each of them forms associates with the metal ion compounds described below. Trehalose and maltitol, which can be used in the present invention, can be obtained by conventional methods, however, commercially available compounds can be arbitrarily used. For example, as a commercially available trehalose, “TREHA®” can be used, a food grade aqueous crystalline trehalose powder (trehalose content 98% or higher by HPLC analysis) sold by Hayashibara Shoji, Inc., Okayama, Japan. MABIT®, a food grade syrup comprising maltitol (74% or higher on a dry solid basis, maltitol content 75% or higher relative to the total sugar content by HPLC analysis) and Crystal MABIT, anhydrous crystalline food grade maltitol (moisture content 1 , 5% or lower, the content of maltitol 99% or higher by HPLC analysis) can be used as maltitol commercially available.

Used in the present invention, the term "compound containing metal ions" means a compound having a metal ion as a cation in compounds having an ionic bond between the cation and the anion, and comprising a salt, alkali or complex. Any compounds containing metal ions can be advantageously used in the present invention, with the exception of calcium bromide, which can form associates with trehalose or maltitol. For example, compounds containing metal ions include one or more metal ions having monovalent (monovalent) or having a high valency ionic charges as a cation, in particular one or more metal ions from groups 1-16 of the periodic table of elements, more specifically one or more metal ions selected from lithium, sodium, potassium, rubidium, etc. from group 1, beryllium, magnesium, calcium, strontium, etc. from group 2, scandium, yttrium, etc. from group 3, titanium, zirconium, hafnium, etc. from group 4, vanadium, niobium, tantalum, etc. from group 5, chromium, molybdenum, tungsten, etc. from group 6, manganese, technetium, rhenium, etc. from group 7, iron, ruthenium, etc. from group 8, cobalt, rhodium, etc. from group 9, nickel, palladium, etc. from group 10, copper, silver, etc. from group 11, zinc, etc. from group 12, aluminum, gallium, etc. from group 13, Germany, etc. from group 14, antimony, etc. from group 15 and polonium, etc. from group 16. In these compounds, compounds containing metal ions, including one or more metal ions selected from groups of alkaline-earth metal ions, such as calcium, magnesium, strontium ions, etc., metal ions related to transition elements such as ions of ferrous iron, copper, nickel, manganese, zinc, etc., and alkali metal ions such as sodium, potassium, etc., can be relatively successfully used as associates, as described in detail below. Since metal compounds, including metal ions having divalent or more charges, are more useful, they can especially be used in the present invention. One or more anions selected from halogen ions such as fluorine ion, chlorine ion and bromine ion (except metal ions having a calcium ion as counterion), inorganic anions such as sulfate ion, sulfite ion, monohydrosulfate ion, ion thiosulfate, carbonate ion, bicarbonate ion, nitrate ion, phosphate ion, monohydrogen phosphate ion, dihydrogen phosphate ion, chlorite ion, hydroxide ion, ammonium ion, and organic anions such as acetate ion, lactate ion, citrate ion, fumaric ion and malate ion, can be used as ve anions for compounds containing metal ions, in the present invention. Since compounds containing metal ions having inorganic anions are relatively useful, as described below, compounds containing metal ions including inorganic anions can advantageously be used. With respect to the use of compounds containing metal ions of the present invention in living organisms, it is desirable to use physiologically acceptable compounds containing metal ions. Hereinafter, the term "compounds containing metal ions" means all compounds containing metal ions, with the exception of calcium bromide.

Used in the present invention, the term "associates" means substances in which trehalose or maltitol and compounds containing metal ions are associated through direct interaction. Such associates in the present invention are essentially constructed with trehalose or maltitol and metal ion compounds. As used herein, the term “direct interaction” means a hydrogen bond, a van der Waals force, an ionic bond, or a coordinate bond and includes bonds in a solid, gaseous, liquid, or pasty state. Also used in the present invention, the term “essentially constructed by trehalose or maltitol and metal ion compounds” means associates that are usually constructed by trehalose or maltitol and metal ion compounds, and, as the case may be, also means compounds which include as molecules other molecules, such as bound water. Compounds containing metal ions in the above associates are usually associated with trehalose or maltitol in a neutralized form (e.g., salts, etc.) of a metal ion and its counterion. Depending on the circumstances, metal ions can be associated with trehalose or maltitol, and the counterion binds to neutralize the resulting associates. Associations of the present invention can be identified as follows: Associates formed in solution can be identified by nuclear magnetic resonance (NMR) methods, as described, for example, in "Jikken-Kagaku-Kohza (Experimental Chemistry Course) 5" edited by the Japanese Chemical Society published by Maruzen Co., Ltd., pp. 221-224 (1991). Associates can be identified by analysis of a solution comprising the associate of the present invention and a solution not including an associate, for example, including only trehalose or maltitol, using NMR, comparing the relaxation times of the constituent atoms and revealing the phenomenon that the atoms of the associate exhibit shorter relaxation times. Further, such associates can be identified by the fact that one or more signals associated with chemical shifts (ppm) exhibit signals with different chemical shifts, compared with the corresponding signals observed in the case of using only trehalose or maltitol. In addition, associates can also be identified by crystallizing them in solutions, isolating the resulting crystals and analyzing their crystallographic structure. In particular, the associates of the present invention can be identified by the steps of their analysis by X-ray diffraction and comparing the X-ray patterns with those in the case of crystalline trehalose, maltitol or a crystalline compound of metal ions, respectively, and confirming that the X-ray diffraction patterns of the associates are not consistent with any of those obtained from trehalose or maltitol and the combination of metal ions and their combined patterns. The above-described associates of the present invention include compounds containing metal ions (or metal ions) in molar ratios with trehalose or maltitol, usually 0.5 or higher, but not higher than 5, preferably 1 or higher, but not higher than 4. As with crystalline associates of trehalose and calcium chloride, which are described in detail below in the "examples", associates can give the prescribed molar ratio of trehalose or maltitol to a compound of metal ions, such as about 1 or 2.

Associations of the present invention can be obtained by mixing trehalose or maltitol with metal ion compounds. Mixing can be accomplished by contacting trehalose or maltitol with metal ion compounds. It is usually preferable to mix them using the same solvent under the conditions under which both components dissolve. As a solvent, water, ethanol, methanol, acetonitrile, dimethyl sulfoxide, dimethylformamide and acetic acid can be used. In the case of obtaining associates for use in living organisms in the fields of food, cosmetics and pharmaceuticals, it is desirable to use physiologically acceptable solvents such as water and ethanol. If an aqueous form of trehalose is used, associates of compounds containing metal ions or compounds containing metal ions can be formed with their inherent hygroscopicity, such as calcium chloride, by mixing them in solid forms. Although the proportional ratio between trehalose or maltitol and metal ion compounds depends on the type of compounds containing metal ions, the molar ratio between metal ion compounds and trehalose or maltitol can preferably be set in the range usually 0.01 or higher, but not more than 1000, preferably 0.1 or higher, but not higher than 10. As in the case of associates of trehalose and calcium chloride, which are described in detail below in the "examples", associates can be effectively obtained by mixing trehalose or maltitol and togetherness containing metal ions, in prescribed molar ratios such as about 1 or 2.

Associations of trehalose or maltitol and compounds containing metal ions formed as described above can be used in intact form, for example in the form of solutions, and they can also be used in the form of isolated forms. For example, extraction, filtration, concentration, centrifugation, dialysis, precipitation, crystallization, hydrophobic chromatography, gel filtration chromatography and affinity chromatography can be used as a method for isolating associates.

Associations formed as described above or fractions containing them can be collected by methods such as crystallization, precipitation, concentration and drying (including spray drying, vacuum drying and lyophilization). Depending on the types of compounds containing metal ions, associates that can be obtained by the methods described above have the following very favorable properties, compared with conventional preparations of compounds containing metal ions:

(1) Reduced hygroscopicity

Alkaline earth metal halides, including calcium chloride, have hygroscopic properties. The hygroscopic properties of compounds containing metal ions are significantly reduced by the formation of associates with trehalose or maltitol. Therefore, the associates of the present invention, which include compounds containing metal ions having their inherent hygroscopicity, are characterized by the presence of a sign of the possibility of satisfactory handling. Such properties can advantageously be used to obtain hygroscopicity suppressants. For example, you can suppress the hygroscopicity of marine products, including the components of the mother liquor.

(2) Inhibition of the formation of sparingly soluble or insoluble compounds containing metal ions

In some cases, metal ions form salts having a low solubility in water, depending on the type of counterions, as in the case of calcium phosphate. When a counterion which forms sparingly soluble or insoluble salts with such metal ions is added to a solution including such metal ions, a substance (salt) having low solubility is rapidly formed and precipitates. The formation of such a sparingly insoluble or insoluble salt can be suppressed by the formation of associates of a compound including such a metal ion and trehalose or maltitol before the formation of a sparingly insoluble or insoluble salt which is formed by a water-soluble compound comprising a metal ion. Therefore, associates of a compound comprising a metal ion which has the ability to form a sparingly insoluble or insoluble salt and trehalose or maltitol can be used as preparations whose deposition or suspension in water can be suppressed. Such properties can be used to obtain a deposition inhibiting agent for sparingly insoluble or insoluble salts.

(3) Improved solubility in water

Compounds containing metal ions, which are in the form of associates with trehalose or maltitol, in many cases have a higher solubility in water than the solubility inherent in compounds containing metal ions. For example, the association improves the water solubility of compounds of transition metal ions such as manganese salts, nickel resins, iron salts and copper salts, calcium salts, magnesium salts and sodium salts. Therefore, trehalose and maltitol can advantageously be used as a solubility improver for such compounds containing metal ions. In addition, the associates of these compounds containing metal ions, and trehalose or maltitol can advantageously be used in the fields of food, cosmetics and pharmaceuticals, while it is desirable to provide a solution comprising compounds containing metal ions in high concentrations.

As a result of extensive research by the authors of the present invention, it was revealed that the above properties of the associates described in paragraphs (2) and (3) consisted in the formation of water-soluble compounds like chelates. It was also revealed that associates could be used predominantly for the following uses because they were not toxic, had relatively high safety, and had a relatively low environmental impact.

<1> Since the solubility in aqueous solutions of compounds containing metal ions, in particular calcium ion compounds, can be improved by the formation of associates with trehalose or maltitol, trehalose and maltitol can be used to prevent precipitation and cloudiness of beverages including such compounds, such as soft drinks, Isotonic drinks and infusion solutions supplemented with minerals.

<2> The precipitation of sparingly soluble salts, in particular compounds of magnesium ions formed in the preparation of food products with their boiling and dishes prepared in dishes, can be suppressed by the formation of associates with trehalose or maltitol. As a result, scale formation can be significantly suppressed.

<3> Precipitation of sparingly soluble salts, in particular magnesium salts of fatty acids, can be suppressed by the formation of associates with trehalose or maltitol when the soap is dissolved in hard water, including compounds containing metal ions. As a result, the formation of soap flakes can be significantly suppressed, and the formation of foam and the washing ability of soap solutions practically do not deteriorate.

<4> The precipitation of sparingly soluble salts, in particular iron salts and magnesium salts, which, by their inherent properties, are formed when hard water is stored or boiled, can be suppressed by the formation of associates with trehalose or maltitol. As a result, turbidity and scale formation can be suppressed.

<5> In the case of insoluble or insoluble substances formed by the association of compounds containing metal ions with organic substances, with the exception of saccharides, for example glycosides and polyphenols, the water solubility of organic substances can be improved by associating compounds containing metal ions with trehalose or maltitol.

<6> Dirt generated by compounds containing metal ions can be prevented and easily removed by washing to form associates of compounds containing metal ions and trehalose or maltitol. Therefore, trehalose and maltitol can advantageously be used as a preventive agent, a removing agent, a washing agent and a means for the bottom layer of the bath when contaminated with metal ion compounds. These agents can preferably be used to prevent or remove contamination of the surfaces of glasses, metals, automobiles, homes, clothing and bodies.

<7> In the case of tartar or plaque formed from compounds containing calcium ions and compounds containing magnesium ions, their adhesion can be suppressed and their dissolution can be promoted by the association of compounds containing metal ions with trehalose or maltitol. Therefore, trehalose and maltitol can mainly be used to rinse the mouth and toothpaste.

(4) Suppression of oxidative or reduction reaction

Ions of transition metals, such as iron and copper and other metals, can be oxidized or reduced, depending on the state. It is possible that such oxidation and reduction reactions spoil other substances that are simultaneously present with such ions. When such compounds containing metal ions form associates with trehalose or maltitol, their oxidative or reductive reactivity is usually suppressed. Therefore, associates of compounds containing metal ions that have oxidation or reduction activity, such as salts of iron and copper, and trehalose or maltitol can advantageously be used as preparations of compounds containing metal ions without affecting the quality of other substances. Properties such as oxidation and spoilage of substances that readily oxidize or deteriorate when a relatively small amount of iron salts or copper salts are combined, such as vitamins such as L-ascorbic acid (hereinafter referred to as “ascorbic acid”) and tocopherols, highly unsaturated fatty acids such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DEC), perfumes and colorants can be suppressed by mixing with trehalose or maltitol to form associates.

Powdered products, including associates of trehalose or maltitol and compounds containing metal ions, which include compounds of magnesium ions and / or compounds of calcium ions (which can be briefly referred to as “powdered product comprising associates”), can be obtained by the steps of mixing trehalose or maltitol with compounds metal ions, which include compounds of magnesium ions and / or compounds of calcium ions, the formation of associates, and then grinding the associates into a powder. It is preferable to mix trehalose or maltitol with a compound (s) of metal ions, including a compound of magnesium ions and / or a compound of calcium ions, which is dissolved in an aqueous solvent, to form associates. The molar ratio between the compound (s) of metal ions, including the compound of magnesium ions and / or the compound of calcium ions, and trehalose or maltitol is preferable to set in the range of usually 0.001-10, preferably 0.01-5. In the case of a molar ratio lower than 0.001, it is inconvenient to use the mixture as an agent rich in minerals, or the like, due to the low content of associate, including a compound of magnesium ions and / or a compound of calcium ions. In the case of a molar ratio higher than 10, the hygroscopicity of the powdery products, including the associate, which is obtained using the mixture, is not improved enough.

Compounds containing metal ions, including magnesium ion compounds and / or calcium ion compounds, can be prepared by mixing commercially available magnesium ion compounds and calcium ion compounds in an appropriate proportion. Uterine saline is an example that includes both compounds in mixed form. Other compounds containing metal ions and organic substances such as saccharides and saccharide-related substances can optionally be added to such a mother liquor.

The mother liquor is usually prepared by the steps of concentrating seawater by heating and / or ion exchange, precipitating sodium chloride, separating the resulting sodium chloride and collecting the residual solution. The mother liquor has a strong, pungent odor and an unpleasant taste, such as a bitter taste, and includes magnesium ion compounds as the main component and calcium ion compounds, potassium ion compounds and sodium ion compounds as other components. The mother liquor was used as a material for the preparation of magnesium salts and potassium salts, improving aroma agents for soy milk, and coagulating agents for the production of “tofu” (bean curd).

Stock salt solution components mean compounds containing metal ions, including saline, and including at least magnesium ion compounds and / or calcium ion compounds. Typically, the mother liquor is sold in liquid form and includes, for example, 17.5% (w / w) magnesium chloride, 8.1% (w / w) calcium chloride, and 3.6% (w / w) as components ./mass.) potassium chloride, 2.9% (w / w) sodium chloride. Dried salt powders, which can be obtained by concentration of an intact mother liquor, followed by crystallization or drying and grinding into a powder, have relatively strong hygroscopicity and quickly turn into liquid form due to their hygroscopicity during storage under relatively high humidity.

Associations formed by the method of the present invention can be obtained in powder form (in addition to liquid and paste forms) by such methods as crystallization, fractional precipitation, concentration and drying (including spray drying, vacuum drying and lyophilization). Undesirable properties, such as hygroscopicity, restoring ability, oxidizing ability and low solubility in water during industrial operations with a conventional powder preparation of compounds containing metal ions, including compounds of magnesium ions and / or compounds of calcium ions, are improved in powdered products, including those obtained way associates. Therefore, powdered products including associates have satisfactory characteristics.

Associations and the powdered products of the present invention containing them that exhibit the effect described above are very useful in various fields in which compounds containing metal ions or mother liquor are used as materials, ingredients and products, for example, food products (including drinks), agricultural and marine products, cosmetics, pharmaceuticals, consumer goods, chemical products, and in the production of materials and ingredients, Used in these areas. They can be used in isolation or, optionally, in the form of a composition along with other ingredients, for example, one or more fillers and carriers, such as calcium carbonate, calcium phosphate, lactose, sugar alcohols, cyclic saccharides, dextrin, starch and cellulose. It is desirable that other ingredients that can be used along with the associates or powder products including the associates of the present invention are biologically acceptable ingredients when such compositions are used in living organisms. When used in the food industry, associates and the powdered products of the present invention containing them can be used along with, for example, sweeteners such as sucrose, glucose, maltose, L-fucose, L-ramnose, stevia, Glycyrrhiza glabia, methyl ester with L aspartyl L-phenylalanine, glycyrrhizinate and sucralose, acidifying agents such as adipic acid, citric acid, glucono-delta-lactone, acetic acid, tartaric acid, fumaric acid and lactic acid, seasonings such as aspartate n triium, alanine, citric acid, glutamic acid, theanine and sodium chloride, one or more coloring agents, flavoring agents, flavor enhancers, swelling agents, preservatives, disintegrants, oxidation inhibitors, decolorizing agents, paste stabilizing agents, stabilizing agents agents and emulsifiers that are commonly used in foods.

The associations and the powdered products of the present invention containing them can also be used for food products; specific examples are various seasonings such as table salt, soy sauce, powdered soy sauce, miso (bean paste), funmatso-miso (powdered miso), moromi (peeled sake), hashio ( refined soy sauce), “furikake” (seasoned fish dish), mayonnaise, seasoning, vinegar, “sanbai-zu” (sugar, soy sauce and vinegar sauce), “funmatso-sushi-zu” (powdered vinegar for sushi) , "Chuka-no-moto" (instant mix for Chinese dishes), "tentsuyu" (sauce for Japanese food fried in excess fat), "Mentsu yu "(sauce for Japanese vermicelli), broth, sauce, ketchup," yakiniku no-tare "(sauce for Japanese meat, grilled), spicy pepper food seasoning, instant mix for stews, instant soup mix," dasha “but-moto” (instant broth mixture), nucleic acid seasoning, mixed seasoning, “mirin” (sweet cookies), “shin-mirin” (artificial mirin), table sugar and coffee sugar; various “vagashi” (Japanese cookies), such as “Senbey” (rice cracker), “Arare” (rice cookies in the form of cubes), “windows” (millet and rice cookies), “urine” (rice paste) and the like , "Manu" (butter bun with bean jam), "wiro" (sweet rice jelly), "ann" (bean jam) and the like, "yokan" (sweet bean jelly), "mizu-yokan" (soft jelly from azuki beans), “kingoku” (a type of yokan), jelly, pao de Castella and “amedama” (Japanese candy); Western confectionery, such as a bun with raisins, biscuit, cracker, cookies, pie, pudding, butter cream, egg and milk cream, cream puff pastry, waffles, sponge cake, donut, chocolate, chewing gum, caramel and candy; frozen desserts such as ice cream and sorbet; syrups such as kajitsu-no-syrup-zuke (canned fruit) and “korimitsu” (sugar syrup for scraped ice); pastes such as flour paste, peanut butter, fruit paste and spreadable product; processed fruits and vegetables, such as jam, marmalade, syrup-zuke (fruit pickles), and toka (canned food); pickles and salted or pickled foods such as “fukujin-zuke” (red radish pickles), “bettara-zuke” (a kind of whole red radish pickles), “Senmai-zuke” (a kind of sliced fresh radish pickles) and "Raccio zuke" (pickled or salted scallots); premix for pickles and pickled or salty foods, such as takuan-zuke-no-moto (premix for pickled or salted radishes) and hakusai-zuke-no-moto (premix for fresh white cabbage pickles); meat products such as ham and sausages; fish meat products, such as fish ham, fish sausages, kamaboko (steamed fish paste), chikuva (a type of fish paste) and tempura (Japanese fish paste fried in excess fat); dried seafood such as dried seaweed, dried whole fish, gutted and dried fish; “Chinmi” (seasoning), such as “uni” (sea urchin), “ika-no-shiokara” (salted squid guts), “su-conbu” (processed sea kale), “saki-surume” (dried squid strips ), “Fugu-no-mirin-boshi” (dried dog-flavored Mirin fish); “Tsukudani” (foods boiled in soy sauce), such as foods made from red seaweed, edible wild plants, dried squid, small fish and aquatic animals that have shells; everyday meals such as nimame (boiled beans), potato salad, and konbu-maki (seaweed rolled up) dairy products such as yogurt and cheese; canned and bottled products, such as fish, animal meat, fruits and vegetables; alcoholic beverages such as sake, artificial sake, liquor, and Western spirits; soft drinks such as coffee, tea, cocoa, juice, isotonic drinks, drinks with mineral additives, drinks enriched with minerals, carbonated drinks, drinks based on fruit juices, sour-milk drinks, drinks containing lactic acid bacteria, vegetable juice, soy milk ; instant food products, such as a mixture for instant cooking pudding, a mixture for instant cooking hot cake, "shokuru sokusuki" (a mixture for instant cooking of azuki bean soup with rice cake), instant soup mixture; solid foods for babies; medicinal foods; wellness drinks such as ginseng extract, bamboo leaf extract, plum extract, pine needles extract, tortoise extract, chlorella extract, aloe extract, propolis extract and other foods and drinks such as peptide foods, frozen foods, wellness foods , viable cells of lactic acid bacteria and yeast, and royal jelly; mineral fortifying agents, including calcium and / or magnesium, a growth promoting agent for Bacillus natto, a taste improving agent, a taste improving agent for soy milk, and a coagulating agent for the production of “tofu” (bean curd).

In the case of the use of the associates and powdered products of the present invention incorporating them in the field of agricultural and marine products, they can advantageously be used intact or in the form of a composition comprising other additional ingredients for food and pet foods or nutritional supplements or activating agents for plants. As other ingredients that can be added to the composition, one or more ingredients can be used that are generally used in the following respective fields, for example food products or food ingredients such as squeezed sugarcane, corncob, rice straw, hay, grain, wheat flour, starch, fatty flour, sugar waste, wheat bran, bean tortilla, various tortillas made using fermentation, chips, leaves and the like, ingredients for pit dietary supplements such as nitrate, ammonium salts, urea, phosphate and potassium salts.

They can also be advantageously used in various materials for concentrated foods, food mixtures and mixtures for domestic animals, for example poultry, honey bees, silkworms, insects and fish; and nutritional supplements and activating agents for plants, for example cultivated plants such as cereals and potatoes and the like, vegetables, tea bushes, fruit trees, garden plants, roadside trees and grass on golf courses.

In the case of the use in the present invention of associates and powdered products comprising them in the form of a composition in the fields of cosmetics and pharmaceutical preparations, one or more of the following ingredients conventionally used in these fields, for example, moisture-retaining agents, detergents, coloring agents, flavoring agents, can usually be used substances, enzymes, hormones, vitamins, ultraviolet (UV) absorbing agents, UV shielding agents, solvents, stabilizers, plasticizers, emollients e agents, solubilizers, reducing agents, buffers, sweeteners, bases, evaporation promoters, adsorbents, flavoring agents, synergists, binders, suspending agents, antioxidant agents, brighteners, coating agents, moisturizers, cooling agents, emollients, emulsifiers excipients, antiseptics and preservatives.

They can also be advantageously used for specific products, for example, cosmetic products, such as milk lotion, cream, shampoo, rinse, skin care products, lipstick, blush, lip cream, lotion, bath agent and toothpaste; products used to produce a pleasant sensation, such as tobacco and cigarettes; pharmaceutical preparations, such as a liquid oral drug, tablet, pill, troche, droplet cod liver oil, oral freshener, capsule, oral rinse, magnesium supplement and mineral enrichment; and stabilizing agents for various enzymes.

To obtain the compositions described above, it is preferable to add associates or powdered products including them in the composition in the range usually 0.00001-75% (w / w), preferably 0.0001-50% (w / w), more preferably 0.001- 25% (wt./wt.), Based on the dry solid base (s.t.o.).

Since trehalose and maltitol inhibit the formation of scale during the preparation of meat and vegetables, soap suds and flakes, they can mainly be used as an agent that inhibits the formation of scale, soap suds and flakes for seasonings for boiled foods and dishes served in dishes, mineral water bath products and soaps.

Further, trehalose inhibits the elution of magnesium ion compounds from food materials such as meat and vegetables during cooking. Therefore, trehalose can advantageously be used as an elution inhibiting agent for magnesium ion compounds for seasonings for cooked foods and dishes cooked in dishes. Elution of magnesium ion compounds, which are mineral components from food materials, is suppressed by the use of said seasonings. Therefore, seasonings can be used to hold nutrients and to preserve the taste inherent in food materials.

The following experiments 1-3 explain the fact that trehalose and maltitol form associates with various compounds of metal ions and components of the mother liquor. Experiments 4-8 explain the possibility of using associates. Further, experiments 9-12 explain the inhibitory effect of trehalose and maltitol on the formation of scale during cooking and the inhibitory effect of trehalose on the elution of magnesium ion compounds.

Experiment 1

Associations formed from trehalose and calcium chloride

Experiment 1-1

Crystalline associate formed from trehalose and calcium chloride

Experiment 1-1 (a)

Isolation of crystalline associate

147 g (one mol) of calcium dihydrochloride was placed in a 1 liter beaker, mixed with 250 g of deionized water and completely dissolved with heating. Under constant heating conditions, 378 g (one mol) of crystalline trehalose dihydrate, simply called "aqueous crystalline trehalose", was added to the solution, and completely dissolved. After stopping heating and leaving the beaker at room temperature (about 25 ° C) for 2 days, a precipitate including crystals was observed at the bottom of the beaker. The crystals were transferred to a bucket-type centrifuge separator and washed by spraying an appropriate amount of water into it and the resulting crystals were collected. The collected crystals were dried in vacuo at 40 ° C for 4 hours. Next, the crystals were thoroughly dried by storage in a desiccator containing phosphorus pentoxide at room temperature for 20 hours. As a result, approximately 200 g of a white crystalline powder was obtained.

294 g (two moles) of calcium dihydrochloride was placed in a 1-liter beaker, mixed with 200 g of deionized water and completely dissolved with heating. Under constant heating conditions, 378 g (one mol) of aqueous crystalline trehalose was added to the solution, completely dissolved and constantly heated. After boiling for about 30 minutes, crystal formation was observed. After stopping heating and leaving the beaker at 60 ° C for 24 hours, the contents of the beaker formed a block comprising crystals and a sugar solution. After removing the block from the beaker and cracking it coarsely, the crystals were collected after washing by spraying an appropriate amount of water using a bucket-type centrifuge separator. The collected crystals were dried in vacuo at 40 ° C for 4 hours, and then thoroughly dried by storage in a desiccator containing phosphorus pentoxide at room temperature for 20 hours. About 400 g of a white crystalline powder were obtained.

Experiment 1-1 (b)

Physicochemical Properties of the Crystalline Associate

(1) X-ray diffraction analysis

2 types of crystals obtained by two different methods described in Experiment 1-1 (a) were respectively analyzed to obtain a X-ray diffraction pattern by a conventional X-ray powder diffraction analysis using an X-ray diffractometer, "RAD-2B" sold by Rigaku Corporation, Tokyo , Japan. X-ray diffraction patterns of aqueous crystalline trehalose and calcium dihydrochloride were also obtained in the same manner. X-ray diffraction patterns of a crystal obtained from a mixture of trehalose and calcium chloride with a molar ratio of 1: 1, which was obtained from a mixture of trehalose and calcium chloride with a molar ratio of 1: 2, aqueous crystalline trehalose and calcium dihydrochloride, all of which were obtained in experiment 1- 1 (a) are shown in FIGS. 1-4, respectively. As is evident from the results shown in FIGS. 1-4, the X-ray diffraction pattern in FIG. 1 shows the main, characteristic diffraction angle (2θ) of 9.02 °, and the other angles of 17.98 ° and 21.90 °, while the x-ray diffraction pattern in figure 2 shows the main diffraction angle of 12.66 °, 21.02 ° and 25.48 °. Both X-ray diffraction patterns were completely different from those in the case of aqueous crystalline trehalose (FIG. 3) and calcium chloride (FIG. 4). These results mean that 2 types of crystals obtained in experiment 1-1 (a) are not a mixture of crystals of aqueous crystalline trehalose and calcium dihydrochloride, and the crystals are completely different from crystals having independent crystal structures.

(2) Component Analysis

Each crystal obtained in two different ways was analyzed to determine the components as follows:

Trehalose

25 mg of each of the above crystals was dissolved in 5 ml of pyridine containing 2 mg / ml of phenyl-β-D-glucoside as an internal standard for gas chromatography. After converting the saccharide into 250 μl of a portion of each solution into the trimethylsilyl derivative in the usual manner, the sample was analyzed by gas chromatography (OV-17 column sold by GL Sciences, Inc., Tokyo, Japan). Separately, aqueous crystalline trehalose as a standard was accurately weighed and analyzed by gas chromatography. The amount of trehalose per 1 g of crystal in each sample was calculated based on the peak areas of the sample and standard.

Calcium

25 mg of each of the above crystals was dissolved in 1% (vol./about.) Hydrochloric acid and the resulting solution was 100 times diluted with 10% (wt./about.) A solution of lanthanum chloride. Then, the calcium content of each diluted solution was measured using atomic absorption photometry (“Model 5100” sold by Perkin-Elmer Japan Co., Ltd., Yokohama, Japan). The amount of calcium chloride per 1 g of the crystal was calculated on the basis of the hypothesis that all calcium contained in the crystal is in the form of calcium chloride.

Moisture

The amount of moisture per 1 g of each of the above crystals was measured by the usual method of loss after drying using 5 g of crystals.

The results obtained in the above analyzes are summarized in table 1.

Table 1 Crystal* Amount (mg) / g of crystal The molar ratio in the crystal Trehalose CaCl ₂ ** Moisture Trehalose CaCl ₂ ** Moisture 1: 1
1: 2 704.6
604.5 276.7
399.0 48.0
0,0 one
one 1.21
2.03 1.29
0.00 * The designations "1: 1" and "1: 2" mean crystals obtained from solutions having molar ratios of trehalose and calcium chloride, respectively, 1: 1 and 1: 2.
** The amount of calcium chloride per 1 g of crystal, calculated on the basis of the hypothesis that all calcium, determined by atomic absorption photometry, is in the form of calcium chloride.

Based on the results presented in table 1, it was found that the first crystal obtained in experiment 1-1 (a) contained trehalose, calcium chloride and water in the form of crystalline associate monohydrate having the above ingredients in molar ratio 1: 1: 1, and that the second crystal contained trehalose and calcium chloride as ingredients in the form of an anhydrous associate crystal having the above ingredients in a 1: 2 molar ratio. Hereinafter, the first and second crystals obtained in experiment 1-1 (a) are called respectively "associate of trehalose and calcium chloride (molar ratio 1: 1)" and "associate of trehalose and calcium chloride (molar ratio 1: 2)."

Experiment 1-2

NMR analysis of associate formed from trehalose and calcium chloride

To analyze the mechanism of association of trehalose and calcium chloride in two types of associates of trehalose and calcium chloride (molar ratios 1: 1 and 1: 2), the following NMR analyzes were performed:

(1) C ¹³ -NMR

50 mg of two types of crystals of trehalose and calcium chloride associates (molar ratios of 1: 1 and 1: 2) and aqueous crystalline trehalose were dissolved in 1 ml of 99.9% deuterium oxide and analyzed for C ^13- NMR as follows. NMR analysis was performed using a Model JNM-AL300 instrument sold by JOEL Ltd., Tokyo, Japan, measuring a C ¹³ core and a resonance frequency of 75.45 MHz. After installing the test tube containing the above solution, the spin-lattice relaxation time (hereinafter referred to simply as the “relaxation time”) of individual carbon atoms of trehalose in the solution was measured in accordance with the inversion recovery method described in the operating manual attached to the device. A single peak (chemical shift, ppm) obtained by analysis was assigned to specific atoms based on data described by JH Bradbery et al. Carbohydrate Research, Vol. 126, 125-126 (1984). The assignment to carbon atoms and their relaxation times are shown in Table 2. (Data for one trehalose, trehalose associate and calcium chloride (molar ratio 1: 1) and trehalose associate and calcium chloride (molar ratio 1: 2) are presented in tables 2, respectively -1, 2-2 and 2-3.)

As shown in table 2, the relaxation time of the carbon atom (s) at position (s) C2 and / or C4 significantly decreased in the two types of associates trehalose and calcium chloride (molar ratios 1: 1 and 1: 2). Therefore, it was assumed that upon the association of trehalose and calcium chloride, a direct interaction occurred between the hydroxyl group bonded to the carbon atom (s) in the position (s) of C2 and / or C4.

(2) H ^1- NMR

50 mg of two types of crystals of trehalose and calcium chloride associates (molar ratios of 1: 1 and 1: 2) and aqueous crystalline trehalose were dissolved in 1 ml of dimethyl sulfoxide-d4 and analyzed by H ¹ -NMR as follows. NMR analysis was performed using a “Model JNM-AL300” instrument sold by JOEL Ltd., Tokyo, Japan, H ¹ core measurements, a resonance frequency of 300.4 MHz and 8 integration times. An individual peak (chemical shift, ppm) obtained as a result of the analysis was assigned to specific atoms in accordance with the two-dimensional NMR method described in "Jikken-Kagaku-Kohza (Course of Experimental Chemistry)" pp. 302-312, edited by the Chemical Society of Japan, published by Maruzen Co., Ltd., (1991) with reference to C ^13- NMR results in table 2. Chemical shifts of trehalose protons, assigned to the corresponding position in the trehalose molecule by analysis, were compared with shifts associates of trehalose and calcium chloride (molar ratios of 1: 1 and 1: 2). Chemical proton shifts, showing a pronounced difference between trehalose and associates, are summarized in table 3.

Table 3 Assignment * Chemical shift (ppm) Tre ** Tre-CaCl ₂ (1: 1) ** Tre-CaCl ₂ (1: 2) ** OH-2 or OH-4 4,808
4,804
4,791
4,791 4,932
4,915
4,887
4,875 4,850
4,833
4,827
4,811 OH-3 4,625
4,624 4,724
4,705 4,657
4,637 OH-6 4,419
4,400
4,381 4,498
4,478
4,459 4,430
4,410
4,391 * The position of the hydroxyl group is presented using the number of its associated carbon.
** The designations "Tre", "Tre-CaCl ₂ (1: 1)" and "Tre-CaCl ₂ (1: 2)" mean trehalose, associate trehalose and calcium chloride (molar ratio 1: 1) and associate trehalose and calcium chloride (molar ratio 1: 2), respectively

As shown in Table 3, the chemical shifts of all the hydroxyl protons of trehalose changed significantly with the association of trehalose with calcium chloride, compared with the chemical shifts of intact trehalose. This result directly indicates that trehalose and calcium chloride form an associate by the interaction of the hydroxyl protons of trehalose with calcium chloride. When considering the above result of C ^13- NMR analysis, it was assumed that the interaction of the hydroxyl proton (s) associated with the carbon atom (s) in the C2 and / or C4 position (s) and calcium chloride to a large extent participated in the formation of two types of associates trehalose and calcium chloride (molar ratios of 1: 1 and 1: 2).

Experiment 2

Associations formed from trehalose and other compounds containing metal ions or components of mother solutions

Experiment 2-1

NMR analysis of an associate formed from trehalose and magnesium chloride, strontium chloride or components of the mother liquor

A mixture of 20.3 g of magnesium hexahydrochloride and 37.8 g of aqueous crystalline trehalose (1: 1 molar ratio) was mixed with 20 g of deionized water and completely dissolved with heating. Similarly, a mixture of 26.6 g of strontium hexahydrochloride and 37.8 g of aqueous crystalline trehalose (1: 1 molar ratio) was mixed with 20 g of deionized water and completely dissolved with heating. After cooling to ambient temperature, these solutions were dried in vacuum at 80 ° C for 15 hours. The resulting dried materials were ground accordingly to obtain two kinds of powder.

20 ml (containing 6.42 g of solid dry matter) of commercially available stock saline components sold by Sanuki Engyou Co., Ltd., Kagawa, Japan, were mixed with 10 g of aqueous crystalline trehalose and completely dissolved with heating. The solution was dried in vacuo at 80 ° C. for 15 hours, and the resulting dried material was ground accordingly to obtain a powder.

(1) C ¹³ -NMR

In accordance with the method described in experiment 1-2, 50 mg of any of the above three types of powders were respectively dissolved in 1 ml of deuterium oxide and the relaxation time of each of the trehalose carbon atoms was analyzed using C ^13- NMR. Thus obtained relative values of the relaxation time of each of the carbon atoms, relative to the values obtained only for trehalose, were calculated based on the results of aqueous crystalline trehalose obtained in experiment 1-2 in table 2-1. The results are summarized in table 4.

Table 4 1. Associate trehalose and magnesium chloride Assignment (carbon atom number) Chemical shift (ppm) Relaxation time (ms) (%) * one
2
3
four
5
6 95,917
75,213
74,843
73,730
72,395
63,230 392.3
462.3
392.0
467.8
418.6
274.6 96
104
92
103
84
101 *: Relative relaxation time, when the corresponding relaxation time of trehalose is taken as 100%. Bold indicates that the relaxation time of the carbon atom has been significantly reduced by association. 2. Associate trehalose and strontium chloride Assignment (carbon atom number) Chemical shift (ppm) Relaxation time (ms) (%) * one
2
3
four
5
6 95,834
75,139
74,760
73,648
72,312
63,172 377.4
422.3
345.5
415.7
398.3
288.6 93
95
81
91
80
107 *: Relative relaxation time, when the corresponding relaxation time of trehalose is taken as 100%. Bold indicates that the relaxation time of the carbon atom has been significantly reduced by association. 3. Associate trehalose and components of the mother liquor Assignment (carbon atom number) Chemical shift (ppm) Relaxation time (ms) (%) * one
2
3
four
5
6 95,886
75,183
74,813
73,700
72,365
63,200 406.8
484.8
410.5
486.1
424.4
273.6 one hundred
109
96
107
85
101 *: Relative relaxation time, when the corresponding relaxation time of trehalose is taken as 100%. Bold indicates that the relaxation time of the carbon atom has been significantly reduced by association.

As is evident from the results presented in table 4, all powders obtained from a mixture of trehalose and magnesium chloride, powders from trehalose and strontium chloride and powders from trehalose and components of the mother liquor by dissolution and drying in vacuum, showed a significantly reduced relaxation time of the carbon atom in a certain position, compared with the case of trehalose alone. From the obtained results, it was revealed that trehalose formed an associate with magnesium chloride, strontium chloride and components of the mother liquor by direct interaction, as in the case of calcium chloride, i.e. the above three types of powder were, respectively, associates of trehalose and magnesium chloride, trehalose and strontium chloride and trehalose and components of the mother liquor. Further, from the results presented in tables 4-1, 4-2 and 4-3, it was assumed that the interaction of the hydroxyl group (s) associated with the carbon atom (s) in the position (s) of C-2 and / or C-4 trehalose and compounds containing metal ions are deeply involved in the formation of an associate of trehalose and magnesium chloride, trehalose and strontium chloride and trehalose and components of the mother liquor.

(2) H ^1- NMR

According to the experimental method, 1-2, 50 mg of any of the above three types of powders were respectively dissolved in 1 ml of dimethyl sulfoxide-d4 and analyzed by H ¹ -NMR. The correlation of proton peaks (chemical shifts, ppm) of trehalose observed at H ¹ -NMR was carried out to specific carbon atoms. The results are presented in table 5.

As in the case of trehalose and calcium chloride associates, the chemical shifts of the hydroxyl protons of trehalose associates and compounds containing metal ions were significantly different from the chemical shifts of trehalose alone. Chemical shifts of these protons are presented in table 5 along with shifts of trehalose alone, shown in table 3.

Table 5 Assignment * 1 Chemical shift (ppm) Tre * 2 Tre-MgCl ₂ * 2 Tre-SrCl ₂ * 2 Triple Salt Components * 2 OH-2 or OH-4 4,808
4,804
4,791
4,791 4,985
4,970
4,867
4,761 4,932 * 3 4,985
4,970
4,867
4,761 OH-3 4,645
4,624 4,661
4,643 4,738
4,720 4,661
4,643 OH-6 4,419
4,400
4,381 4,514
4,495
4,475 4,487 * 3 4,514
4,495
4,475 * 1 The position of the hydroxyl group is represented using the number of the carbon atom associated with it.
* 2 The designations "Tre", "Tre-MgCl ₂ ", "Tre-SrCl ₂ " and "Tre-components of the mother liquor" mean respectively the associate of trehalose and magnesium chloride, the associate of trehalose and strontium chloride and a powder product comprising the associate of trehalose and components of the mother liquor.
* 3 A capital letter means that the multiple peaks (signals) observed in the case of trehalose were grouped in one position.

As shown in Table 5, all chemical shifts of the hydroxyl protons of trehalose significantly changed when associates were formed from trehalose and magnesium chloride, strontium chloride, or uterine saline components, compared with the case of trehalose alone. The results directly indicate that trehalose also formed associates with magnesium chloride, strontium chloride and components of the mother liquor. Taking into account the above results of C ^13- NMR analyzes, it was assumed that the interaction of the hydroxyl proton (protons) bound to the carbon atom (s) at the C-2 and / or C-4 trehalose positions and compounds containing metal ions was particularly deeply involved in the formation of the above trehalose associates and compounds containing metal ions.

Experiment 2-2

Changes in the solubility of compounds containing metal ions by association with trehalose

Changes in the solubility in water of trehalose and / or compounds containing metal ions were investigated in the presence of trehalose and compounds containing metal ions. For these tests used aqueous crystalline trehalose. Strontium hexachlorohydrate, monovalent copper dichlorohydrate, ferrous tetrachlorohydrate, manganese tetrachlorohydrate and nickel hexachlorohydrate were used as compounds containing metal ions for these tests. 37.8 g of aqueous crystalline trehalose (0.1 mol) and 0.1 mol of any of the above compounds containing metal ions were placed in a 100 ml glass beaker and mixed with deionized water to obtain 30 g of water per beaker taking into account the bound water of trehalose and compounds containing metal ions, and then the contents of the beakers were dissolved with heating. Solutions obtained by dissolving the same amount of trehalose alone, or solutions of certain compounds containing metal ions, were prepared as controls. After complete dissolution of the contents, all the beakers were allowed to stand at room temperature (25 ° C) for 24 hours. Then, the precipitation of the crystals was judged by microscopic observation. In the case of crystal deposition, the resulting crystals were collected and analyzed to identify the specified component (s) in the usual way. The results are presented in table 6.

Table 6 A compound containing metal ions Crystal deposition In the presence of trehalose In the absence of trehalose Strontium chloride Crystalline strontium chloride precipitated slightly. Precipitation (strontium chloride) Monovalent Chloride Crystalline monovalent copper chloride was slightly precipitated. Precipitation (monovalent copper chloride) Ferrous chloride Crystalline ferrous chloride precipitated slightly. Precipitation (ferrous chloride) Manganese Chloride No Precipitation (manganese chloride) Nickel chloride No Precipitation (nickel chloride) No (control) Precipitation of crystalline trehalose ---

Turning to the case of strontium chloride, which, as was confirmed by NMR analysis (experiment 2-1), forms an associate with trehalose, crystals of strontium chloride were clearly observed in the absence of trehalose. However, the number of crystals decreased significantly in the presence of trehalose. The result indicates that the association of compounds containing metal ions and trehalose can be judged from the study of changes in water solubility of compounds containing metal ions in the presence of trehalose. Turning to the results of studying monovalent copper chloride, ferrous chloride and nickel chloride (Table 6, from a series of monovalent copper chloride to a series of nickel chloride), the solubility in water of these compounds containing metal ions improved significantly in the presence of trehalose. Accordingly, based on the above judgment, it was found that these compounds containing metal ions also formed associates with trehalose in the presence of trehalose. Compared to the control results (table 6, the bottom row), not including compounds containing metal ions, trehalose was precipitated from a solution containing one trehalose under the available experimental conditions, while trehalose was not precipitated in the presence of the above compounds containing metal ions. Based on the result, it was found that the solubility in water inherent in trehalose, as well as compounds containing metal ions used in this experiment, improved as a result of association.

Experiment 3

Maltitol Association and Metal Ion Compound

A mixture of 100 mg of maltitol (s.t.o.) and 85.3 mg of calcium chloride (s.t.o.) was dissolved in 1 ml of deuterium oxide. The solution was analyzed according to C ¹³ NMR described in Experiment 1-2, and the relaxation time of each carbon atom of maltitol was analyzed. A single peak (chemical shift, ppm) observed in this analysis was correlated to a specific carbon atom based on data described by JH Bradbery et al. in Carbohydrate Research, vol. 126, 125-126 (1984). A solution prepared with only 100 mg of maltitol (s.t.o.) was analyzed in a similar manner as a control. The results are summarized in table 7.

As shown in table 7, in a solution of a mixture of maltitol and calcium chloride, the relaxation times of carbon atoms at position C-4 of the glucose residue and at positions C-3 'and C-5' of the sorbitol residue were significantly reduced compared to the case of maltitol alone. Based on the results, it was revealed that maltitol formed an associate with calcium chloride by direct interaction. Further, from the results described above, it was assumed that the direct interaction of hydroxyl groups bonded to carbon atoms at position C-4 of the glucose residue and at positions C-3 'and C-5' of the sorbitol residue and calcium chloride was mainly deeply involved in the formation of maltitol associate and compounds containing metal ions.

Experiment 4

Hygroscopicity of the associate trehalose and calcium chloride or components of the mother liquor

To compare the hygroscopicity (the ability to disperse in humid air) of a powder comprising an associate of trehalose and calcium chloride, or an associate of trehalose and components of a mother salt solution, a dried powder of calcium chloride or mother salt solution, which is known to have high hygroscopicity, was carried out the following hygroscopicity tests. Two types of crystalline associates of trehalose and calcium chloride (molar ratios of 1: 1 or 1: 2) obtained in accordance with the method described in experiment 1-1 or 1-2 were used as test samples, the powders included associates of trehalose and uterine components saline, calcium dichlorohydrate or a powder of the dried components of the mother liquor. A powder of the dried components of the mother liquor was obtained by drying the mother liquor in vacuo at 60 ° C. for 15 hours, grinding into powder and drying in the usual manner for use as a control. The moisture content (moisture mass per 1 g of sample) in each sample was measured in the usual way to determine the loss during drying. The moisture content in the associate of trehalose and calcium chloride (molar ratio 1: 1), in the associate of trehalose and calcium chloride (molar ratio 1: 2), in a powder comprising the associate of trehalose and components of the mother liquor, calcium dichlorohydrate or in the dried components of the mother liquor the solution was respectively 0.048 g, 0.000 g, 0.061 g, 0.245 g and 0.214 g. These samples, approximately 1.5 g each, respectively, were placed in an aluminum cup and stored at 25 ° C for 7 days in a desiccator, which was adjusted for supported by I have a relative humidity of 33.0% or 52.8%. The mass of contents in each dish was measured at the beginning of storage (0 day storage) and 1, 2, 4, and 7 days after the start of storage. The amount of moisture per 1 g of each sample after 1-7 days of storage was calculated based on the assumption that the increased amount, measured relative to 0 days of storage, was the amount of moisture absorbed by each sample. The results are presented in table 8.

Table 8 Relative humidity Sample* Moisture Content / g sample (g) 0 day 1 day 2 day 3 day 3 day 33.0% CaCl ₂ · 2H ₂ O 0.245 0.289 0.312 0.343 0.364 Tre-CaCl ₂ (1: 1) 0,048 0,048 0,048 0,048 0,048 Tre-CaCl ₂ (1: 2) 0,000 0.010 0.010 0.011 0.011 DPBC ** 0.214 0.299 0.349 0.378 0.398 Tre-BC *** 0,061 0.164 0.182 0.182 0.175 52.8% CaCl ₂ · 2H ₂ O 0.245 0.319 0.359 0.405 0.430 Tre-CaCl ₂ (1: 1) 0,048 0,054 0.059 0.059 0,060 Tre-CaCl ₂ (1: 2) 0,000 0.016 0.017 0.018 0,021 DPBC ** 0.214 0.412 0.462 0.495 0.523 Tre-BC *** 0,061 0.253 0.294 0.337 0.356 * The designations "CaCl ₂ · 2H ₂ O", "Tre-CaCl ₂ (1: 1)", "Tre-CaCl ₂ (1: 2)" and "Tre-BC" mean calcium dihydrochloride, associate trehalose and calcium chloride ( molar ratio 1: 1), associate trehalose and calcium chloride (molar ratio 1: 2) and a powdery product comprising the associate trehalose and components of the mother liquor.
** Dried powder components of the mother liquor.
*** Components of uterine saline.

As shown in table 8, calcium dihydrochloride began to absorb moisture from the beginning of storage under all the above conditions of relative humidity. The moisture content per 1 g of each sample reached 0.364 g at a relative humidity of 33.0% and 0.430 g at a relative humidity of 52.8% after 7 days of storage. On the other hand, two types of associates of trehalose and calcium chloride showed almost no moisture absorption after 7 days of storage and there was almost no increase in moisture content. The degree of moisture absorption of the samples was obviously low compared with the case of calcium chloride. Further, two types of associates of trehalose and calcium chloride showed almost no hygroscopicity upon macroscopic observation, while calcium chloride showed it. The above results indicate that the inherent property of calcium chloride, the hygroscopicity decreases in the associates of trehalose and calcium chloride.

The dried powder of the mother liquor began to absorb moisture from the beginning of storage under all the above conditions of relative humidity. The moisture content per 1 g of each sample reached a high level of 0.398 g at a relative humidity of 33.0% and 0.523 g at a relative humidity of 52.8% after 7 days of storage. On the other hand, the moisture content of the powder, including the associate of trehalose and the components of the mother liquor, reached 0.175 g at a relative humidity of 33.0% and 0.356 g at a relative humidity of 52.8% after 7 days of storage. The moisture content of the samples was obviously low compared to the case of dried mother liquor powder. Further, the powder, including the associate of trehalose and the components of the mother liquor, did not show hygroscopicity under macroscopic observation, while the dried powder of the mother saline showed it. The above results indicate that the hygroscopic property inherent in dried mother liquor powder is reduced in the powder, including associates of trehalose and mother saline components. The above property of trehalose associates and components of the mother liquor can advantageously be used for the production of dried marine food products, i.e. dried seaweed such as dried brown seaweed, dried brown seaweed, dried ulva, red seaweed and the like; dried whole fish or dried gutted fish such as flying fish, barracuda, syllagic fish, horse mackerel, mackerel, hockey, sardine, mackerel, half-handed, flounder, octopus, squid and the like, whose hygroscopicity is reduced by using marine contact food products with trehalose in an aqueous solution, preferably with a trehalose solution having a trehalose concentration of 2% (w / w) or higher, forming an associate of trehalose and the components of the mother liquor contained in marine food products, and drying with Mashi to produce dried seafood such as seaweed and fish.

Experiment 5

The inhibitory effect of trehalose and maltitol on the formation of calcium phosphate precipitate

When a phosphate ion is added to an aqueous solution of calcium chloride from an calcium ion and a phosphate ion, an insoluble calcium phosphate salt is formed and precipitates. The effects of trehalose, maltitol and other saccharides on the phenomenon were investigated as follows. An aqueous solution of calcium chloride was prepared by stepwise adding 3.68 g of calcium dihydrochloride to deionized water to dissolve in it and adding deionized water to the solution to a total volume of 200 ml. Aqueous crystalline trehalose, anhydrous crystalline maltitol, an aqueous crystalline maltose and anhydrous crystalline sucrose were used as saccharides for testing. A phosphate solution (pH 6.8) was prepared by stepwise mixing 250 ml of a 0.2 M solution of potassium dihydrogen phosphate and 118 ml of a 0.2 M solution of sodium hydroxide, bringing the resulting solution to 1 L with deionized water.

26 g of any saccharide (s.t.o.) for the test was added to 5 ml of the above calcium chloride solution and dissolved by adding an additional amount of deionized water. The resulting aqueous solutions were supplemented to obtain a total volume of 50 ml. A control solution was prepared by the stepwise addition of deionized water to only 5 ml of the above calcium chloride solution and the addition of the resulting solution with deionized water to a total volume of 50 ml. Then, 40 ml of the above phosphate solution was mixed with 10 ml of calcium chloride solution. After stirring at 37 ° C for 3 hours, each solution was centrifuged at 10,000 rpm for 10 minutes and the resulting supernatant was collected. The calcium concentration (solubilized calcium concentration) in each supernatant was measured using a ZEEMAN 5100 instrument, an atomic adsorption photometer sold by Perkin-Elmer Japan Co. Ltd., Kanagawa, Japan. Samples for measurement were prepared by the stepwise addition of 2 ml of a 10% (w / v) lanthanum chloride solution to 5 ml of each of the above supernatants after centrifugation and the addition of the final solution with deionized water to 25 ml.

The above procedure was performed for each individual sample (4 types of saccharides and control) 3 times and the average concentration of solubilized calcium was calculated. The results are summarized in table 9.

Table 9 Saccharide The concentration of solubilized calcium (mg / l, mean ± standard deviation) Saccharide-free (control) 6.86 ± 0.49 Trehalose 23.90 ± 2.54 Maltitol 20.13 ± 1.17 Maltose 6.79 ± 0.52 Sucrose 6.54 ± 0.31

As shown in table 9, it was revealed that trehalose and maltitol were able to suppress the precipitation of calcium phosphate, which is formed in the joint presence of calcium ion and phosphate ion. Based on the results obtained in experiments 1-3, which showed the formation of trehalose and maltitol associates with compounds containing metal ions, it was believed that trehalose and maltitol inhibited the formation of an insoluble salt (calcium phosphate) formed by the ionic bond between the calcium ion and the phosphate ion association with a solubilized calcium salt (in this experiment, calcium chloride).

Experiment 6

The action of trehalose and maltitol to improve the solubility of the calcium salt of an organic acid

The effect of trehalose, maltitol and other saccharides on the solubility of calcium salts of organic acids was investigated as follows. Three types of saccharide solutions, including various saccharides, were prepared by dissolving 5 g (bar) of trehalose, maltitol and maltose in 35 ml of deionized water. Then 5 g of commercially available calcium pentahydro-DL-lactate or calcium monohydrogluconate, used as the calcium salts of organic acids, was added to each saccharide solution, followed by suspension. Then the pH of each solution was adjusted to 3.5, and the solution was supplemented with deionized water to a volume of 50 ml. After stirring at 25 ° C for 16 hours, insoluble calcium salts of organic acids were removed by centrifugation (15,000 rpm for 30 minutes). The pH values of the resulting supernatants were measured. Calcium concentrations in the supernatant were measured using the atomic adsorption photometer described in Experiment 5. In a solution prepared without saccharide, calcium concentration was also measured in the same manner as in the control. The results are presented in table 10.

Table 10 Calcium lactate Calcium gluconate pH Ca concentration (mg / ml) Relative concentration (%) pH Ca concentration (mg / ml) Relative concentration (%) No saccharides 3,7 10.44 one hundred 3,7 4,54 one hundred Trehalose 3,7 13.46 129 3,7 5.07 112 Maltitol 3,7 12.82 123 3,7 5.83 128 Maltose 3,7 10.19 98 3,7 4.73 104

As shown in table 10, the pH of all supernatants was 3.7. The concentration of calcium in the supernatant increased with the addition of trehalose or maltitol. In the case of calcium lactate, the concentration of calcium in the supernatant increased by 29% in the case of trehalose and by 23% in the case of maltitol compared with the concentration of calcium in the control. In the case of calcium gluconate, the concentration of calcium in the supernatant increased by 12% in the case of trehalose and by 28% in the case of maltitol compared with the concentration of calcium in the control. Trehalose and maltitol were found to have the function of improving the solubility of calcium salts of organic acids such as calcium lactate and calcium gluconate. The function of trehalose and maltitol could be used to prevent turbidity of soft drinks, including calcium salts of organic acids, sports drinks and drinks with mineral additives, which occurs during storage for a long period of time.

Experiment 7

The effect of suppression of trehalose and maltitol oxidation of a ferrous ion

In general, ferrous ion (divalent, Fe ²⁺ ) and ferric ion (ferric, Fe ³⁺ ) are known as ions of the iron element. The bivalent iron ion is easily oxidized by light or heat and turns into a ferric ion. The effects of trehalose and maltitol on the phenomenon were investigated as follows. An aqueous solution comprising ferrous tetrahydrochloride (FeCl ₂ ), corresponding to an amount of 1% (w / v) in the form of a ferrous ion, and including trehalose or maltitol, corresponding to an amount of 5% (w / v), (p. thus), was prepared as a test solution. Along with this, as a control solution, a solution was prepared including ferrous chloride with the same concentration as the test solution. After preparing the test and control solutions, small portions of which were respectively taken as samples, the amount of ferrous ions was measured using the Nitroso-DMAP method described below. Then 10 ml of each of the test and control solutions were placed separately in a 20 ml bottle and sealed. After storing these vials at 37 ° C for 4 hours with light irradiation of approximately 9000 lux, the amount of ferrous ion in each solution was measured by the Nitroso-DMAP method. Measurement by the Nitroso-DMAP method was carried out as follows. After accurate 100-fold dilution of the test or control solution, 0.5 ml of diluted solution was placed in a 50 ml volumetric flask. Then, 5 ml of 0.2% (w / v) nitroso-dimethylaminophenol in a 0.1 N hydrochloric acid solution and 4 ml of 3 N ammonium buffer (pH 8.5) were quickly added to the diluted solution and carefully added with deionized water to a volume 50 ml After the above procedure, the spectral absorbance of the solution was measured at 750 nm (within the range of visible light). Standard solutions obtained by stepwise dilution of a solution of ferrous chloride with a known concentration were used for measurement in the same way to obtain a standard curve for quantitative analysis. The amount of ferrous ions in the test or control solution was determined by a standard curve. The results are presented in table 11.

Table 11 Saccharide The amount of ion Fe ²⁺ (mg / ml) Before light exposure After light exposure Trehalose 10.1 4.4 Maltitol 10,2 4.3 Saccharide-free (control) 10,2 3.8

As shown in Table 11, in the test solution, including trehalose or maltitol, the ferrous ion remained in obviously large amounts after light irradiation compared to its amount in the control solution. Taking into account these results and the results of experiment 2-2, which showed the formation of an associate from trehalose and an iron salt, it was believed that the above inhibitory effect of trehalose and maltitol is the result of the formation of associates of these saccharides and an iron salt.

Experiment 8

The inhibitory effect of trehalose and maltitol on the destruction of ascorbic acid in the presence of a metal ion

L-ascorbic acid is rapidly destroyed by oxidative decomposition in the presence of iron and copper ions and causes darkening. The effects of trehalose and maltitol on the phenomenon were studied as follows. 10 types of aqueous solutions were prepared having the corresponding compositions described in Table 12. Aqueous solutions of L-ascorbic acid or L-ascorbic acid alone and compounds containing metal ions were used as controls. Test solutions were prepared by adding trehalose or maltitol to control solutions. 10 ml of each of these test and control solutions were placed in various 20 ml vials and sealed. The vials were stored at 50 ° C. Control and test solutions containing ferrous chloride and solutions containing ferrous chloride or copper sulfate were stored for 96 hours and 40 hours, respectively. After storage, the degree of staining of each solution was measured. In the case of a control solution containing one L-ascorbic acid, staining was measured through storage periods of 40 hours and 96 hours. The absorbance at 420 nm (within the visible light range) of each sample was measured as an estimate of the degree of staining. The results are presented in table 12.

Table12 The composition of the solution * Note Degree of staining (Abs. ** at 420 nm) Storage for 40 hours Storage for 96 hours 14.8 mm AsA The control 0,021 0.166 14.8 mm AsA + 10 mm CuSO ₄
14.8 mM AsA + 10 mM CuSO ₄ + 100 mM Tre
14.8 mM AsA + 10 mM CuSO ₄ + 100 mM Mal The control
Test
Test 0,800
0.311
0.258 -
-
- 14.8 mm AsA + 10 mm FeCl ₃
14.8 mm AsA + 10 mm FeCl ₃ + 100 mm Tre
14.8 mm AsA + 10 mm FeCl ₃ + 100 mm Mal The control
Test
Test 0.529
0.226
0.198 -
-
- 14.8 mm AsA + 10 mm FeCl ₂
14.8 mm AsA + 10 mm FeCl ₂ + 100 mm Tre
14.8 mm AsA + 10 mm FeCl ₂ + 100 mm Mal The control
Test
Test -
-
- 0.588
0.380
0.291 * The designations "AsA", "Tre" and "Mal" respectively mean L-ascorbic acid, trehalose and maltitol.
** Spectral Absorption

As shown in table 12, the degree of staining of test solutions containing trehalose and maltitol was significantly lower compared to staining control. Considering these results and the results of experiment 2-2, which showed the formation of an associate of trehalose and an iron salt or copper salt, it is believed that the above inhibitory effects of trehalose and maltitol are the result of the formation of associates of these saccharides and iron salts and copper salts.

Experiment 9

The inhibitory effect of trehalose on the formation of scale during boiling food

The scale is formed by boiling one meat or meat with vegetables. If excess scale is formed, it should be removed. The effect of trehalose on the above phenomenon was studied as follows. 30 g of pork and 20 g of spinach were added to 400 ml of water, and then 2% (w / w) or 10% (w / w) sucrose were mixed into them. Then the mixture was heated, boiled for 1 min, stopped heating, and then cooled to room temperature. After cooling, the scale was isolated by stepwise collection on a KIRIYAMA filter by washing with 500 ml of deionized water and drying at 40 ° C for 18 hours. The scale obtained in the same way without using saccharide was used as a control. The scale weight and the amount of the main components contained in the scale were measured. The results are presented in table 13.

Table 13 Saccharide Amount% (w / w) Limescale Fat (g) Protein (g) Ash (g) Ca (mg) Mg (mg) (g) Rel wt. * (%) Trehalose 2 0.506 46 0.406 0,076 0.009 1,613 0.810 10 0.315 29th 0.244 0,048 0.005 1,593 0.156 Sucrose 2 1,060 97 0.871 0.170 0.013 1,672 2,475 No saccharides 0 1,091 one hundred 0.899 0.166 0.012 1,326 2,550 * Relative weight (%)

As shown in table 13, the scale mass decreased with increasing amount of trehalose. At the same time, sucrose did not have the effect of reducing the amount of scale. The amount of scale formed using sucrose was almost the same as in the control. From the results obtained, it was revealed that trehalose had the property of inhibiting the formation of scale. From an analysis of scale components, it is believed that calcium ion and magnesium ion are deeply involved in inhibiting scale formation by trehalose. Trehalose is also believed to inhibit the formation of insoluble compounds containing magnesium ions, in particular magnesium salts of fatty acids.

Experiment 10

The inhibitory effect of trehalose and maltitol on the formation of scale during the preparation of boiled foods

The effects of trehalose and maltitol on the formation of scale were compared with the action of other saccharides as follows. After adding 30 g of pork to 400 ml of each solution, which included 10% (w / w) of one of trehalose, maltitol, neotrehalose, sucrose, maltose or glucose, and soaking for 10 minutes, the solution was heated and boiled for 5 minutes. After the termination of heating and cooling to room temperature, the obtained scum was isolated by stepwise collection on a KIRIYAMA filter, washing with 500 ml of deionized water and drying at 40 ° C for 18 h. The scum obtained in a similar way without using saccharide was used as a control. The scale weight and the amount of minerals (calcium, magnesium, sodium, and potassium) contained in the scale were measured. The results are presented in table 14.

Table 14 Limescale Calcium Magnesium Sodium Potassium (g) (%) (mg) (%) (mg) (%) (mg) (%) (mg) (%) No saccharides 2,252 one hundred 0.177 one hundred 0.056 one hundred 0.247 one hundred 0,023 one hundred Trehalose 0.579 26 0,048 41 0.011 twenty 0.182 74 0.017 74 Maltitol 0.802 36 0,030 26 0,029 52 0.183 74 0.015 65 Neotregalose 1,942 86 0,090 77 0,042 75 0.237 96 0.024 104 Sucrose 1,718 76 0.113 97 0,052 93 0.299 121 0,025 109 Maltose 2,126 94 0,092 79 0,050 89 0.283 115 0,025 109 Glucose 2,171 96 0.118 101 0,048 86 0.263 106 0.019 83

As shown in table 14, in the case of using trehalose or maltitol, the mass of scale formed decreased to less than half in the case of control (without saccharide). At the same time, neotrehalose, sucrose, maltose and glucose did not have an effect on reducing the amount of scale. The amount of scale formed when using these saccharides was almost at the same level as in the control (without saccharide). As a result of the analysis of the minerals contained in the scale, it was found that the content of calcium and magnesium was low. Trehalose and maltitol are believed to inhibit scale formation by inhibiting the formation of insoluble compounds containing calcium and magnesium ions.

Experiment 11

The inhibitory effect of trehalose on the elution of magnesium from foods boiled during cooking

The corresponding filtrates obtained by descaling in experiment 10 were supplemented with water to obtain a total volume of 500 ml, and the amount of minerals (calcium, magnesium, sodium, and potassium) contained in the filtrates was measured. The results are presented in table 15. It is believed that the total amount of minerals eluted from 30 g of pork can be calculated by summing the values in table 14 (amount in scale) and the values in table 15 (amount in filtrate). Therefore, the total quantities and relative values calculated using control values (without saccharide) as having 100 parts are presented in table 16.

Table 15 Ca Mg Na K (mg) % (mg) % (mg) % (mg) % Without saccharide 0.964 one hundred 1,158 one hundred 3,442 one hundred 6,325 one hundred Trehalose 0.788 82 0.485 42 3,490 101 6.035 95 Maltitol 1,425 148 1,523 132 3,412 99 6,150 97 Neotregalose 0.957 99 1,148 99 3,880 113 6,060 96 Sucrose 0.977 101 1,150 99 3,420 99 6,165 97 Maltose 0.942 98 1,152 99 3,437 one hundred 6,160 97 Glucose 1,051 109 1,149 99 3,426 one hundred 6,285 99 Table 16 Ca Mg Na K (mg) % (mg) % (mg) % (mg) % Without saccharide 1,081 one hundred 1,214 one hundred 3,689 one hundred 6,348 one hundred Trehalose 0.836 77 0.496 41 3,672 one hundred 6,052 95 Maltitol 1,455 135 1,552 128 3,595 97 6,165 97 Neotregalose 1,047 97 1,190 98 4,117 112 6,084 96 Sucrose 1,090 101 1,202 99 3,719 101 6,190 98 Maltose 1,034 96 1,202 99 3,720 101 6,185 97 Glucose 1,169 108 1,197 99 3,689 one hundred 6,304 99

As shown in table 16, in the case of the use of saccharides, with the exception of trehalose and maltitol, the total amounts of the corresponding minerals eluted from pork were almost the same as in the case of control (without saccharide). At the same time, especially in the case of using trehalose, the amount of magnesium was less than half the control, and trehalose inhibited the elution of compounds containing magnesium ions. On the other hand, in the case of maltitol, the amounts of calcium and magnesium eluted from pork were greater than in the control, and maltitol facilitated the elution of compounds containing calcium and magnesium ions from pork. According to the results, it was suggested that maltitol inhibits scale formation by suppressing the insolubility of compounds containing calcium and magnesium ions, even though maltitol promotes their elution from pork. Trehalose is also believed to inhibit scale formation by suppressing elution from pork of compounds containing calcium and magnesium ions, in particular compounds containing magnesium ions.

Experiment 12

The inhibitory effect of trehalose on the elution of magnesium from vegetables that are boiled during cooking

The inhibitory effect of trehalose on magnesium elution was investigated in vegetables. After adding 20 g of “shungiku” (garland chrysanthemum) or spinach to 400 ml of an aqueous solution including 10% (w / w) trehalose and soaking for 10 minutes, the solution was heated and boiled for 5 minutes. After stopping heating and cooling to room temperature, the resulting scale was isolated in stages by collecting on a KIRIYAMA filter, washing the collected scale with 500 ml of deionized water and drying at 40 ° C for 18 hours. The scale weight and the amount of minerals contained in the scale were measured with the same as in Example 9. The filtrates obtained by descaling were supplemented with water to a total volume of 500 ml, and the amounts of minerals (calcium, magnesium, sodium, and potassium) were measured in the same manner as in Experiment 10. Samples prepared without saccharide, andsam ples prepared using sucrose instead of trehalose were used as controls, respectively 1 and 2. The total amounts of minerals contained in scum and filtrate were defined as the amount of minerals eluted from vegetables during the cooking. The amounts of minerals contained in the scale and filtrate are presented in tables 17 and 18, respectively. The sums of the indicated values (total amount of eluted minerals) are presented in table 19.

Table 17 Vegetable Saccharide Limescale Calcium Magnesium Sodium Potassium (g) (%) (mcg) (%) (mcg) (%) (mcg) (%) (mcg) (%) Garland chrysanthemum Without saccharide 0.014 one hundred 0.410 one hundred 0,092 one hundred 0.197 one hundred 0.380 one hundred Trehalose 0.008 57 0.156 38 0,034 37 0,074 37 0,300 79 Sucrose 0.010 71 0.299 73 0.059 63 0.058 29th 0.288 76 Spinach Without saccharide 0,034 one hundred 1,140 one hundred 0.823 one hundred 0.830 one hundred 1,204 one hundred Trehalose 0,022 65 0.553 48 0,501 61 0.727 88 0.804 67 Sucrose 0,022 65 0.886 78 0.542 64 0.461 56 0.726 60

Table 18 Vegetable Saccharide Calcium Magnesium Sodium Potassium (mg) (%) (mg) (%) (mg) (%) (mg) (%) Garland chrysanthemum Without saccharide 13,109 one hundred 1,299 one hundred 3,231 one hundred 0.707 one hundred Trehalose 11,928 91 0.628 48 3,314 103 0.615 87 Sucrose 12,683 97 1,440 111 3,213 99 0.655 93 Spinach Without saccharide 4,426 one hundred 6,986 one hundred 1,954 one hundred 0.778 one hundred Trehalose 3,850 87 3,264 47 1,879 96 0.752 97 Sucrose 4,604 104 6,954 one hundred 1,918 98 0.825 106

Table 19 Vegetable Saccharide Calcium Magnesium Sodium Potassium (mg) (%) (mg) (%) (mg) (%) (mg) (%) Garland chrysanthemum Without saccharide 13,109 one hundred 1,299 one hundred 3,231 one hundred 0.707 one hundred Trehalose 11,928 91 0.628 48 3,314 103 0.615 87 Sucrose 12,683 97 1,440 111 3,213 99 0.656 93 Spinach Without saccharide 4,427 one hundred 6,987 one hundred 1,955 one hundred 0.779 one hundred Trehalose 3,851 87 3,265 47 1,879 96 0.753 97 Sucrose 4,605 104 6,955 one hundred 1,919 98 0.825 106

As shown in tables 17, 18 and 19, it was revealed that trehalose suppressed the formation of scale from “shungiku” (garland chrysanthemum) and spinach and, in particular, the elution of compounds containing magnesium ions. Trehalose showed the ability to suppress the elution of compounds containing magnesium ions from vegetables during cooking, as in the case of meat described in experiment 11. Turning to the color of the garland chrysanthemum and spinach after boiling, boiled vegetables prepared using trehalose retained their green color well compared to vegetables prepared without the use of saccharide and using sucrose.

Experiment 13

The inhibitory effect of trehalose on the elution of magnesium from Japanese wheat noodles when boiled

The inhibitory effect of trehalose on magnesium elution was investigated on boiling Japanese wheat noodles. 5 g of raw Japanese wheat noodle was added to 40 ml of an aqueous solution, including 10% (w / w) trehalose, heated and boiled for 2 minutes. After stopping heating and cooling to room temperature, the noodles were removed and filtered through a glass fiber filter. The resulting filtrate was supplemented with water to a total volume of 50 ml. Among the minerals contained in the filtrate, only the amount of magnesium was measured in the same manner as in experiment 10. The filtrate prepared without saccharide was used as a control. The results of measuring the amount of magnesium contained in the filtrates are presented in table 20.

Table 20 Saccharide Magnesium (mcg) (%) Without saccharide 162.6 one hundred Trehalose 51.9 48

As shown in table 20, it was revealed that trehalose inhibited the elution of compounds containing magnesium ions from Japanese wheat noodles during boiling. Trehalose has shown the ability to suppress the elution of compounds containing magnesium ions from Japanese wheat noodles during boiling, as in the case of meat and vegetables described in experiments 11 and 12, respectively.

The following examples explain in detail the associates of the present invention and their use.

Example 1

Trehalose and Calcium Chloride Association

In accordance with the method described in experiment 1-1, crystals of two types of associates of trehalose and calcium chloride were obtained in molar ratios of 1: 1 and 1: 2. A tablet was prepared in the usual way by mixing 2.5 mg of each of the preparations with 200 mg of potassium chloride as an excipient and molding the mixture into a tablet. The infrared absorption spectra of the preparations were measured using a FT-IR 8200 Fourier transform infrared spectrophotometer. The results are presented, respectively, in FIGS. 5 and 6.

Since the above products have less hygroscopicity, they are characterized by a satisfactory ability to manipulate them when stored or mixed with various compositions. Further, since the above products are unlikely to form an insoluble salt, such as calcium phosphate, when mixed with a composition comprising phosphoric acid, phosphate salt or phosphorus ion, end products whose clouding or precipitation was prevented can be obtained using products containing aqueous solutions with calcium, such as isotonic drinks, nutritional supplements and topical preparations applied to the skin. Therefore, the above crystals of the two types of associates of trehalose and calcium chloride are very useful as components for calcium products in various fields of food production, cosmetics, pharmaceuticals, etc.

Example 2

Associations of trehalose and various compounds containing metal ions

One part of the mass. (h wt.) of aqueous crystalline trehalose was mixed with equimolar and trehalose amounts of each of magnesium hemihydrochloride, strontium hexahydrochloride, ferrous tetrahydrochloride, copper tetrahydrochloride, nickel hexahydrochloride or manganese hexahydrochloride, mixed with 0.53 h of mass. deionized water and completely dissolved with heating. After cooling, each solution obtained was dried in vacuum at 80 ° C for 15 hours. 7 types of powdery associates were obtained by grinding the obtained dried materials into powder. A part of these samples was taken respectively and used to analyze the absorption spectrum of infrared light in accordance with the method described in example 1. The results are presented in Figs.

Since the solubility of these associates in water is improved compared to compounds containing metal ions alone, end products whose clouding and precipitation are prevented can be obtained by using associates as components of aqueous solutions with compounds containing metal ions, such as isotonic drinks, nutritional supplements and preparations for external use with application to the skin. Therefore, associates are very useful as components for products with compounds containing metal ions in various fields of food production, cosmetics, pharmaceuticals, etc.

Example 3

Associations of maltitol and various compounds containing metal ions

One part of the mass. anhydrous crystalline maltitol was mixed with equimolar with maltitol amounts of each of calcium dihydrochloride or tetrahydrochloride of ferrous iron, mixed with 0.53 part of the mass. deionized water and completely dissolved with heating. After cooling, each resulting solution was dried in vacuum at 80 ° C for 15 hours. 2 types of powdery associates were obtained by grinding the obtained dried materials into powder. A part of these samples was taken, respectively, and used to analyze the absorption spectrum of infrared light in accordance with the method described in example 1. The results are presented in Figs. 13 and 14, respectively.

Since the solubility of these associates in water is improved compared to certain compounds containing metal ions, end products whose clouding and precipitation are prevented can be obtained by using associates as components of aqueous solutions with compounds containing metal ions, such as isotonic drinks, nutritional supplements and preparations for external use with application to the skin. Therefore, associates are very useful as components for products with compounds containing metal ions in various fields of food production, cosmetics, pharmaceuticals, etc.

Example 4

Powdered Isotonic Drink

In accordance with the composition described below, a powder composition was prepared by mixing a sufficient amount of each component.

Aqueous crystalline trehalose 6000 h wt. Sucrose 5000 parts by weight Vitamin B1 0.1 h wt. Vitamin B2 0.3 h wt. Vitamin B6 0.4 h wt. Vitamin C 200 h wt. Niacin 4 h wt. Disodium phosphate (anhydrate) 93 h wt. Potassium Phosphate (Anhydrate) 62 parts by weight Associated trehalose and magnesium chloride obtained by the method of example 2 90 h wt. The associate trehalose and calcium chloride (molar ratio 1: 2) obtained by the method of example 1 55 h wt.

The above powder composition was dispensed into 200 ml plastic bottles equipped with screw caps for the manufacture of isotonic powdered drinks. The product can be drunk after mixing approximately 100 ml of water with 10 g of the product and dissolving. Since the associates of trehalose and compounds containing metal ions contained in the product have low hygroscopic properties, the product can be stored for a long period of time. Also, the associates contained in the product are convenient because they quickly dissolve in water. Further, since the associate of trehalose and calcium chloride contained in the product is unlikely to form insoluble salts from phosphate ions and precipitates upon dissolution in water, the product is unlikely to degrade the absorption of each component when the product solution is drunk after dissolving and storing it for a relatively long time time.

Example 5

Skin Lotion (Outer Skin Lotion)

In accordance with the composition described below, a liquid composition is prepared by mixing and dissolving.

Lemon acid 0.02 h wt. Sodium citrate 0.08 h wt. 1,3-butylene glycol 2 h wt. Ethanol 2 h wt. Anhydrous Crystalline Maltitol 1 h wt. Aqueous crystalline trehalose 0.2 h wt. L-ascorbic acid 2-glucoside 0.5 h wt. The maltitol and ferrous chloride association obtained by the method of example 3 0.0035 h wt. Purified water The rest of Total 100 h wt.

The above liquid composition was poured into 100 ml glass bottles equipped with screw caps to obtain skin lotions. Since the product provides an adequate refreshing sensation and has the ability to retain moisture, it can be used as the main means for skin care to maintain a healthy skin condition. Since the associate of maltitol and ferrous chloride contained in the product is unlikely to cause damage to other components, the described effects can be obtained after storage of the product for a relatively long period of time.

Example 6

Vitamin supplement

In accordance with the composition described below, a powder composition was obtained by mixing a sufficient amount of each component.

Folic acid 0,0004 h wt. L-ascorbic acid 0.2 h wt. Associated trehalose and magnesium chloride obtained by the method of example 2 5 h wt. Associated trehalose and manganese chloride obtained by the method of example 1 0.008 parts by weight Aqueous crystalline trehalose 5 h wt.

The above powder composition was dispensed into 80 ml glass bottles equipped with screw caps to obtain a vitamin supplement. The product is taken orally with an approximate rate of about 10 g per day, and can be drunk after adding approximately 100 ml of water or hot water to 10 g of the product and dissolving it. Since the associates of trehalose and compounds containing metal ions in the product can be quickly dissolved in water, the use of the product is very easy.

Example 7

Powder, including the associate of trehalose and components of the mother liquor

In accordance with the method described in the experiment 2-1, 4 hours of mass. aqueous crystalline trehalose and 25 hours of mass. a commercially available mother liquor sold by Sanuki Engyou Co., Ltd., Kagawa, Japan, was mixed and completely dissolved by heating. The resulting solution was dried in vacuo at 60 ° C for 15 hours, and then the resulting dried substance was pulverized to obtain a powder including associate. In accordance with the method described in example 1, the analysis of the absorption spectrum of infrared light of the product was carried out. The result is shown in FIG.

Since the product has less hygroscopicity compared to the control, dried powder of the mother liquor obtained by the method of experiment 4, it can be satisfactorily manipulated during storage and mixing with various compositions. Also, since the unpleasant taste properties inherent in the mother liquor, such as the pungent taste and the bitter taste, were suppressed and improved by the formation of an associate with trehalose, the product can be used as a mineral fortifier, including relatively large amounts of magnesium and calcium; seasoning material, isotonic drinks, nutritional supplements, food, pet food; and a taste-improving product for the production of "ann" (sweetened bean paste), "natto" (fermented soybeans), soy milk and "tofu" (cottage cheese from beans); in particular, as a coagulant for "tofu" (bean curd). In addition, the product is very useful as a component of various products in various areas of food production, agricultural and marine products, cosmetics, pharmaceuticals, etc., as a mineral enrichment of minerals such as magnesium and calcium, plant nutritional supplements activating agents for plants, moisture holding agents, an allergy suppressing agent such as hay fever (pollen disease), etc.

Example 8

Powder, including the associate of trehalose and components of the mother liquor

1 h mass. aqueous crystalline trehalose and 1 h of mass. a commercially available mother liquor sold by Sanuki Engyou Co., Ltd., Kagawa, Japan, was mixed and completely dissolved by heating. The resulting solution was sprayed for 300 hours of mass. anhydrous crystalline trehalose and mixed to obtain a dried powder, including associate.

Since the product has less hygroscopicity compared to the control, dried powder of the mother liquor obtained by the method of experiment 4, it can be satisfactorily manipulated during storage and mixing with various compositions. Also, since the unpleasant taste properties inherent in the mother liquor, such as the pungent taste and the bitter taste, were suppressed and improved by the formation of an associate with trehalose, the product can be used as a mineral fortifier, including large amounts of magnesium and calcium; seasoning material, isotonic drinks, nutritional supplements, food, pet food; and a taste-improving agent for the production of "ann" (sweetened bean paste), "natto" (fermented soybeans), soy milk and "tofu" (bean curd); in particular, as a coagulant for "tofu" (bean curd). In addition, the product is very useful as a component of various products in various areas of food production, agricultural and marine products, cosmetics, pharmaceuticals, etc., as a mineral enrichment of minerals such as magnesium and calcium, plant nutritional supplements activating agents for plants, moisture holding agents, an allergy suppressing agent such as hay fever (pollen disease), etc.

Example 9

A solution comprising the associate of trehalose and components of the mother liquor

In accordance with the method described in experiment 2-1, 144 hours of mass. aqueous crystalline trehalose and 202 hours of mass. a commercially available mother liquor sold by Sanuki Engyou Co., Ltd., Kagawa, Japan, was mixed and completely dissolved by heating. The resulting solution was concentrated under reduced pressure, and then at 60 ° C. for 15 hours, and then a concentrated solution containing 63% (w / w) of a dry solid was obtained.

Since the unpleasant taste properties inherent in the mother liquor, such as the pungent taste and the bitter taste, were suppressed and improved by the formation of an associate with trehalose, the product can be used as a mineral fortifier, including large amounts of magnesium and calcium; seasoning material, isotonic drinks, nutritional supplements, food and pet food; and a taste-improving agent for the production of "ann" (sweetened bean paste), "natto" (fermented soybeans), soy milk and "tofu" (bean curd); in particular, as a coagulant for "tofu" (bean curd). In addition, the product is very useful as a material for various products in various areas of food production, agricultural and marine products, cosmetics, pharmaceuticals, etc., as a mineral enrichment of minerals such as magnesium and calcium, plant nutritional supplements activating agents for plants, moisture holding agents, an allergy suppressing agent such as hay fever (pollen disease), etc.

Example 10

Powder comprising maltitol associate and stock saline components

2 h mass. anhydrous crystalline maltitol and 1 h of mass. a commercially available mother liquor was mixed and completely dissolved by heating. The resulting solution was dried in vacuo at 80 ° C for 15 hours, and then the obtained dried substance was pulverized to obtain a powder including associate.

Since the product has less hygroscopicity compared to the control, dried powder of the mother liquor obtained by the method of experiment 4, it can be satisfactorily manipulated during storage and mixing with various compositions. Also, since the unpleasant taste properties inherent in the mother liquor, such as the pungent taste and the bitter taste, were suppressed and improved by the formation of an associate with maltitol, the product can be used as a mineral fortifier, including relatively large amounts of natural magnesium and calcium; seasoning material, isotonic drinks, nutritional supplements, food, pet food; and a taste-improving agent for the production of "ann" (sweetened bean paste), "natto" (fermented soybeans), soy milk and "tofu" (bean curd); in particular as a coagulating agent for tofu (bean curd). In addition, the product is very useful as a component of various products in various areas of food production, agricultural and marine products, cosmetics, pharmaceuticals, etc.

Experiment 11

Table salt

In accordance with the composition described below, solids were prepared by mixing a sufficient amount of each component and drying under reduced pressure. The resulting solids were ground to obtain powdered table salt.

Sodium chloride 90 h wt. A solution containing the associate of trehalose and components of the mother liquor obtained by the method of example 9 12 h wt.

Table salt has low hygroscopicity and satisfactory flowability. Since the unpleasant tastes of the mother liquor, such as the pungent taste and bitter taste associated with sodium chloride and the components of the mother liquor, were suppressed and the product tastes good due to the adequate harmonization of sodium chloride, trehalose and the components of the mother saline, the product can be used for cooking and as a seasoning for foods (including grilled foods) and drinks, and it gets their taste. Also, since the product has a composition similar to the components of sea water, it is a soft salt for living organisms. For example, an aqueous solution comprising a product at a concentration of approximately 3% can advantageously be used to remove sand from marine animals having a shell.

Example 12

Low Sodium Chloride Seasoning Salt

In accordance with the composition described below, a low sodium chloride seasoning salt was prepared by mixing a sufficient amount of each component.

Sodium chloride 60 h wt. Potassium chloride 9 h wt. Monosodium L-Glutamate 1 h wt. A powder comprising the associate of trehalose and components of the mother liquor obtained by the method of example 8 5 h wt.

Seasoning salt with a low sodium chloride content has low hygroscopicity and satisfactory flowability. The bitter taste of the product, derived from the components of the mother liquor, is suppressed. Since the product includes sodium chloride, trehalose, potassium chloride and monosodium L-glutamate, the overall taste of the product improves in addition to the salty taste. The product can be used to improve the palatability of foods and drinks, as well as conventional products, despite the fact that the product has a low sodium chloride content and it gets their taste. Also, the product can be mainly used to help cure patients with diseases of the circulatory system, prevent diseases in adults and, in addition, to maintain and strengthen beauty and health.

Example 13

Anne (sweetened bean paste)

In accordance with the composition Ann described below (sweetened bean paste) is prepared by mixing each component and processing.

Commercially available white unpaste "Anne" paste 1000 parts by weight Sucrose 700 h wt. "SUNMALT-S" (aqueous crystalline maltose) 100 h wt. Starch syrup (75% (w / w) dry solid) 100 h wt. A powder containing the associate of trehalose and components of the mother liquor obtained by the method of example 8 100 h wt. Agar 2.5 hours wt.

Since “ann” includes trehalose and components of the mother liquor, in particular magnesium, it has a satisfactory taste, color, storage ability and low sweetness. Anne is preferred for Japanese confectionery such as Monaka (Japanese cake).

Example 14

Processed soy milk

Processed soy milk was obtained in accordance with the procedure described below. The peel was removed from 10 hours of mass. soybean substances. After autoclaving at 130 ° С for 10 min, 90 h of mass was added to the beans during grinding. hot water. About 60 hours of mass. Soy milk was obtained by removing residues (squeezing cottage cheese from beans) from a solution of the mixture by centrifugation. 10 h mass. maltodextrin (DE (dextrose equivalent) 20), 5 hours mass. "SUNMALT®", a powdered crystalline maltose sold by Hayashibara Shoji Inc., Okayama, Japan, 0.05 parts by weight. table salt obtained by the method of example 11, 0.02 h of mass. soybean oil and a suitable amount of lecithin were added to soy milk and dissolved. Processed soy milk was obtained by the steps of sterilizing the above mixture by heating, deodorizing in vacuo, mixing with a suitable amount of flavoring, homogenizing, cooling, pouring into a vessel and wrapping.

Unlike regular, similar soy milk, processed soy milk includes trehalose and a small amount of magnesium. Therefore, it is a drink that provides a good taste without bitterness, harsh taste and scratching sensation and which can be drunk in one gulp.

Example 15

Tofu (bean curd)

“Tofu” (bean curd) was prepared according to the procedure described below. 1 h mass. soybeans were washed with water, soaked in water for 12 hours, and then crushed. After adding 5 hours of the mass. water to the crushed material and boiling for 5 min, the resulting mixture was filtered through a cloth to obtain soy milk. "Tofu" was obtained by the stepwise addition of 1 h of mass. each of pullulan and powder, which includes the associate trehalose and components of the mother liquor obtained by the method of example 7, to 100 hours of mass. soy milk, as a coagulating agent at 70 ° C, causing its coagulation.

The processing efficiency in the production of real "tofu" is increased, because the time required for coagulation of soy milk is extended to approximately 7 minutes, compared with the case of the use of mother saline. Since tofu includes pullulan and trehalose, it exhibits low syneresis and high yield and has a satisfactory texture, gloss and aroma. The product has satisfactory storage stability and can be used to make chilled tofu, diced, boiled tofu, miso soup.

Example 16

Pullulan film

An aqueous solution of the film material, including pullulan, was prepared according to the composition described below and the bubbles were removed under reduced pressure. Then, a 30 μm thick pullulan film was obtained by the steps of continuously pouring the solution onto a synthetic plastic plate and drying by means of hot air having a temperature of 60 ° C.

"PULLULAN PI-20", a pullulan product sold by Hayashibara Shoji Inc., Okayama, Japan 1000 parts by weight Sugar ester (sucrose monolaurate) 1 h wt. A solution containing the associate of trehalose and components of the mother liquor obtained by the method of example 9 20 h wt. Purified water 3400 h wt.

The pullulan film has satisfactory resistance to changes in moisture and solubility in water. Further, the film tastes good because it includes the associate of trehalose and the components of the mother liquor. The film can be used as a food product and material for recycling. In addition, since the product includes the components of the mother liquor, it can be used as a mineral supplement for minerals such as magnesium, calcium and potassium, and an agent that suppresses an allergic reaction such as rhinitis and swelling of the nasal mucosa caused by hay fever (pollen disease) )

Example 17

Feed mixture

In accordance with the composition described below, a feed mixture was prepared by mixing each component.

Gluten Powder 40 h wt. Skim milk 38 h wt. Lactosaccharose 12 h wt. Vitamin Agent 10 h wt. Fish flour 5 h wt. Calcium Diphosphate 5 h wt. Liquid fat 3 h wt. Calcium carbonate 3 h wt. Sodium chloride 2 h wt. A powder containing an associate of maltitol and components of the mother liquor obtained by the method of example 10 2 h mass.

The above feed mixture is difficult to denature, because the powder, including the associate of maltitol and the components of the mother liquor, which is mixed as minerals in the composition, does not show hygroscopicity. The product is highly preferred in domestic animals and poultry, in particular in pigs. The product has the function of promoting the growth of bifidobacteria, and it can mainly be used to prevent infection and diarrhea in domestic animals, stimulate appetite, deposition of fat in them and suppress the smell of their excrement. The product can optionally be mixed with other feed materials, for example grain, wheat flour, starch, oil sludge and molasses, for the manufacture of fortified feed. The product can also be used along with untreated feed materials such as straw, hay, squeezed sugarcane and the core of corncobs, for the manufacture of other feed mixtures.

Example 18

Cosmetic cream

In accordance with the composition described below, the components are mixed and processed to produce a cosmetic cream. 2 h mass. polyoxyethylene glycol monostearate, 5 parts by weight self-emulsified glycerol monostearate, 2 hours mass. "αG-HESPERIDINE®", α-glucosyl hesperidin sold by Hayashibara Shoji Inc., Okayama, Japan, 1 hr. liquid paraffin, 10 hours mass. glycerol trioctanoate and a suitable amount of preservative were mixed and dissolved with heating in the usual manner. To 2 hours of the mass. L-sodium lactate, 5 hours of mass. 1,3-butylene glycol, 2 hours a powder comprising the maltitol associate and the components of the mother liquor obtained by the method of example 10, and 66 hours of mass. deionized water was mixed into the above mixture and emulsified using a homogenizer. A suitable amount of flavoring agent was further mixed with the resulting mixture and mixed to make a cosmetic cream. The product has moisture retention properties because it includes maltitol and magnesium, and it can be used as a sunburn and skin care and moisturizing agent.

Example 19

Therapeutic ointment (drug for external use)

A therapeutic ointment (preparation for external use) was prepared by mixing the components in accordance with the composition described below. Mixed 200 hours of the mass. powder, including the associate of trehalose and components of the mother liquor obtained by the method of example 8, 300 hours of mass. maltose and 50 hours of mass. methanol, including 3 hours of mass. iodine. Further, to 200 hours of mass. an aqueous solution containing pullulan in an amount of 10% (wt./wt.) mixed the above mixture for the manufacture of ointments for the treatment of wounds, which has an adequate property, ensuring its application to the wound surface, and adhesion to it.

Since the product includes the associate of trehalose and the components of the mother liquor, it includes minerals derived from the mother liquor. In addition to the disinfecting activity of iodine, the maltose contained in the product can be used as an energy-adding agent for cells. Therefore, the use of the product provides the possibility of shortening the treatment period and satisfactory healing of wounds.

Example 20

Plant Nutritional Supplement

A plant nutritional supplement in liquid form was prepared by mixing the components in accordance with the composition described below.

Diammonium phosphate 132 h wt. Ammonium nitrate 17.5 parts by weight Potassium chloride 71.5 parts by weight A solution containing the associate of trehalose and components of the mother liquor obtained by the method of example 9 360 h wt. Water 1000 parts by weight

The product includes nitrogen (N), phosphate (P ₂ O ₅ ), potassium (K ₂ O) and magnesium (MgO) in a ratio of 10: 20: 15: 3, respectively. The product has activity that promotes plant growth and root sprouting when plants take root or transplant, and improve flowering and fruit yields. The product can be used with appropriate dilution with water as a nutritional supplement for plants such as crops, including cereals and potatoes, vegetables, fruit trees, garden plants, garden and roadside trees, grasses at golf courses.

Example 21

Bath agent

A bath agent was prepared by mixing the components in accordance with the composition described below.

Bicarbonate of soda 80 h wt. Dried sodium sulfate 12 h wt. Potassium chloride 4 h wt. Precipitated Calcium Carbonate 2 h wt. Aqueous crystalline trehalose 50 h wt. "αG-HESPERIDINE®", α-glucosyl hesperidin 2 h wt. A powder containing the associate of trehalose and components of the mother liquor obtained by the method of example 8 100 h wt. Coloring agents and perfumes Right amount

Since the product contains trehalose and magnesium, it has a satisfactory ability to retain moisture and retain heat and is suitable as a skin care product and whitening agent. The product can be used with a dilution of 1000-10000 times with warm water to take a bath. The product has the advantage of reducing the amount of soap precipitation, flakes. Further, the product can also be used as cleaning lotions and lotions by dilution.

Example 22

Soy sauce

Soy sauce was prepared in accordance with the composition described below. Aqueous crystalline trehalose is added to TOKUSEN-MARUDAIZU-GENEN-SHOYU, a low salt soy sauce sold by Kikkoman Co. Ltd., Chiba, Japan, which does not contain trehalose, to a concentration of 10% (w / w) and dissolved to obtain soy sauce.

Since the product contains a relatively large amount of trehalose, compared with trehalose-free soy sauce, it inhibits plaque formation, in particular the precipitation of compounds containing magnesium ions during cooking of boiled foods and dishes cooked in dishes. Although the product is a low salt soy sauce, it can advantageously be used to season boiled foods, for daily meals, fried foods, soups, and to preserve the taste of foods as is the case with conventional foods.

Example 23

Miso (soya bean paste)

"Miso" (soybean paste) was prepared in accordance with the composition described below. Aqueous crystalline trehalose is added to TAKEYA-MISO-SHIO-HIKAEME, a low salt miso sold by Takeya Miso Co. Ltd., Nagano, Japan, which does not contain trehalose, until a concentration of 8% (w / w) is obtained and mixed until uniform to form a “miso”.

Since the product includes a relatively large amount of trehalose compared to miso, which does not include trehalose, it inhibits plaque formation, in particular the precipitation of compounds containing magnesium ions during cooking of boiled foods and dishes cooked in dishes. Although the product is a low-salt miso, it can be used predominantly for seasoning boiled foods, for daily meals, fried foods, soups, and to preserve the taste of foods as in the case of conventional foods.

Example 24

Mineral water

Mineral water was prepared in accordance with the procedure described below. Aqueous crystalline trehalose was added to the ground (spring) water, which was pumped out in the mountain to obtain a concentration of 0.5% (w / w) and diluted. The resulting solution was sterilized by filtration through a membrane filter. Sterilized bottles were filled with filtrate for the manufacture of bottled mineral water. The content of the main compounds containing metal ions in mineral water was 40.9 ppm. calcium, 12.5 ppm sodium and 11.6 ppm magnesium.

Since the product includes trehalose, associates of trehalose and compounds containing metal ions are formed. The product does not cloud during storage for an extended period because the solubility of the associates improves. This is a high-quality mineral water, including suitable amounts of minerals, which gives a pleasant taste sensation and quenches thirst well.

Example 25

Isotonic drink

An isotonic beverage was prepared by mixing and dissolving the components in accordance with the composition described below.

Isomerized Sugar (Fructose-Glucose Syrup) 2 h wt. Aqueous crystalline trehalose 3 h wt. Maltitol 3 h wt. Lemon juice 1 h wt. L-ascorbic acid 0.1 h wt. Lemon acid 0.06 h wt. Sodium citrate 0.03 h wt. Sodium chloride 0.05 h wt. Monosodium Phosphate 0.05 h wt. Calcium lactate 0.015 parts by weight Magnesium chloride 0.01 h wt. Coloring agents and flavoring agents Suitable quantity Water 90.685 h wt.

Since the product includes trehalose and maltitol, associates of trehalose and compounds containing metal ions are formed. The product does not cloud during storage for an extended period because the solubility of the calcium salts of organic acids improves. This is a high-quality isotonic drink with a pleasant taste.

Example 26

Dried Wakame (brown seaweed)

Aqueous crystalline trehalose was added to sea water to obtain a concentration of 8% (w / w) and dissolved with heating. After bleaching “wakame” in a solution, the temperature of which was maintained at the level of 80-85 ° С, it was dried to obtain dried “wakame”.

Since trehalose and the components of the mother liquor contained in seawater form an associate on the wakame surface, the hygroscopicity of the product after drying is reduced, and the product does not exhibit tackiness caused by moisture adsorption during storage. The product can mainly be used as a material for salad and as an ingredient for miso soup, and it is unlikely to form scale during cooking. Further, the product can be used as food products, such as confectionery and food materials.

Example 27

Dried Kombu (seaweed)

Aqueous crystalline trehalose was added to sea water to obtain a concentration of 6% (w / w) and dissolved at ambient temperature. After impregnating the “combo” in the solution, it was dried in the sunlight to make a dried “combo”.

Since trehalose and the components of the mother liquor contained in seawater form associates, the hygroscopicity of the product after drying was reduced, and the product did not exhibit tackiness caused by moisture adsorption during storage. The product can mainly be used as a “combo” for soup, and it is unlikely to form scale during cooking. The product is a useful food material for “kobujime” (pickled foods with seaweed), “kobumaki” (rolled seaweed) and “kobucha” (tea made from seaweed) and can be used as food products such as confectionery product and food materials.

Example 28

Soap

Soap was prepared by mixing the components until uniform in accordance with the composition described below.

Pure soap obtained from a mixture of beef fat and palm oil in a mass ratio of 2: 1, by the method of saponification-salting out 80 h wt. Aqueous crystalline trehalose 10 h wt. Maltitol 9 h wt. L-ascorbic acid 2-glucoside 0.5 h wt. Sucrose 0.5 h wt. KANKO-SO No. 201 0.0001 h wt. Flavoring additives Suitable quantity

The product is a high quality soap having a satisfactory foam formation and washing ability. The precipitation of sparingly soluble salts, in particular compounds containing magnesium ions, which have the property of precipitation when the soap is dissolved in hard water, including compounds containing metal ions, can be suppressed with the help of the product. As a result, the product reduces the formation of soap flakes, and its foam formation and washing ability are unlikely to deteriorate. Further, the product can advantageously be used as a soap that prevents body odor and itching, because it inhibits the formation of volatile aldehydes and / or the breakdown of fatty acids that come from sweat fluid, dirt and sebum.

Example 29

Toothpaste

Toothpaste was prepared by mixing the components in accordance with the composition described below.

Calcium Phosphate (CaHPO ₄ ) 48 h wt. Sodium Lauryl Sulfate 1.5 hours wt. Glycerol 25 h wt. Polyoxyethylene Sorbitan Laurate 0.5 h wt. Aqueous crystalline trehalose 10 h wt. Maltitol 10 h wt. Preservatives 0.05 h wt. Water 13 h wt.

The unpleasant taste of the product improves, and it has satisfactory availability without reducing the detergency of the detergents. Since trehalose and maltitol, which are contained in the product, form associates with compounds containing metal ions, the product has the ability to suppress the adhesion of tartar and plaque, which are formed by compounds containing calcium and magnesium ions, and facilitate their dissolution. Therefore, the product has a satisfactory ability to brush teeth with the application of it on the toothbrush.

Example 30

Nabemono broth (Japanese dish cooked in a bowl)

The Nabemono broth (a Japanese dish cooked in a bowl) was prepared according to the procedure described below. To 2.4 hours of the mass. Udon Soup, a commercially available powdered udon soup (Japanese wheat noodle) sold by Hagashimary Shoyu, Co., Ltd., Hyogo, Japan, which does not include trehalose, and 10 parts by weight. aqueous crystalline trehalose was mixed with 90 hours of mass. water and dissolved to prepare the broth for Nabemono (a Japanese dish cooked in a bowl).

Since the product contains a relatively large amount of trehalose, it inhibits the formation of scale, in particular the precipitation of compounds containing magnesium ions from meat and vegetables during the preparation of Nabemono (a Japanese dish cooked in dishes). The product also inhibits the elution of compounds containing magnesium ions from food materials. The product can mainly be used for cooking boiled foods, Nabemono (a Japanese dish cooked in dishes), everyday foods, soup, and to improve the taste of foods.

Industrial applicability

As described above, the present invention revealed that both trehalose and maltitol formed associates with compounds containing metal ions, or components of a mother salt solution, by direct interaction in the presence of compounds containing metal ions, or components of a mother salt solution. Since the associates of the present invention have reduced hygroscopicity, high solubility in water, and reduced reactivity against oxidation and reduction, they are also very useful in view of the possibility of industrial manipulation of them compared to conventional compounds containing metal ions or components of the mother salt solution. The associations of the present invention can advantageously be used in various fields in which compounds containing metal ions or components of the mother liquor are used as materials, ingredients, and products, for example, in food products (including drinks), agricultural and marine products, and cosmetic products , in medicines, in consumer goods, in the chemical industry and in the industrial sectors for the production of materials and ingredients that use sya in the specified areas.

The present invention, having these positive functions and effects, is a significant important invention that makes a great contribution to this field.

Claims (2)

1. Crystalline associate monohydrate containing trehalose, calcium chloride and water in a molar ratio of 1: 1: 1, where the specified crystalline associate in the analysis of powder material by x-ray diffraction has the main diffraction angles (2θ) of 9.02 °, 17.98 ° and 21.90 °. 2. An anhydrous associate crystal containing trehalose and calcium chloride in a molar ratio of 1: 2, where the specified crystalline associate in the analysis of powder material by x-ray diffraction has the main diffraction angles (2θ) of 12.66 °, 21.02 ° and 25.48 ° .

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