DE1202627B - Process for seasoning foods and for developing the flavor of foods - Google Patents

Description

Process for seasoning food and for developing its own flavor of Food The invention has a method of flavoring food and for developing the flavor of foods according to which the foods deoxy-5'-inosinic acid, deoxy-5'-guanylic acid, deoxy-5'-xanthylic acid or salts of these acids are added.

It is widely known that monosodium glutamate or sodium succinate have the ability to develop the natural flavor of food, and that both for the development of the taste or the aroma of food in the Household and in restaurants as well as in the processing of, for example, wine, Meat and canned food are used. Sodium inosinate is also known to have one similar effect.

It is believed that the rich aroma of soups of all kinds of soluble components, in particular of the chemical compounds mentioned above, originates. Hydrolysates of animal or vegetable proteins produced by exposure from acids formed by microorganisms or from protease, or Their processed products are also used as chemical condiments for food known and used as such. Chemical condiments of this type usually contain various amino acids as the main component.

All previously known condiments are used in the food industry on their own or used in household cooking, but they can sometimes be used together be used with two or more kinds of similar chemical flavorings. For example 5'-inosinic acid can be used in combination with monosodium glutamate. Sometimes known chemical seasonings are also used together with a natural seasoning, e.g. B. dried bonito fish (so-called »Katsuobushi (o, to improve the taste or the flavor of food. It is believed that in this Case the taste or aroma improvement through the synergy between the chemical Seasoning and the 5'-inosinic acid contained in dried bonito fish is effected.

All known chemical condiments improve the taste or that Aroma of food, but it is always a different taste, which is improved or emphasized by their addition. In other words, each of them have their own specific effects in flavoring foods.

The inventors searched in a wider area, particularly within of deoxyribonucleic acids and their hydrolysates, according to other chemical compounds, which are able to improve the taste or aroma of food. Here Surprisingly, the following was found: a) The taste or aroma of food can by adding deoxy-5'-inosinic acid, deoxy-5'-guanylic acid or salts or derivatives of these acids are improved or increased. These connections have never been used as chemical condiments because of their ability to change the taste or improving the flavor of food was unknown.

b) Deoxy-5'-xanthylic acid, its salts or derivatives give food have a high palatability so that they can be used as chemical condiments.

c) 5'-deoxyribonucleotides, such as deoxy-5'-uridylic acid, deoxy-5'-cytidylic acid or their derivatives hardly taste good as such, but can it is used in the form of a mixture with deoxy-5'-inosinic acid etc. as a chemical flavoring will.

According to the invention, the inherent flavor of foods is obtained by adding them of deoxy-5'-inosinic acid or deoxy-5'-guanylic acid or its Derivatives improved or increased. The invention is thus of particular value for the food industry and household cooking.

Deoxy-5'-inosinic acid and deoxy-5'-guanylic acid can be obtained from a hydrolyzate from deoxyribonucleic acid or oligodeoxyribonucleotides which from organisms or organs or tissues, such as bacteria, thymus glands of animals, the semen of cattle, herring, etc. are extracted. The hydrolysis can help with an enzyme system of snake venom or a microorganism. The hydrolysis cannot be carried out by a purely chemical process, as it is a chemical one Hydrolysis does not give 5'-deoxyribonueleotides. As the enzyme system from snake venom difficult to obtain, it is preferable to use that of microorganisms. The enzyme system, the deoxyribonucleic acids or oligodeoxyribonucleotides to 5'-deoxyribonucleotides capable of hydrolyzing, etc., is produced by microorganisms belonging to the class of Schizomycetes, Ascomycetes, etc. belong, in particular of microorganisms that belong to the Order Fungi Imperfecti (e.g. genus Fusarium, Verticillium, Gliomastix or Helminthosporium), order Eubacteriales (e.g. genus Bacillus), order Actinomycetales (e.g. genus Streptomyces), order Sphaeriales (e.g. genus Anixiella, Botryosphaeria, Chaetomidium, Glomerella, Neurospora, Ophiobolus, Sordaria, Tilaclidium etc.) and Order Plectascales (e.g. genus Aspergillus) belong.

Deoxyribonucleic acids or oligodeoxynucleotides can be beneficial are hydrolyzed by the enzyme system of the microorganisms mentioned. The hydrolysis can be carried out as follows: 1. Incubation of the microorganism on a medium, containing deoxyribonucleic acid and / or oligodeoxynucleotides.

2. Implementation between the culture broth, the filtered broth or Cell or mycelium suspension of the microorganism and deoxyribonucleic acids and / or oligodeoxyribonucleotides or 3. Reaction of the enzyme system after purification with deoxyribonucleic acids and / or oligodeoxyribonucleotides.

Of these, the second method is the most advantageous for industrial purposes. The procedure is as follows: The microorganism is submerged by aerobic Culture in an aqueous medium at a suitable temperature for sufficient Time incubated to enrich the desired enzyme system. The culture broth can used as an enzyme source or filtered using a crude enzymatic solution and a cell or mycelial body can be obtained, both as an enzyme source for the Hydrolysis can be used. The enzyme source thus obtained becomes one Given a solution containing deoxyribonucleic acids and / or oligodeoxynucleotides. The mixture is left to stand at a suitable temperature until the desired hydrolysis is achieved is finished. If the enzyme source is contaminated by phosphoric monoesterase, become the desired deoxy-5'-ribonucleotides to the corresponding deoxyribonucleosides further hydrolyzed, so that it is necessary to make a treatment that suppresses the effectiveness of phosphoric monoesterase. This is achieved, for example by adding an inhibitor for phosphoric monoesterase, e.g. B. of arsenates, phosphates, Cyanates, fluorides or phenolic compounds, such as phenol itself, cresol, etc., for Reaction mixture or by heat treatment at a temperature of 40 to 60 ° C and a pH of 3.5 to 5.0.

Since there is also an amine-decomposing substance (deaminase) in the above-mentioned Enzyme sources is included, the amine group in the deoxy-5'-adenylic acid, a Component of deoxyribonucleic acid, destroyed, whereby deoxy-5'-inosinic acid is formed will. This process, in which one of the named enzyme sources is used, is thus very advantageous for the production of deoxy-5'-inosinic acid in very good yield.

The desired acids, namely deoxy-5'-inosinic acid, are formed in the reaction mixture and deoxy-5'-guanylic acid, together with other 5'-deoxyribonucleotides, such as deoxy-5'-adenylic acid, Deoxy-5'-uridylic acid, deoxy-5'-thymidylic acid, etc., which, however, have the desired effectiveness show only to a small extent. The reaction mixture contains various impurities, like proteins, sugars, cells or mycelium, inorganic salts, some other culture products etc. Of course, deoxy-5'-inosinic acid or deoxy-5'-guanylic acid can be used for the Purposes of the invention can be used as long as they are not supported by a component or Components contaminated that have an unpleasant or undesirable taste or have a smell or are toxic or harmful. If such components do not are present, the filtrate of the reaction mixture in the usual way to a liquid or powdery substance are concentrated or dried, the deoxy-5'-inosinic acid and / or contains deoxy-5'-guanyl acid and can be used as a seasoning according to the invention is. However, if the reaction mixture is contaminated with components that one have an unpleasant smell or taste, it is appropriate to add the reaction mixture or to subject its filtrate to one or more purification processes.

The purification of the obtained deoxy-5'-ribonucleotides can be done with the help of a strongly acidic cation exchange resin. Such a resin can be deoxy-5'-inosinic acid, Adsorb deoxy-5'-guanylic acid, deoxy-5'-uridylic acid and deoxy-5'-cytidylic acid, and the solution obtained by eluting the resin with an aqueous solvent contains deoxy-5'-inosinic acid and / or deoxy-5'-guanylic acid. It is also possible, to treat the reaction mixture with a weakly acidic ion exchange resin, to remove basic impurities. In the mass that is not adsorbed are Contain deoxy-5'-ribonucleotide. Crude deoxy-5'-inosinic acid, Deoxy-5'-guanylic acid etc. can be obtained separately or simultaneously by concentration. The solution can also be neutralized using the alkali metal salts of deoxy-5'-inosinic acid and deoxy-5'-guanylic acid. According to another embodiment can the reaction mixture can be processed by electrophoresis using an ion exchange resin is used as a partition and pure deoxy-5'-inosinsä.ure and / or deoxy-5'-guanylic acid can be obtained. Further purification can be carried out by adsorption or Partition chromatography on a suitable adsorbent such as activated carbon, silica gel and cellulose powder. The production of the invention the Seasonings added to food are not the subject of the protection request.

Deoxy-5'-inosinic acid or deoxy-5'-guanylic acid are according to the invention for example in the form of the free acid, alkali salts, histidine salts, alkaline earth salts, Ammonium salts or acid amides are suitable. In addition to these acids in pure form you can Acids containing impurities can also be used when these impurities do not have an unpleasant smell or taste, or are non-toxic. To the Allowable contaminants include inorganic salts, nucleotides, or nucleosides. According to the invention, a crude hydrolyzate of deoxyribonucleic acid can thus also be used or used by oligonucleotides from which undesired constituents are removed have been.

It is true that deoxy-5'-xanthylic acid was never considered a natural component Deoxyribonucleic acid is found, however, it can be derived from deoxy-5'-guanylic acid will. The semi-synthesis of deoxy-5'-xanthylic acid from deoxy-5'-guanyl acid can For example, be carried out as follows: Deoxy-5'-guanylic acid is first converted into its 2-diazonium salt with the help of a nitrite and an acid. That the latter is then hydrolyzed with an acid. The one that improves taste and aroma The effect of deoxy-5'-xanthylic acid seems to be somewhat weaker than that of deoxy-5'-guanylic acid. The taste or aroma improved with deoxy-5'-xanthylic acid however, it is very good.

The chemical condiments used in the present invention are heat resistant and can therefore be readily obtained from the hydrolyzate of deoxyribonucleic acid etc. and add to food when cooking or before storage.

The taste or aroma of all foods and beverages, for which the previously known chemical condiments were used is independent of the type or shape of the food and luxury goods - z. B. soups, sauces, pastes, Sausage, canned food, salads, cooked food, preserves, alcoholic beverages, Vinegar, table salt, bread, fruit juices, fermented foods - by adding them the chemical seasonings according to the invention improved or increased. The chemical Seasonings according to the invention can be added to the foodstuffs or luxury items during cooking or added after cooking, d. i.e., they can be the raw or already added to cooked foods.

The amount of new chemical condiments to be added to the food can easily be according to the shape, type and other properties of the Identify food. A more or less large excess of the added However, the amount of seasoning hardly leads to an unpleasant taste of the prepared food. The taste or aroma of deoxy-5'-inosinic acid or deoxy-5'-guanylic acid is noticeable at a concentration of about 0.015%, but the amount used is Concentration when added to liquid foodstuffs and luxury foods about 0.2 to 0.0020 / ".

The new chemical seasonings have a taste similar to that the 5'-inosinic acid and are used to improve or increase the taste and aromas beneficial together with the heretofore known chemical seasonings such as Monosodium glutamate, sodium succinate, sodium inosinate, etc. are used. So it is also possible; the new chemical condiments known condiments, e.g. B. such on the Based on amino acids. Especially when mixed with sodium glutamate its effect is excellent.

The present invention creates a new class of materials in technology made available, which is very suitable as a condiment and a valuable flavor Rounds off the seasoning of food. It was by no means to be foreseen that the 5'-deoxy compounds added to foods according to the invention at all have any flavoring power, as from French patent specification 1219 220 the flavoring power of the 5'-nucleotides is known, on the other hand very closely related others Connections, e.g. B. 2 'and 3' nucleotides, have no flavoring power.

When the new chemical condiments fermented food and luxury foods, such as bean paste (»miso«), sake (Japanese rice beer), whiskey, soy (made from soybeans Japanese dish) are added, it is advisable to do this before Addition to deactivate the phosphorus monoesterase in the food and luxury items or remove them from it.

The concentrations of sodium deoxy-5'-inosinate to be used in various foods and luxury foods are listed below along with those of sodium glutamate. Sodium mono- Nutritional or desoxy sodium Luxury food 5'-inosinate glutamate ° / o ° / o Soy (made from soybeans posed Japanese right) ................ 0.1 0.3 Soup (both according to Japanese nischer as well as western of a kind). . . . . . . . . . . . 0.03 0.1 Bean paste soup ...... 0.05 0.1 Marinated dishes ..... 0.1 0.1 Sake (Japanese rice beer) 0.014 0.1 The implementation of the process according to the invention, provided that the product manufactured according to this is not intended for delivery to areas outside the scope of the Food Act, is currently prohibited on the basis of the ordinance on the approval of foreign substances as additives to food of December 19, 1959.

Example 1 To 100 g of deoxyribonucleic acid obtained from herring spawn 101 culture filtrate of Streptomyces aureus ([W a k s m a n and C u r t i s, W a k s m a n and H e n r i c i] 117O-3303, ATCC-13404). aside from that the mixture is sodium; Arsenate to a final concentration of 10 millimoles admitted. After adjusting the pH of the mixture to 8.5, it becomes 8 hours held at 37 ° C. The hydrolyzate is covered by an activated carbon layer directed, to adsorb the deoxyribonucleotides. The activated carbon comes with a mixture of ammonia and ethanol. eluted and the eluate evaporated to dryness, with a powdery seasoning is obtained, the deoxy-5'-guanylic acid and deoxy-5'-inosinic acid contains, the total amount of these components about 50% of the powdery Wort amounts. Raw soy, as it is produced after normal fermentation and through a Filter press is heated to remove the phosphorus monoesterase used in the clear mowed rice. In 11 of the raw soy treated in this way 4 g of the seasoning prepared in the manner described dissolved to give the taste or to improve the aroma of the soy. Example 2 For 100 g of deoxyribonucleic acid, made from herring spawn becomes 101 Aspergillus culture filtrate quercinus (Rainier [T h o m and C h u r c h] IFO-4363). After hiring the pH of the mixture to 8.5, the mixture is hydrolyzed at 37 ° C for 8 hours and then mixed with 50 g of mycelium. The mixture obtained is after Adjustment of the pH to 5.0 1 hour at 37 ° C hydrolyzed to the deoxy-5'-adenylic acid to convert into dexoxy-5'-inosinic acid, and then passed through an activated carbon layer, in which the deoxy-5'-inosinic acid is adsorbed. The activated carbon comes with a Mixture of ammonia and ethanol eluted and the eluate evaporated to dryness, whereby a powdery seasoning is obtained, the deoxy-5'-guanylic acid and deoxy-5'-inosinic acid contains in a total amount of about 40% of the powdered wort. Refined Sake is heated to deactivate the phosphorous monoesterase. To 11 of the so treated Sake is given 0.2 g of the seasoning prepared in the manner described, whereby an improvement in the aroma of the sake is achieved. Example 3 To 11 of a vegetable soup, which was prepared with the addition of a sufficient amount of common salt, are 0.2 g the wort obtained according to Example 2 and 0.5 g of monosodium glutamate added. Through this the taste or aroma of the soup is greatly improved. Example 4 to 100 g of deoxyribonucleic acid obtained from herring spawn becomes 101 culture filtrate from Botryosphaeria ribis chromogena G. and D. (IFO-4837, ATCC-13834). the Mixture is hydrolyzed for 10 hours at 37 ° C, keeping its pH at about 8.5 will. The hydrolyzate is passed through an activated carbon layer on which the formed Deoxyribonucleotides are adsorbed. The activated charcoal is mixed with an ammonia and ethanol eluted and the eluate concentrated.

With the help of an ion exchange resin, the concentrate is divided into four Components of deoxyribonucleotides fractionated. From the original deoxyribonucleic acid Derived deoxy- 5'-adenylic acid is obtained by destroying the amino group with nitric acid converted to deoxy-5'-inosinic acid. In 11 raw soy, 2 g of the obtained Deoxy-5'-inosinic acid and deoxy-5'-guanylic acid dissolved, which makes the taste or the aroma of the soy is improved. Example s To 50g deoxyribonucleic acid, the from calf thymus, 201 culture filtrate from Helminthosporium sigmoideum var. irregular Cralley and T u 11 i s (IFO-5273, ATCC-13406). After adding sodium sulfate to the mixture up to a concentration of 10 millimoles the mixture is hydrolyzed for 15 hours at 37 ° C, its pH at about 8.0 is held. Then deoxy-5'-inosinic acid and deoxy-5'-guanylic acid obtained in the manner described in Example 4.

To 11 one prepared with the addition of a sufficient amount of table salt Vegetable soup are 0.2 g of deoxy-5'-guanylic acid, 0.2 g of deoxy-5'-inosinic acid and 0.5 g monosodium gluatamate is added, which changes the taste or aroma of the soup is greatly improved. Example 6 To 100 g of deoxyribonucleic acid obtained from herring spawn 101 culture filtrate of Streptomyces aureus [W a k s m a n and C u r t i s, W a k s m a n and H e n r i c i] (IFO-3303, ATCC-13404)]. Sodium arsenate is added to the mixture to a concentration of 10 millimoles. After the pH of the mixture has been adjusted to 8.5, it is kept at 37 ° C. for 8 hours. The hydrolyzate is passed through an activated carbon layer on which the deoxyribonucleoride are adsorbed. The activated carbon is made with a mixture of ammonia and ethanol eluted. The eluate is allowed to flow through a formate type anion exchange resin. The resin adsorbs deoxy-5'-inosinic acid and deoxy-5'-guanylic acid and becomes with an aqueous solution containing 0.01 N-formic acid and 0.05 N-sodium formate to give deoxy-5'-inosinic acid to separate. The eluate is again passed through activated charcoal, with the deoxy-5'-inosinic acid is adsorbed. The activated carbon is eluted with ammoniacal ethanol. The eluate is concentrated to dryness to give deoxy-5'-inosinic acid.

For the preparation of a soup, 100 mg of the resulting broth are added to 11 chicken broth Deoxy-5'-inosinic acid, 1 g of sodium glutamate and a suitable amount of table salt and Given spices. Example ? The resin treated according to Example 6 is treated with an aqueous Solution containing 0.1 N formic acid and 0.1 N sodium formate further eluted, to dissolve out the deoxy-5'-guanylic acid. The eluate is given through activated charcoal, which adsorbs the deoxy-5'-guanylic acid. The activated carbon is made with ammoniacal Ethanol eluted. The eluate is concentrated to dryness, with deoxy-5'-guanylic acid is obtained.

50 mg of the deoxy-5'-guanylic acid obtained are added to 889 cms of chicken broth and 1 g sodium glutamate as well as 7.2 g dry milk, 29 g rice flour, 0.8 g table salt, Add 0.82 g of onion powder, 0.25 g of black pepper and 0.2 g of sage. the mixture is cooked to make a creamy chicken soup.

Claims (2)

Claims: 1. Method for seasoning food and for Development of the inherent flavor of food, characterized in that one the foods deoxy-5'-inosinic acid, deoxy-5'-guanylic acid, deoxy-5'-xanthylic acid or adding their salts. 2. The method according to claim 1, characterized in that sodium glutamate is added in addition to the seasoning. Documents considered: French Patent No. 1219 220; British Patent No. 519,771; Japanese Patent Publication Nos. 139,757, 222,094; Hoffmann-Ostenhof, "Enzymology", 1954, pp. 209 to 211.