JP5889593B2 - Flavor improver for alcoholic beverages - Google Patents

Description

  The present invention relates to a flavor improving agent for alcoholic beverages. More specifically, a flavor improving agent and / or a pH adjusting agent for use in applications such as reduction of unpleasant odor of alcoholic beverage, enhancement of preferred fragrance, imparting aging, enhancement of taste, reduction of sourness, etc. used by adding to alcoholic beverage About.

  The aging of the alcoholic beverage is due to the fact that the properties of the alcoholic beverage change depending on the storage state and acquire various characteristics. Specifically, the substances in the alcoholic beverage chemically react with external factors such as temperature, light (ultraviolet light), storage container, and humidity to generate complex components. In the reaction process, not only a simple oxidation reaction but also a reaction at the interface between ethanol and water, a reaction due to volatilization of volatile components into the atmosphere, a radical reaction due to ultraviolet rays, etc. occur intermittently. It is believed that substances such as higher alcohols and esters are produced.

  There are three types of aging of alcoholic beverages. For example, in Japanese sake, a deep-ripening type (a rich liquor with a dramatic change in flavor caused by room temperature storage) and an intermediate type (from low-temperature storage to room-temperature storage, Or, the reverse is called “mature and light-ripened middle type liquor”, and light-ripe type (low-temperature storage of ginjo sake with a moderate bitter taste while maintaining its taste).

  The aging of alcoholic beverages is a reaction that changes year by year due to various factors as described above, so that it is difficult to verify chemically and has not been elucidated in detail. In addition, aging takes a very long time, and there are disadvantages such as an increase in unpleasant odors such as oxidized odor due to long-term storage. Development of a flavor improving agent for alcoholic beverages and the like has been desired and studied.

  As a substance (agent) for use in improving the flavor of alcoholic beverages as well as imparting a sense of aging, organic acid fermentation broth (Patent Document 1) for the purpose of imparting a fermentation flavor and aging, and masking of unpleasant odors, etc. Although sucralose for the purpose (Patent Document 2) and the like are known, development of a new flavor improving agent and the like that is more effective and highly safe is currently required.

  On the other hand, fucoidan, which is one of the dietary fibers, is Okinawa Mozuku (Cladosiphon okamuranus), Thread Mozuku (Fine Mozuku Mosque: Nemacistus decipiens), and thick Mozuku (Tinocitahicus). Is a heterosulfated polysaccharide composed of fucose having a molecular weight of several hundreds of thousands, which is present in brown algae such as Kjellmaniella crassifolia and Kunabu (Undaria pinnatifida), and is a safe function derived from seaweed with abundant food experience In recent years, it has attracted attention as a natural ingredient. In addition, development of a low-molecular fucoidan in which fucoidan is reduced in molecular weight by an enzyme or the like, and development of a food such as a functional food using the low-molecular fucoidan are underway.

  As described above, a large number of pharmaceutical agents and health foods utilizing the physiological function of fucoidan have been developed so far, but applications other than the physiological function of fucoidan are hardly known.

JP 2007-289181 A JP 2010-042021 A

  The present invention is a novel and highly safe flavor-improving agent and / or pH-adjusting agent for alcoholic beverages that can easily and effectively improve its aroma, taste, sourness, etc., simply by adding it to an alcoholic beverage. The purpose is to provide.

  In order to achieve the above object, as a result of earnest research, the present inventors have added a predetermined amount of an agent containing mozuku-derived fucoidan as an active ingredient to an alcoholic beverage, thereby causing an unpleasant odor (ethanol-stimulated odor, acid odor, (Sulfur odor, musty odor, fatty odor, etc.) is reduced, preferable fragrance is enhanced, ripening is given, taste is enhanced, sourness is reduced, and the flavor, taste and sourness are improved easily and effectively. As a result, the present invention has been achieved.

That is, the embodiment of the present invention is as follows.
(1) A flavor improving agent for alcoholic beverages, characterized by comprising mozuku-derived fucoidan as an active ingredient.
(2) Flavor improvement of alcoholic beverages increases the volatility of isoamyl alcohol in alcoholic beverages and / or reduces at least one volatility selected from ethanol, isobutyric acid, isovaleric acid, caproic acid And / or imparting a sense of maturity to the alcoholic beverage and / or reducing the acidity of the alcoholic beverage and / or enhancing the umami and / or salty taste of the alcoholic beverage ( The agent according to 1).
(3) The alcoholic beverage is a distilled liquor (boiled shochu, barley shochu, rice shochu, buckwheat shochu, awamori, whiskey, bourbon, rum, brandy, tequila, etc.) or a diluted product thereof ( The agent according to 1) or (2).
(4) The agent according to any one of (1) to (3), wherein the mozuku-derived fucoidan is a mozuku hot water extract and / or a processed product thereof.
(5) The hot water extract of Mozuku is a liquid obtained by heating a mixture of Mozuku and water and then filtering the mixture, and desalting the obtained filtrate, The agent according to (4) .
(6) The agent according to (4) or (5), wherein fucoidan derived from mozuku is a purified product obtained by further purifying the hot water extract of mozuku and / or a processed product thereof .
(7) Any one of (4) to (6), wherein the treated product is at least one selected from a concentrate, a paste, a dried product, an emulsion, a liquid, and a diluted product. The agent described in 1.
(8) The mozuku-derived fucoidan is a high molecular fucoidan having a molecular weight of 50,000 or more and has a sulfate group content of 10 to 20%. The agent described.
(9) The agent according to any one of (1) to (8), wherein the mozuku is at least one of yarn mozuku, thick mozuku, and Okinawa mozuku.
(10) Alcohol having an improved flavor, wherein the agent according to any one of (1) to (9) is added as Mozuku-derived fucoidan so as to be 0.0001 to 15.0 w / v%. Beverages.
(11) A method for improving the flavor of an alcoholic beverage, comprising adding Mozuku-derived fucoidan to an alcoholic beverage so as to be 0.0001 to 15.0 w / v%.
(12) A pH adjuster for alcoholic beverages, comprising mozuku-derived fucoidan as an active ingredient.
(13) The agent according to (12), wherein the alcoholic beverage is distilled liquor or a diluted one thereof.
(14) A method of adjusting an alcoholic beverage to pH 4.5 to 6, comprising adding mozuku-derived fucoidan to the alcoholic beverage so as to be 0.0001 to 15.0 w / v%.

  According to the present invention, reduction in unpleasant odor of alcoholic beverages (especially distilled liquor such as whiskey and shochu), enhancement of preferred aromas such as ginjo aroma, imparting aging, reduction of sourness, enhancement of umami and saltiness, solution pH Can be adjusted. In other words, it becomes possible to provide an alcoholic beverage with an improved flavor and the like, which has an aged feeling like old liquor, with the entire taste of the alcoholic beverage being rounded.

It is the graph which compared the amount of ethanol volatilization of wheat shochu. From the left, an additive-free product (control), an alginate-added product (alginic acid), a sodium alginate-added product (sodium alginate), and a mozuku-derived fucoidan-added product (fucoidan) are shown. It is the graph which compared the amount of isoamyl alcohol volatilization of wheat shochu. From the left, an additive-free product (control), an alginate-added product (alginic acid), a sodium alginate-added product (sodium alginate), and a mozuku-derived fucoidan-added product (fucoidan) are shown. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of beer to which a mozuku-derived fucoidan-containing liquid is added. The vertical axis shows the rate of change in sensory evaluation (mozuku-derived fucoidan added product / non-added product) (the same applies to FIGS. 4 to 10 below). It is a sensory evaluation result graph of each evaluation item (horizontal axis) of sake to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of red wine to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of white wine to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of whiskey (water split) to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of whiskey (straight) to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of shochu shochu (water split) to which a mozuku-derived fucoidan-containing liquid is added. It is a sensory evaluation result graph of each evaluation item (horizontal axis) of shochu shochu (straight) to which a mozuku-derived fucoidan-containing liquid is added. It is an analysis result graph by the taste sensor of the shochu shochu (straight) which added the mozuku origin fucoidan containing liquid 1, 2, 4 v / v%. It is a graph which shows the solution pH change at the time of adding a mozuku origin fucoidan containing liquid to water or potato shochu (straight). It is a graph which shows each solution pH change at the time of adding a mozuku origin fucoidan containing liquid to distilled liquor (boiled shochu, barley shochu, rice shochu, soba shochu, awamori, whiskey, bourbon, rum, brandy, tequila). It is the graph which showed the amount of volatilization of isobutyric acid at the time of adding a mozuku origin fucoidan containing liquid to potato shochu (straight). It is the graph which showed the isovaleric acid volatilization amount at the time of adding a mozuku origin fucoidan containing liquid to potato shochu (straight). It is the graph which showed the caproic acid volatilization amount at the time of adding a mozuku origin fucoidan containing liquid to shochu shochu (straight).

  Hereinafter, the present invention will be described in detail.

  In the present invention, fucoidan derived from mozuku, which is a seaweed with abundant food experience and high safety, is used as an active ingredient of a flavor improving agent and / or a pH adjusting agent for alcoholic beverages. The mozuku is preferably Okinawa mozuku (Cladosifon okamuranus), thread mozuku (fine mozuku) (Nemocystus decipiens), and thick mozuku (Tinocladia crassa).

  Mozuku-derived fucoidan can be used as a purified fucoidan product (including commercial products) extracted, isolated and purified from mozuku, as well as a hot water extract of mozuku and its processed product. Although not limited to this, the Mozuku-derived fucoidan has a molecular weight of 50,000 or more, preferably 100,000 or more, more preferably 200,000 to 2,000,000 (for example, 300,000 to 1,000,000) based on pullulan. And the sulfate group content is 10% to 20%, preferably 11% to 17%, more preferably 13% to 14%.

  In order to extract fucoidan from mozuku, it is adjusted to acidic (pH 3.0 to 6.0) with an acetic acid aqueous solution or hydrochloric acid, and is 50 ° C. or higher, preferably 60 to 100 ° C., more preferably 60 to 90 ° C., for example 60 After extracting fresh mozuku (which may be cut, pasted, dried, or frozen) using hot water at ˜75 ° C. for 30 minutes to 3 hours (for example, 100 ° C. for 45 minutes to 1 hour 30 in an autoclave) After treating for about minutes), the obtained extract is desalted by electrodialysis. The hot water extract of the present invention includes an extract obtained by simply extracting mozuku with hot water as described above, its filtrate, and an extract obtained by further desalting the above (etc.). Also included are purified products purified by quaternary ammonium salt treatment, alcohol precipitation, ion exchange resin chromatography, gel filtration chromatography, ultrafiltration, ultrafine filtration, and the like.

  In the present invention, a processed product of mozuku hot water extract can also be used. Examples of the treated product include concentrates, pasted products, dried products (spray dried products, freeze dried products, vacuum dried products, drum dried products, etc.), emulsions, liquid products, and diluted products. In particular, a dry product has the lightest weight and a small volume, so that the suitability for manufacturing and processing is high, and the transportation cost can be reduced.

  Examples of alcoholic beverages to which a flavor improving agent and / or a pH adjusting agent containing mozuku-derived fucoidan as an active ingredient are added include beer, sparkling liquor, liqueurs, sake, wine (fruit wine), shochu shochu, barley shochu, rice shochu, Examples include buckwheat shochu, awamori, whiskey, bourbon, brandy, spirits, vodka, tequila, gin, rum, white liquor, etc., but not limited as long as they contain alcohol, especially distilled liquor (boiled shochu, barley shochu, rice Shochu, soba shochu, awamori, whiskey, bourbon, brandy, spirits, vodka, tequila, gin, rum, white liquor, etc.) are preferred. Moreover, what diluted these with non-alcoholic drinks, such as water and a fruit juice drink, is also included. Furthermore, what mixed 2 or more types of the said alcoholic beverages (for example, cocktail etc.) is also included.

  The amount of the flavor improving agent and / or pH adjuster added with mozuku-derived fucoidan as an active ingredient is not particularly limited as long as the effect is exerted, but for example 0.0001 as mozuku-derived fucoidan. Examples of the addition amount are ˜15.0 w / v%. In addition, the addition amount which becomes 0.001-1 w / v% as a mozuku origin fucoidan is more preferable, and 0.002-0.3 w / v% is still more preferable. If the addition amount of mozuku-derived fucoidan is too small, the effect is not sufficiently exerted, and if it is too large, an excessive increase in viscosity or coloring occurs in the alcoholic beverage, which is not preferable.

  In this way, by simply adding a predetermined amount of a flavor improving agent and / or a pH adjusting agent containing mozuku-derived fucoidan as an active ingredient to an alcoholic beverage, the unpleasant odor of alcoholic beverages can be reduced easily and efficiently, ginjo aroma, etc. Preferred aroma enhancement, improvement of taste and aftertaste, improvement of texture, impartation (enhancement) of sweetness, umami and saltiness, reduction of acidity and bitterness, provision of aging, adjustment of solution pH (particularly pH 4.5 to 6), and the like and the like can be improved.

  Examples of the present invention will be described below, but the present invention is not limited to these examples, and various modifications can be made within the technical idea of the present invention.

(Manufacture of mozuku-derived fucoidan)
In the test shown in Example 2 below, the seafood Kimura Co., Ltd. and the polymer Mozuku Fucoidan “Sea Algaf (registered trademark)” are used. A certain polymer mozuku fucoidan “fucomin (registered trademark)” was used as a mozuku-derived fucoidan-containing liquid. These products were manufactured as follows.

Okinawa mozuku (Cladosiphon okamuranus) was used as the mozuku. This mozuku was suspended in 1 to 5 times its wet weight of water and adjusted to acidic by adding an acetic acid aqueous solution. Subsequently, the mixture was kept heated at 60 to 90 ° C. to elute fucoidan, and then centrifuged to remove precipitates. Fucoidan was concentrated and desalted by removing low molecular components from the supernatant by electrodialysis to obtain a mozuku-derived fucoidan-containing liquid.
The molecular weight of the obtained mozuku-derived fucoidan was about 300,000 as a converted molecular weight based on the pullulan molecular weight, and the sulfate group content was 13%.

(Addition test to alcoholic beverage I)
In order to compare and confirm the flavor of barley shochu added with mozuku-derived fucoidan and barley shochu added with other seaweed-derived polysaccharides, the following tests were conducted.

  First, 10 ml of mozuku-derived fucoidan-containing solution (containing 270 mg of mozuku-derived fucoidan in a dry weight per 10 ml) or 10 ml of sodium alginate (manufactured by Kimika Co., Ltd.) (270 mg of sodium alginate in a dry weight per 10 ml) with respect to 2000 ml of commercially available barley shochu. Were added (each concentration was 0.0135 w / v%), and the flavor immediately after the addition and after storage at room temperature for one month was subjected to sensory evaluation by two trained panelists. As a control, an additive-free barley shochu was used.

  As a result, as compared with the additive-free product, the mozuku-derived fucoidan-added product and the sodium alginate-added product all had a sharp alcohol flavor (ethanol-stimulated odor), and the taste was rounded as a whole. In addition, the mozuku-derived fucoidan-added product, unlike the sodium alginate-added product, has a deeper taste and an aged flavor like old sake. This tendency in flavor was particularly noticeable after storage at room temperature for one month.

  Next, as a similar test, 2,000 mg of mozuku-derived fucoidan, 270 mg of sodium alginate, and 270 mg of alginic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were respectively added to 2000 ml of commercially available barley shochu. The amount of was measured using gas chromatography / mass spectrometry (GC / MS). As a control, an additive-free barley shochu was used.

  The measurement results are shown in FIGS. First, compared to the additive-free product, the amount of ethanol volatilization of the mozuku-derived fucoidan-added product and the sodium alginate-added product both decreased (FIG. 1, compared to the additive-free product, the product of mozuku-derived fucoidan-added product was approximately 3%. %, Sodium alginate decreased by about 12%). However, the product with sodium alginate had a reduced volatility of the entire volatile components, and the scent almost disappeared, while the product with mozuku-derived fucoidan was a representative component of higher alcohols classified as ginjo incense. The amount of volatilization of a certain isoamyl alcohol was about twice that of the additive-free product (FIG. 2). In addition, as for the alginic acid addition goods, both ethanol and isoamyl alcohol increased a little compared with the additive-free goods (FIG. 1, FIG. 2).

  From the above, by adding mozuku-derived fucoidan to barley shochu, the ethanol-stimulated odor is reduced and the isoamyl alcohol odor is increased, and the taste of barley shochu is rounded and improved to a mature flavor like old sake It has been shown. In particular, the addition of mozuku-derived fucoidan significantly promoted the provision of a ripening feeling during storage of alcoholic beverages.

(Addition test to alcoholic beverage II)
In order to confirm the flavor when mozuku-derived fucoidan was added to various alcoholic beverages, the following tests were conducted.

  Mozuku-derived fucoidan-containing liquid is added to commercially available beer, sake, red wine, white wine, whiskey (straight, water split), and shochu (straight, water split) to a concentration of 0.1 v / v%. (The mozuku-derived fucoidan concentration was 0.0027 w / v%). Immediately after the addition, a comparative sensory test with an additive-free product was conducted by five trained panelists. The sensory test is conducted in a closed panel test format, and the evaluation items are isoamyl acetate odor, ethyl caproate odor, alcohol odor, seaweed odor, caramel odor, aroma, spice fragrance, aldehyde odor, acid odor, raw fish odor, sulfur Odor, resin odor, mold odor and fatty odor were selected as appearance and color tone and turbidity as taste, and sweet and spicy taste, aftertaste, texture, acidity, bitterness, astringency, umami taste, salty taste and carbonated taste were selected as tastes. Then, as a comparison with the additive-free product, the rate of change (sensory evaluation point of mozuku-derived fucoidan-added product / sensory evaluation point of additive-free product) was calculated.

  The result of the change rate of the evaluation item of each sample is shown in FIGS. From this result and the standard deviation of the rate of change of evaluation items between samples, the most significant change was observed in the addition of mozuku-derived fucoidan, and the overall trend was whiskey and distilled spirits (including water split) as distilled liquor. ) Was significant.

  Furthermore, when the evaluation items were examined in detail, overall improvement in aftertaste (becomes cleaner) and improvement in texture (rounded and smoothened) were observed as changes in flavor. In addition, so-called unpleasant odors (bad odors) such as acid odor, sulfur odor, mold odor, and fatty odor tended to be suppressed. The rate of change in beer and wine was small compared to distilled liquor, but there was a slight improvement in taste. It was also shown that even when mozuku-derived fucoidan was added, the seaweed odor did not change, and the slight flavor of mozuku-derived fucoidan itself did not affect the flavor improvement of the added alcoholic beverage.

  From the above, by adding mozuku-derived fucoidan to various alcoholic beverages (especially distilled liquor), aftertaste improving effect, texture improving effect, ethanol odor reduction, isoamyl acetate and ethyl caproate odor increase, unpleasant odor reduction effect, etc. Was demonstrated and the flavor was shown to improve.

(Additional test to alcoholic beverage III)
In order to confirm the taste when mozuku-derived fucoidan was added to shochu, the following tests were conducted.

  A mozuku-derived fucoidan-containing liquid was added to commercially available potato shochu (straight) so that the concentration would be 1.0, 2.0, 4.0 v / v% (mozuku-derived fucoidan concentration was 0.027, 0.054, 0.108 w / v%), immediately after the addition, the taste comparison with the non-added product was analyzed by a taste sensor (TS-5000Z, manufactured by Intelligent Sensor Technology Co., Ltd.). The evaluation items were 5 points of acidity, bitter taste, astringency stimulation, umami, salty taste, and sweetness as the taste, and bitterness, astringency, and delicious taste as the aftertaste.

  The analysis results of each sample are shown in FIG. From these results, it was revealed that the addition of fucoidan greatly reduces the sourness of shochu shochu and slightly enhances umami and saltiness.

(Additional test IV to alcoholic beverages)
In order to confirm the change in solution pH when mozuku-derived fucoidan was added to distilled liquor, the following test was performed.

  Mozuku-derived fucoidan-containing liquid has a concentration of 1.0, 2.0, for each commercially available distilled liquor (sake shochu, barley shochu, rice shochu, soba shochu, awamori, whiskey, bourbon, rum, brandy, tequila). Each solution was added so as to be 4.0 v / v% (mozuku-derived fucoidan concentrations were 0.027, 0.054, 0.108 w / v%), and the solution pH was measured. As a comparison, the solution pH of each of the water-containing fucoidan-containing liquids added to water so as to have a concentration of 2.0 and 4.0 v / v% was also measured.

  The results are shown in FIGS. From this result, it was revealed that the addition of mozuku-derived fucoidan increases the pH of each distilled liquor having a pH of about 4.0 to 5.0 by about 0.5. Moreover, in the case of water, on the contrary, it becomes clear that the pH is lowered to around 5.5, and the mozuku-derived fucoidan-containing agent is used as a pH adjuster (in particular, a buffering effect adjuster to a pH range of 4.5 to 6). It was also shown that the effect of.

(Addition test to alcoholic beverage V)
In order to confirm the volatilization amount of the unpleasant odor of the firewood shochu added with mozuku-derived fucoidan, the following test was conducted.

  To the 2000 ml of commercially available shochu shochu, liquids containing mozuku-derived fucoidan were added so that the concentration would be 2.0-20.0 v / v% (mozuku-derived fucoidan concentration was 0.054-0.54 w). / V%), the amount of volatile unpleasant odor components (isobutyric acid, isovaleric acid, caproic acid) immediately after the addition was measured using gas chromatography / mass spectrometry (GC / MS).

  The measurement results are shown in FIGS. For all of isobutyric acid, isovaleric acid, and caproic acid, the volatilization amount is reduced by the addition of mozuku-derived fucoidan, and the volatilization is suppressed by the addition of mozuku-derived fucoidan-containing liquid of about 4.0 to 10.0 v / v%. The effect was maximized, and the volatilization amount was suppressed to 65 to 75%. Further, it has been clarified that the effect does not increase much even if it is added more.

  From the above, it was shown that addition of mozuku-derived fucoidan to shochu shochu can suppress (reduce) the volatilization amount of not only ethanol but also other volatile unpleasant odor components (isobutyric acid, isovaleric acid, caproic acid).

  The present invention is summarized as follows.

  The present invention is a novel and highly safe flavor-improving agent and / or pH-adjusting agent for alcoholic beverages that can easily and effectively improve its aroma, taste, sourness, etc., simply by adding it to an alcoholic beverage. The purpose is to provide.

  And by adding a predetermined amount (for example, 0.0001 to 15.0% (w / v) as mozuku-derived fucoidan) of an agent comprising mozuku-derived fucoidan as an active ingredient, the scent, taste, Acidity etc. can be improved simply and effectively. In particular, it is possible to reduce the unpleasant odor of alcoholic beverages, enhance the preferred aroma, impart a ripening sensation, enhance taste, reduce acidity, adjust the solution pH, and the like.

Claims (5)

  A high molecular fucoidan having a molecular weight of 100,000 or more and a mozuku-derived fucoidan having a sulfate group content of 10 to 20% as an active ingredient, increasing the volatility of isoamyl alcohol in alcoholic beverages, and ethanol, iso A flavor improver for alcoholic beverages characterized by reducing at least one volatility selected from butyric acid, isovaleric acid, and caproic acid.   2. The agent according to claim 1, wherein the alcoholic beverage is distilled liquor or a diluted one thereof.   The agent according to claim 1 or 2, wherein the mozuku is at least one of yarn mozuku, thick mozuku, and Okinawa mozuku.   Adding a mozuku-derived fucoidan having a molecular weight of 100,000 or more and a sulfate group content of 10 to 20% to an alcoholic beverage in an amount of 0.0001 to 15.0 w / v%. A method for producing an alcoholic beverage in which the volatility of isoamyl alcohol in a characteristic alcoholic beverage is increased and at least one of the volatility selected from ethanol, isobutyric acid, isovaleric acid, and caproic acid is reduced.   Adding a mozuku-derived fucoidan having a molecular weight of 100,000 or more and a sulfate group content of 10 to 20% to an alcoholic beverage in an amount of 0.0001 to 15.0 w / v%. A method for increasing volatility of isoamyl alcohol in a characteristic alcoholic beverage and reducing at least one volatility selected from ethanol, isobutyric acid, isovaleric acid, and caproic acid.

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