Preventing oxidation of flavor and food ingredients

Abstract

Various forms presented herein relate to methods and compositions for reducing, preventing and / or inhibiting oxidation of perfume ingredients, formulated perfumes, formulated body care products, formulated skin care products, formulated home care products, essential oils, food ingredients, formulated food products, and natural extracts.

Description

[0001] The present invention is a divisional application of invention patent application No. 201980072698.9 filed on October 31, 2019, with the invention name “Preventing Oxidation of Spice Raw Materials and Food Raw Materials”. Technical Field

[0002] Various aspects presented herein relate to methods and compositions for reducing, preventing and / or inhibiting oxidation of fragrance ingredients, formulated fragrances, formulated body care products, formulated skin care products, formulated home care products, essential oils, food ingredients, formulated food products, and natural extracts. Background Art

[0003] Many formulated fragrances (daily fragrances), body care products, home care products, fragrance raw materials (e.g., essential oils, natural extracts and synthetic ingredients) and food raw materials (e.g., oils and fats derived from animal or plant sources and their derivatives, including monoglycerides, diglycerides, lecithins, phosphatidylethanolamine or other phospholipids, and modified triglycerides) may undergo oxidation, resulting in the formation of chemicals including peroxides, organic hydroperoxides, peroxyhemiacetals, hemiacetals, acetals or transesterification products. Chemicals formed as a result of oxidation may alter the sensory properties or appearance of the fragrance ingredient, formulated fragrance, formulated body care product, formulated skin care product, formulated home care product, essential oil, food raw material, formulated food product or natural extract, or be harmful, irritating or allergenic.

[0004] Peroxide value (POV) is defined as the equivalent amount of oxidation potential per 1 kg of material, which indicates the degree of oxidation. Due to skin sensitivity issues, such as contact dermatitis, the POV of formulated fragrances, body care products and fragrance raw materials is or may be limited by regulations. For example, too high a POV may cause a fragrance raw material to fail quality control testing and therefore be considered unusable. In another example, too high a POV may cause a food raw material to have an unpleasant rancid taste.

[0005] Therefore, there is a need to reduce the incidence of flavor ingredients, formulated flavors, formulated body care products, formulated skin care products, formulated home care products, essential oils, food ingredients, formulated foods, and natural extracts that fail quality control testing or cause skin irritation by reducing the POV in flavor ingredients, formulated flavors, formulated body care products, formulated skin care products, formulated home care products, essential oils, food ingredients, formulated foods, and natural extracts. Additionally, there is a need to reduce the incidence of rancid odors in food ingredients by reducing the POV in food ingredients. Summary of the invention

[0006] A form proposed in this paper provides a method:

[0007] wherein the method reduces the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material;

[0008] wherein the method comprises the steps of: adding to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material having a first POV level at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid; and

[0009] The at least one restorative agent is mixed into the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a time sufficient to reduce the first POV level to a predetermined second lower level.

[0010] A form proposed in this paper provides a method,

[0011] wherein the method reduces, prevents and / or inhibits oxidation of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material,

[0012] The method comprises adding to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material at least one repair agent selected from the group consisting of: α-oxocarboxylic acid, inorganic salts of α-oxocarboxylic acid, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters and salts thereof, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid, the addition amount being sufficient to reduce, prevent and / or inhibit oxidation of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0013] In one aspect, the reduction, prevention and / or inhibition of oxidation increases, enhances and / or improves the stability and / or shelf life of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material.

[0014] One approach proposed here is to:

[0015] Wherein the method reduces, prevents or ameliorates skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material to a subject in need thereof:

[0016] The method comprises the following steps:

[0017] (a) adding to the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid; and

[0018] (b) mixing the at least one restorative agent into the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material for a period of time sufficient to reduce the first POV level to a predetermined second lower level, wherein the predetermined second lower level is sufficient to reduce, prevent or ameliorate skin irritation of the subject caused by the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material.

[0019] In one aspect, the fragrance raw materials are selected from synthetic ingredients, natural products, essential oils and natural extracts.

[0020] In one form, the body care product is a skin cream.

[0021] In one aspect, the food material is selected from fats, oils, or derivatives thereof.

[0022] In one aspect, the derivative is selected from the group consisting of monoglycerides, diglycerides and phospholipids.

[0023] In one form, the phospholipid is selected from phosphatidylcholine, phosphatidylethanolamine and modified triglycerides.

[0024] In one aspect, the fragrance raw materials are processed prior to incorporation into a fragrance.

[0025] In one aspect, the fragrance raw material is treated after incorporation into the fragrance.

[0026] In one form, the food material is processed prior to incorporation into a flavored product, nutritional supplement, or the like.

[0027] In one aspect, the food material is processed prior to incorporation into a flavored product, nutritional supplement, or the like.

[0028] In one form, the at least one restorative agent is present in a concentration of 0.001 to 10% by weight upon addition to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material.

[0029] In one aspect, the flavor raw material is a citrus oil.

[0030] In one aspect, the food material is edible oil.

[0031] In one form, the predetermined second lower level is 5 to 20 mmol / L.

[0032] In one form, the predetermined second lower level is 0 to 6 mmol / L.

[0033] In one form, the method further comprises removing excess at least one restorative agent from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material having a predetermined second, lower POV level.

[0034] In one aspect, excess at least one restorative agent is removed from a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material by liquid-liquid extraction.

[0035] In one embodiment, the method further comprises treating to reduce the acidity of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food material after removing the at least one restorative agent from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food material.

[0036] In one aspect, a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material is treated with a carbonate salt to reduce the acidity of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0037] One aspect presented herein provides a composition comprising: (a) a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material, and (b) at least one repair agent selected from the group consisting of: α-oxocarboxylic acid, organic ammonium salt of α-oxocarboxylic acid, inorganic salt of α-oxocarboxylic acid, thiol, sulfur-containing peptide, sulfur-containing protein, phosphorylated ascorbic acid analog, ascorbic acid ester, ascorbic acid salt, oxalic acid monoester, oxalic acid monoester salt, silane hydride, oxaloacetic acid diester, oxaloacetic acid diester salt, glyoxylic acid and glyoxylic acid salt, wherein the at least one repair agent is present in the composition in an amount sufficient to reduce POV from a first level to a predetermined second lower level.

[0038] One embodiment presented herein provides a composition comprising: (a) a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material, and (b) at least one repair agent selected from the group consisting of: α-oxocarboxylic acid, organic ammonium salt of α-oxocarboxylic acid, inorganic salt of α-oxocarboxylic acid, thiol, sulfur-containing peptide, sulfur-containing protein, phosphorylated ascorbic acid analog, ascorbic acid ester, ascorbic acid salt, oxalic acid monoester, oxalic acid monoester salt, silane hydride, diester of oxaloacetic acid, salt of diester of oxaloacetic acid, glyoxylic acid and salt of glyoxylic acid, wherein the at least one repair agent is present in the composition in an amount sufficient to reduce, prevent or ameliorate an increase in POV of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0039] In one form, at least one restorative agent is added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material at a concentration ranging from 0.001 to 10% by weight.

[0040] In one aspect, the flavor raw material is a citrus oil.

[0041] In one form, the at least one repair agent is present in the composition in an amount sufficient to prevent the predetermined second lower level from changing over time.

[0042] In one form, the concentration of the at least one repair agent in the composition is 0.001 to 10% by weight.

[0043] In one form, at least one alpha-oxocarboxylic acid is added as an organic salt to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material.

[0044] In one form, the at least one α-oxocarboxylic acid is present in the composition as an organic salt.

[0045] In one aspect, the organic salt is an ammonium salt formed by reacting at least one α-oxocarboxylic acid with a compound selected from the group consisting of 2-(dimethylamino)ethanol, N,N-dimethyldodecylamine, tri[2(2-(methoxyethoxy)ethyl]amine and N-methyldiethanolamine.

[0046] In one embodiment, the organic salt is an ammonium salt formed by reacting at least one α-oxocarboxylic acid with a compound selected from the group consisting of N-methyldiethanolamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol.

[0047] In one aspect, the at least one salt of an α-oxocarboxylic acid is ornithine or creatine.

[0048] In one form, the organic salt further comprises citric acid.

[0049] In one embodiment, the organic salt further comprises a polymer selected from the group consisting of gelatin, agarose, alginate, polyacrylamide, acrylate, and combinations thereof.

[0050] In one form, at least one alpha-oxocarboxylic acid is added as a salt of a monovalent or divalent cation to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material.

[0051] In one aspect, at least one α-oxocarboxylic acid is present in the composition in the form of a salt of a monovalent or divalent cation.

[0052] In one embodiment, the at least one α-oxocarboxylic acid is selected from the group consisting of pyruvic acid, 2-oxopentanoic acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid, 2-oxoglutaric acid, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid and mixtures thereof.

[0053] In one embodiment, the thiol is selected from the group consisting of glutathione, N-acetylcysteine ​​methyl ester and cysteine ​​ethyl ester hydrochloride.

[0054] In one embodiment, the ascorbyl ester may be ascorbyl palmitate.

[0055] In one embodiment, the ascorbate salt may be triethanolammonium ascorbate.

[0056] In one embodiment, the salt of oxaloacetate diester may be diethyl oxaloacetate sodium salt.

[0057] In one embodiment, the salt of glyoxylic acid may be triethanolamine glyoxylate.

[0058] The present invention also relates to methods of using hydrolyzable esters of 2-oxoacids and / or oxalic acid to reduce POV by hydrolysis of the ester moiety to produce controlled and / or prolonged in situ release of 2-oxoacids, oxalate monoesters or oxalic acid.

[0059] In one aspect of the present invention, there is provided a method for reducing the POV of a fragrance, a body care product, a cosmetic, a home care product, a fragrance raw material, a flavored product, a nutritional supplement or a food raw material, the method comprising:

[0060] a. adding at least one hydrolyzable ester of a 2-oxo acid and / or a hydrolyzable ester of oxalic acid to a fragrance, a body care product, a cosmetic, a home care product, a fragrance raw material, a flavored product, a nutritional supplement or a food raw material having a first POV level; and

[0061] b. mixing the at least one hydrolyzable ester of 2-oxoacid and / or hydrolyzable ester of oxalic acid into the fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a sufficient period of time to reduce the first POV level to a predetermined second lower level.

[0062] In another aspect, a method of reducing, preventing or ameliorating skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material in a subject in need thereof, the method comprising:

[0063] a. adding at least one hydrolyzable ester of a 2-oxo acid and / or a hydrolyzable ester of oxalic acid to a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level; and

[0064] b. mixing the at least one hydrolyzable ester of 2-oxoacid and / or hydrolyzable ester of oxalic acid into the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material for a period of time sufficient to reduce the first POV level to a predetermined second, lower level, wherein the predetermined second, lower level is sufficient to reduce, prevent or ameliorate skin irritation of a subject caused by the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material.

[0065] In some embodiments, at least one hydrolyzable ester of 2-oxo acid and / or hydrolyzable ester of oxalic acid is an aryl or alkyl ester. In other embodiments, the at least one hydrolyzable ester of 2-oxo acid and / or hydrolyzable ester of oxalic acid is selected from the group consisting of di-n-butyl α-ketoglutarate, di-tert-butyl α-ketoglutarate, dibenzyl α-ketoglutarate, dimethyl oxalate, dibutyl oxalate, diethyl oxalopropionate, diethyl oxalopropionate, diethyl α-ketoglutarate, and combinations thereof.

[0066] In the form of the present invention where the treatment substance is insoluble in the treated substance, it may be necessary to coat the treatment substance on a carrier material. Such a carrier material may be, but is not limited to, glass, metal, ceramic, plastic or paper. A thickener or gelling agent may help the treatment substance adhere to the carrier material. In the case where it is necessary to completely dissolve the treatment material, a solubilizing agent or chemical group may be added to the treatment material or covalently linked to the treatment material to make it more soluble. For example, a long alkyl chain may be covalently added to the treatment chemical portion to make it more soluble in a hydrophobically treated material such as a triglyceride.

[0067] In certain embodiments, the contact surface area between the treating material and the material being treated is maximized, or the treating material is completely dissolved in the material being treated. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 An exemplary proposed reaction between an α-oxocarboxylic acid and an organic hydroperoxide according to some of the morphologies proposed herein is shown.

[0069] Figure 2 Shown is a representation of the rate of reduction of POV in perfume raw materials according to some of the morphologies proposed herein.

[0070] Figure 3 Shown is a POV of a skin cream going through a method according to some aspects of the invention.

[0071] Figure 4 Shown is a POV of a skin cream going through a method according to some aspects of the invention.

[0072] Figure 5 Shown are the changes in POV of a model fragrance treated by methods according to some aspects presented herein.

[0073] Figure 6 Shown are the changes in POV of a model fragrance treated by methods according to some aspects presented herein.

[0074] Figure 7 Shown is a POV of a liquid soap formulation processed by a method according to some aspects presented herein.

[0075] Figure 8 Shown are the percentage reductions in POV for liquid soap formulations treated by methods according to some aspects presented herein.

[0076] Fig. 9 Shown is a POV of a shampoo formulation processed by a method according to some aspects presented herein.

[0077] Fig.10 Shown are the percentage reductions in POV for shampoo formulations treated by methods according to some aspects presented herein.

[0078] Fig.11 Shown is a POV of a general cleaning spray formulation processed by a method according to some aspects presented herein.

[0079] Fig.12 Shown are the percentage reductions in POV for a general-purpose cleaning spray formulation treated by a method according to some aspects presented herein.

[0080] Fig.13 Shown is a POV of a skin cream formulation processed by a method according to some aspects presented herein.

[0081] Fig.14 Shown are the percentage reductions in POV for skin cream formulations treated by methods according to some aspects presented herein.

[0082] Fig.15 Shown is a POV of an antiperspirant stick formulation processed by a method according to some aspects presented herein.

[0083] Fig.16 Shown are the percent POV reductions for antiperspirant stick formulations treated by methods according to some aspects of the present disclosure.

[0084] Fig.17 Shown is a linear and / or branched series of at least one α-oxocarboxylic acid bonded to a polydentate amine compound via an ionic bond, according to one embodiment presented herein.

[0085] Fig.18 Shown is a linear and / or branched series of at least one α-oxocarboxylic acid bonded to a polydentate amine compound via an ionic bond, according to one embodiment presented herein.

[0086] Fig.19 Shown is a linear and / or branched series of at least one α-oxocarboxylic acid bonded to a polydentate amine compound via an ionic bond, according to one embodiment presented herein.

[0087] Fig. 20Shown is a linear and / or branched series of at least one α-oxocarboxylic acid bonded to a polydentate amine compound via an ionic bond, according to one embodiment presented herein.

[0088] Fig.21 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (90%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140 07 8) in a molar ratio of 1:1.8:0.1 according to the method described in Example 27.

[0089] Fig. 22 Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (90%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140078) in a molar ratio of 1:1.8:0.1 according to the method described in Example 27.

[0090] Fig.23 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140 07 8) in a molar ratio of 1:1.6:0.2, according to the method described in Example 27.

[0091] Fig.24 Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140 07 8) in a molar ratio of 1:1.6:0.2, according to the method described in Example 27.

[0092] Fig.25Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (10%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.6:0.1:0.067, according to the method described in Example 27.

[0093] Fig.26 Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (10%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.6:0.1:0.067, according to the method described in Example 27.

[0094] Fig. 27 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (60%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.2:0.2:0.134, according to the method described in Example 27.

[0095] Fig.28Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (60%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.2:0.2:0.134, according to the method described in Example 27.

[0096] Fig.29 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt made from alpha-ketoglutaric acid (AKG, CAS#328-50-7) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140 07-8) in a 1:1 molar ratio according to the method described in Example 27.

[0097] Fig.30 Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of α-ketoglutaric acid (AKG, CAS#328-50-7) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#14007-8) in a 1:1 molar ratio according to the method described in Example 27.

[0098] Fig.31 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt of α-ketoglutaric acid (AKG, CAS#328-50-7) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:0.8:0.13, according to the method described in Example 27.

[0099] Fig.32Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of α-ketoglutaric acid (AKG, CAS#328-50-7) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:0.8:0.13, according to the method described in Example 27.

[0100] Fig.33 Shown is the reduction in POV observed over time in a mixed citrus oil treated with the diammonium salt made from alpha-ketoglutaric acid (AKG, CAS# 328-50-7) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS# 67151 63-7) in a molar ratio of 1:0.67 according to the method described in Example 27.

[0101] Fig.34 Shown is the change in POV observed over time in a mixed citrus oil treated with the diammonium salt of alpha-ketoglutaric acid (AKG, CAS#328-50-7) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151 63-7) in a molar ratio of 1:0.67 according to the method described in Example 27.

[0102] Fig.35 Shown is the reduction in POV observed over time in a mixed citrus oil flavor treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 9:0.67:20, according to the method described in Example 28.

[0103] Fig.36 Shown is the change in POV over time observed in a mixed citrus oil flavor treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 9:0.67:20, according to the method described in Example 28.

[0104] Fig.37Shown is the reduction in POV observed over time in a mixed citrus oil flavor treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9:0.67:10, according to the method described in Example 28.

[0105] Fig.38 Shown is the change in POV over time observed in a mixed citrus oil flavor treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9:0.67:10, according to the method described in Example 28.

[0106] Fig.39 Shown is the reduction in POV observed over time in a mixed citrus oil flavor treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3, according to the method described in Example 28.

[0107] Fig.40 Shown is the change in POV over time observed in a mixed citrus oil flavor treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3, according to the method described in Example 28.

[0108] Fig.41Shown is the reduction in POV observed over time in a mixed citrus oil flavor treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7, according to the method described in Example 28.

[0109] Fig.42 Shown is the change in POV over time observed in a mixed citrus oil flavor treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7 according to the method described in Example 28.

[0110] Fig.43 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3 according to the method described in Example 29.

[0111] Fig.44 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3, according to the method described in Example 29.

[0112] Fig.45Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7 according to the method described in Example 29.

[0113] Fig.46 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7 according to the method described in Example 29.

[0114] Fig.47 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (99%, AKG, CAS#328-50-7) and polyacrylic acid (1%, PAA, CAS#:9003-01-4) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9.9:0.2:10, according to the method described in Example 30.

[0115] Fig.48 Shown is the change in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (99%, AKG, CAS#328-50-7) and polyacrylic acid (1%, PAA, CAS#:9003-01-4) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9.9:0.2:10, according to the method described in Example 30.

[0116] Fig.49Shown is the reduction in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#:9003-01-4) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9.5:1:6.7 according to the method described in Example 30.

[0117] Fig.50 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#:9003-01-4) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9.5:1:6.7 according to the method described in Example 30.

[0118] Fig.51 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (95%, THED, CAS#140 07-8) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:9.5:1 according to the method described in Example 31.

[0119] Fig.52 Shown is the change in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (95%, THED, CAS#140 07-8) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:9.5:1 according to the method described in Example 31.

[0120] Fig.53Shown is the reduction in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with 1-[bis[3-(dimethyl(amino)propyl]amino]-2-propanol (BDMPP, CAS#6715163-7) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:6.3:1 according to the method described in Example 31.

[0121] Fig.54 Shown is the change in POV observed over time in a mixed citrus oil treated with a crosslinked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with 1-[bis[3-(dimethyl(amino)propyl]amino]-2-propanol (BDMPP, CAS#6715163-7) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:6.3:1 according to the method described in Example 31.

[0122] Fig.55 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) and polyethyleneimine (PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:20 according to the method described in Example 31.

[0123] Fig.56 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) and polyethyleneimine (PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:20 according to the method described in Example 31.

[0124] Fig.57 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyethyleneimine (PEI, CAS#: 9002-98-6) in a 1:2 molar ratio according to the method described in Example 31.

[0125] Fig.58 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyethyleneimine (PEI, CAS#:9002-98-6) in a 1:2 molar ratio according to the method described in Example 31.

[0126] Fig.59 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and sebacic acid (5%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9.5:0.5:10, according to the method described in Example 32.

[0127] Fig.60 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and sebacic acid (5%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9.5:0.5:10, according to the method described in Example 32.

[0128] Fig.61 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from alpha-ketoglutaric acid (90%, AKG, CAS#328-50-7) and sebacic acid (10%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9:1:10 according to the method described in Example 32.

[0129] Fig.62 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and sebacic acid (10%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9:1:10, according to the method described in Example 32.

[0130] Fig.63 Shown is the reduction in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from α-ketoglutaric acid (80%, AKG, CAS#328-50-7) and sebacic acid (20%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 8:2:10 according to the method described in Example 32.

[0131] Fig.64 Shown is the change in POV observed over time in a mixed citrus oil treated with a cross-linked diammonium salt made from α-ketoglutaric acid (80%, AKG, CAS#328-50-7) and sebacic acid (20%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 8:2:10, according to the method described in Example 32.

[0132] Fig.65 The viscosity and shear rate relationship of selected at least one ammonium salt of an α-oxocarboxylate tested according to the method described in Example 33 is shown.

[0133] Fig.66 The viscosity and shear rate relationship of selected at least one ammonium salt of an α-oxocarboxylate tested according to the method described in Example 33 is shown.

[0134] Fig.67 The viscosity and shear rate relationship of selected at least one ammonium salt of an α-oxocarboxylate tested according to the method described in Example 33 is shown.

[0135] Fig.68 Shown is the decrease in POV observed over time in mixed citrus oils treated with 2-phospho-L-ascorbic acid trisodium salt (Vc-PTNa) according to the method described in Example 39.

[0136] Fig.69 Shown is the change in POV over time observed in mixed citrus oils treated with 2-phospho-L-ascorbic acid trisodium salt (Vc-PTNa) according to the method described in Example 39.

[0137] Fig.70 Shown is the decrease in POV observed over time in mixed citrus oils treated with L-ascorbic acid 2-phosphate sesquimagnesium salt hydrate (Vc-PSeMg) according to the method described in Example 39.

[0138] Fig.71 Shown is the change in POV observed over time in mixed citrus oils treated with L-ascorbic acid 2-phosphate sesquimagnesium salt hydrate (Vc-PSeMg) according to the method described in Example 39.

[0139] Fig.72 Shown is the decrease in POV observed over time in a model citrus flavor treated with 2-phospho-L-ascorbic acid trisodium salt (Vc-PTNa) according to the method described in Example 39.

[0140] Fig.73 Shown is the change in POV over time observed in a model citrus flavor treated with 2-phospho-L-ascorbic acid trisodium salt (Vc-PTNa) according to the method described in Example 39.

[0141] Fig.74 Shown is the decrease in POV observed over time in a model citrus flavor treated with L-ascorbic acid 2-phosphate sesquimagnesium salt hydrate (Vc-PSeMg) according to the method described in Example 39.

[0142] Fig.75 Shown is the change in POV observed over time in a model citrus flavor treated with L-ascorbic acid 2-phosphate sesquimagnesium salt hydrate (Vc-PSeMg) according to the method described in Example 39.

[0143] Fig.76 Shown is the change in POV over time observed in mixed citrus oils treated with dimethylethylsilane (DMESi) according to the method described in Example 40.

[0144] Fig.77 Shown is the reduction in POV observed over time in mixed citrus oils treated with dimethylethylsilane (DMESi) according to the method described in Example 40.

[0145] Fig.78 Shown is the change in POV observed over time in mixed citrus oils treated with pentamethyldisiloxane (PMDSi) according to the method described in Example 40.

[0146] Fig.79 Shown is the reduction in POV observed over time in mixed citrus oils treated with pentamethyldisiloxane (PMDSi) according to the method described in Example 40.

[0147] Fig.80 Shown is the change in POV observed over time in mixed citrus oils treated with methylhydrogensiloxane polymer (PMHS) according to the method described in Example 40.

[0148] Fig.81 Shown is the reduction in POV observed over time in mixed citrus oils treated with methylhydrogensiloxane polymer (PMHS) according to the method described in Example 40.

[0149] Fig.82 The change in POV observed over time in mixed citrus oils treated with methylhydrogensiloxane polymers (PMHS) (average Mn 1,700-3,200) according to the method described in Example 40 is shown.

[0150] Fig.83 The reduction in POV observed over time in mixed citrus oils treated with methylhydrogensiloxane polymers (PMHS) (average Mn 1,700-3,200) according to the method described in Example 40 is shown.

[0151] Fig.84 Shown is the change in POV over time observed in a model citrus flavor treated with dimethylethylsilane (DMESi) according to the method described in Example 40.

[0152] Fig.85 Shown is the reduction in POV observed over time in a model citrus flavor treated with dimethylethylsilane (DMESi) according to the method described in Example 40.

[0153] Fig.86 Shown is the change in POV over time observed in a model citrus flavor treated with pentamethyldisiloxane (PMDSi) according to the method described in Example 40.

[0154] Fig.87 Shown is the reduction in POV observed over time in a model citrus flavor treated with pentamethyldisiloxane (PMDSi) according to the method described in Example 40.

[0155] Fig.88 Shown is the change in POV observed over time in a model citrus flavor treated with a methylhydrogensiloxane polymer (PMHS) according to the method described in Example 40.

[0156] Fig.89 Shown is the reduction in POV observed over time in a model citrus flavor treated with a methylhydrogensiloxane polymer (PMHS) according to the method described in Example 40.

[0157] Fig.90Shown is the change in POV observed over time in a model citrus flavor treated with methylhydrogensiloxane polymer (PMHS) (average Mn 1,700-3,200) according to the method described in Example 40.

[0158] Fig.91 The reduction in POV observed over time in a model citrus flavor treated with methylhydrogensiloxane polymer (PMHS) (average Mn 1,700-3,200) according to the method described in Example 40 is shown.

[0159] Fig.92 Shown is the change in POV over time observed in mixed citrus oils treated with monobutyl oxalate (2-butoxy-2-oxoacetic acid) according to the method described in Example 42.

[0160] Fig.93 Shown is the decrease in POV observed over time in mixed citrus oils treated with monobutyl oxalate (2-butoxy-2-oxoacetic acid) according to the method described in Example 42.

[0161] Fig.94 Shown is the change in POV over time observed in mixed citrus oils treated with monobenzyl oxalate (2-(benzyloxy)-2-oxoacetic acid) according to the method described in Example 42.

[0162] Fig.95 Shown is the decrease in POV observed over time in mixed citrus oils treated with monobenzyl oxalate (2-(benzyloxy)-2-oxoacetic acid) according to the method described in Example 42.

[0163] Fig.96 The observed HPLC peak areas for an oxidized limonene sample processed according to the method described in Example 43 are shown.

[0164] Fig.97 Shown is a graph of the POV of di-n-butyl alpha-ketoglutarate plotted against time.

[0165] Fig.98 Shown is a graph of the percent reduction in POV for di-n-butyl alpha-ketoglutarate plotted against time.

[0166] Fig.99 Shown is a graph of the POV of di-tert-butyl alpha-ketoglutarate plotted against time.

[0167] Fig.100 Shown is a graph of POV of dibenzyl alpha-ketoglutarate plotted against time. Fig.101 Shown is a graph of the POV of dimethyl oxalate plotted against time.

[0168] Fig.102 Shown is a graph of the percent reduction in POV for dimethyl oxalate plotted against time.

[0169] Fig.103 Shown is a graph of the POV of dibutyl oxalate plotted against time.

[0170] Fig.104 Shown is a graph of the percent reduction in POV for dibutyl oxalate plotted against time.

[0171] Fig.105 Shown is a graph of the POV of diethyl oxalopropionate plotted against time.

[0172] Fig.106 Shown is a graph of the percent reduction in POV for diethyl oxalopropionate plotted against time.

[0173] Fig.107 Shown is a graph of the POV of diethyl alpha-ketoglutarate plotted against time.

[0174] Fig.108 Shown is a graph of the percent reduction in POV for diethyl alpha-ketoglutarate plotted against time. DETAILED DESCRIPTION

[0175] In the following description, reference is made to specific embodiments that can be implemented, which are shown by way of example. These embodiments are described in detail to enable those skilled in the art to implement the invention described herein, and it is understood that other embodiments can be utilized and logical changes can be made without departing from the scope of the configurations proposed herein. Therefore, the following description of the example embodiments should not be considered to have a limiting meaning, and the scope of each configuration proposed herein is defined by the appended claims.

[0176] The Abstract is provided to comply with 37 CFR § 1.72(b) and to allow the reader to quickly ascertain the nature and gist of the technical disclosure. The Abstract is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.

[0177] Many formulated fragrances, body care products, home care products, fragrance raw materials (e.g., essential oils, natural extracts, and synthetic ingredients) can undergo oxidation, resulting in the formation of chemical substances, including peroxides, organic hydroperoxides, peroxy hemiacetals. In addition, it is known that many food raw materials, such as, for example, fats and oils or their derivatives, undergo autoxidation processes, resulting in the formation of the intermediate chemical substance glycerol hydroperoxide. Glycerol hydroperoxide can further degrade into aldehydes and ketones. Without intending to be bound by any particular theory, the autoxidation process can lead to unpleasant and unpalatable rancidity of food raw materials.

[0178] Peroxide value (POV) is defined as the equivalent amount of oxidation potential per 1 kg of material, which indicates the degree of oxidation. Due to skin sensitivity issues, such as contact dermatitis, the POV of formulated fragrances, body care products, home care products, cosmetics and fragrance raw materials is subject to regulatory restrictions. For example, too high a POV may cause the fragrance raw material to fail the quality control test and is therefore considered unusable. In another example, too high a POV may cause a food raw material or formulated food product (also referred to herein as a seasoned product, nutritional supplement) to have a rancid taste.

[0179] Skin exposure may be the result of accidental exposure (such as, for example, exposure to hard surface cleaners or dish soap when the user does not wear gloves when using the product). Alternatively, skin exposure may be the result of chronic or intentional exposure (such as, for example, exposure to shampoo or skin moisturizer).

[0180] As used herein, the term "peroxide value" or "POV" refers to the equivalent amount of oxidation potential per 1 kg of material. Without being limited to any particular theory, the POV of a material can be determined analytically. The term "POV" does not refer to a chemical compound or a group of compounds, but is often used interchangeably with the products of self-oxidation in a sample that cause a response during a POV test. These self-oxidation products vary depending on the specific material being tested. During a POV test, many types of compounds will produce a response, including but not limited to organic and inorganic hydroperoxides, organic and inorganic peroxides, peroxy hemiacetals, peroxy hemiketals, and hydrogen peroxide itself.

[0181] As an illustration, one POV test is the iodometric redox titration. All compounds that are sensitive to POV have the property of being able to oxidize iodide ions to molecular iodine within the time specified in the test. In fact, the oxidation reaction of iodide is the basis of the test. Therefore, "POV" is a numerical value that represents the molar sum of all iodide oxidizing species in a particular sample.

[0182] As an illustration, limonene and linalool are unsaturated terpenes, which are usually found as the main components in many essential oils. Both limonene and linalool are easily oxidized by atmospheric oxygen to form hydroperoxides. It is known that the hydroperoxides of limonene and linalool are sensitizers that can cause contact dermatitis. Therefore, limonene and natural products containing limonene can only be used as fragrance raw materials when the recommended organic hydroperoxide level is lower than 20mmol / L (or 10mEq / L). Similarly, essential oils and isolates from the Pinacea family (including the genus Pinus and the genus Abies) can only be used as fragrance raw materials when the recommended organic hydroperoxide level is lower than 10mmol / L (or 5mEQ / L).

[0183] By another illustration, fats and oils or their derivatives are known to undergo an auto-oxidation process which results in unpleasant and unpalatable rancidity. Without intending to be bound by any particular theory, glycerol hydroperoxide is an intermediate chemical in the auto-oxidation process which further degrades into aldehydes and ketones which produce a rancid odor.

[0184] The POV of a fragrance raw material can be determined by any method readily selected by one of ordinary skill in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

[0185] An example of a method for determining the POV of a fragrance raw material is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, p 121-130.

[0186] Fragrance raw materials include, but are not limited to, essential oils, natural extracts, and synthetic ingredients.

[0187] The POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material can be determined by any method readily selected by one of ordinary skill in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

[0188] An example of a method for determining the POV of a formulated fragrance is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, p 121-130.

[0189] The POV of a formulated body care product can be determined by any method readily selected by one of ordinary skill in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

[0190] An example of a method for determining the POV of a formulated body care product is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, pp 121-130.

[0191] Without intending to be bound by any particular theory, the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material is reduced by treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material with at least one repairing agent. The at least one repairing agent reacts with the organic hydroperoxide, thereby consuming the organic hydroperoxide and reducing the oxidation potential of the organic hydroperoxide.

[0192] As used herein, the term "remediant" refers to an agent that is capable of reducing the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. The POV can be reduced by treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material and / or by reducing lipid hydroperoxides formed by auto-oxidation. The remediant can also react with and remove rancid aldehydes produced by the decomposition of lipid hydroperoxides.

[0193] For example, by way of illustration, the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material is reduced by treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material with an α-oxocarboxylic acid. The α-oxocarboxylic acid reacts with the organic hydroperoxide by oxidative decarboxylation, thereby consuming the organic hydroperoxide and reducing the oxidation potential of the organic hydroperoxide. The resulting reaction results in the oxidation of the α-oxocarboxylic acid to carbon dioxide and the corresponding carboxylic acid containing one less carbon atom, and the reduction of the organic hydroperoxide to its corresponding organic alcohol. Exemplary proposed reactions using pyruvic acid as the α-oxocarboxylic acid and limonene-hydroperoxide as the organic hydroperoxide are as follows: Figure 1 shown.

[0194] Therefore, a morphology proposed in this paper provides a method:

[0195] wherein the method reduces the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material;

[0196] wherein the method comprises the steps of: adding to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material having a first POV level at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid; and

[0197] The at least one restorative agent is mixed or contacted with the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a time sufficient to reduce the first POV level to a predetermined second lower level.

[0198] Alternatively, a morphology proposed in this paper provides a method,

[0199] wherein the method reduces, prevents and / or inhibits oxidation of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material,

[0200] The method comprises adding to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material at least one repair agent selected from the group consisting of: α-oxocarboxylic acid, inorganic salts of α-oxocarboxylic acid, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters and salts thereof, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid, the addition amount being sufficient to reduce, prevent and / or inhibit oxidation of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0201] A form proposed in this paper provides a method:

[0202] Wherein the method reduces, prevents or ameliorates skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material to a subject in need thereof:

[0203] The method comprises the following steps:

[0204] (a) adding to the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid; and

[0205] (b) mixing or contacting the at least one restorative agent with the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material for a period of time sufficient to reduce the first POV level to a predetermined second, lower level, wherein the predetermined second, lower level is sufficient to reduce, prevent or ameliorate skin irritation of the subject caused by the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material.

[0206] Alternatively, a pattern proposed in this paper provides a method:

[0207] wherein the method reduces the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material;

[0208] wherein the method comprises the steps of: adding at least one alpha-oxocarboxylic acid to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material having a first POV level; and

[0209] The at least one alpha-oxocarboxylic acid is admixed into a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a time sufficient to reduce the first POV level to a predetermined second lower level.

[0210] Alternatively, a morphology proposed in this paper provides a method,

[0211] wherein the method reduces, prevents and / or inhibits oxidation of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material,

[0212] The method comprises adding at least one α-oxocarboxylic acid to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material in an amount sufficient to reduce, prevent and / or inhibit oxidation of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0213] A form proposed in this paper provides a method:

[0214] Wherein the method reduces, prevents or ameliorates skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material to a subject in need thereof:

[0215] The method comprises the following steps:

[0216] (a) adding at least one α-oxocarboxylic acid to a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level; and

[0217] (b) mixing or contacting the at least one α-oxocarboxylic acid with the formulated fragrance, body care product, home care product, cosmetic, or fragrance raw material for a period of time sufficient to reduce the first POV level to a predetermined second lower level, wherein the predetermined second lower level is sufficient to reduce, prevent, or ameliorate skin irritation of the subject caused by the formulated fragrance, body care product, home care product, cosmetic, or fragrance raw material.

[0218] In one embodiment, the method is performed at room temperature. In one embodiment, the method is performed at a temperature of -20 degrees Celsius to 78 degrees Celsius.

[0219] In one aspect, the fragrance raw materials are selected from synthetic ingredients, natural products, essential oils and natural extracts.

[0220] In one aspect, the flavor raw material is a citrus oil.

[0221] In one form, the body care product is a skin cream.

[0222] In one aspect, the fragrance raw materials are processed prior to incorporation into a fragrance.

[0223] In one aspect, the fragrance raw material is treated after incorporation into the fragrance.

[0224] In one form, the predetermined second lower level is 5 to 20 mmol / L. In another form, the predetermined second lower level is 5 to 19 mmol / L. In another form, the predetermined second lower level is 5 to 18 mmol / L. In another form, the predetermined second lower level is 5 to 17 mmol / L. In another form, the predetermined second lower level is 5 to 16 mmol / L. In another form, the predetermined second lower level is 5 to 15 mmol / L. In another form, the predetermined second lower level is 5 to 14 mmol / L. In another form, the predetermined second lower level is 5 to 13 mmol / L. In another form, the predetermined second lower level is 5 to 12 mmol / L. In another form, the predetermined second lower level is 5 and 11 mmol / L. In another form, the predetermined second lower level is 5 to 10 mmol / L. In another form, the predetermined second lower level is 5 to 9 mmol / L. In another form, the predetermined second lower level is 5 to 8 mmol / L. In another form, the predetermined second lower level is 5 to 7 mmol / L. In another form, the predetermined second lower level is 5 to 6 mmol / L.

[0225] In one form, the predetermined second lower level is 6 to 20 mmol / L. In another form, the predetermined second lower level is 7 to 20 mmol / L. In another form, the predetermined second lower level is 8 to 20 mmol / L. In another form, the predetermined second lower level is 9 to 20 mmol / L. In another form, the predetermined second lower level is 10 to 20 mmol / L. In another form, the predetermined second lower level is 11 to 20 mmol / L. In another form, the predetermined second lower level is 12 to 20 mmol / L. In another form, the predetermined second lower level is 13 to 20 mmol / L. In another form, the predetermined second lower level is 14 to 20 mmol / L. In another form, the predetermined second lower level is 15 to 20 mmol / L. In another form, the predetermined second lower level is 16 to 20 mmol / L. In another form, the predetermined second lower level is 17 to 20 mmol / L. In another form, the predetermined second lower level is 18 to 20 mmol / L. In another form, the predetermined second lower level is 19 to 20 mmol / L.

[0226] In one form, the predetermined second lower level is 20mmol / L. In another form, the predetermined second lower level is 19mmol / L. In another form, the predetermined second lower level is 18mmol / L. In another form, the predetermined second lower level is 17mmol / L. In another form, the predetermined second lower level is 16mmol / L. In another form, the predetermined second lower level is 15mmol / L. In another form, the predetermined second lower level is 14mmol / L. In another form, the predetermined second lower level is 13mmol / L. In another form, the predetermined second lower level is 12mmol / L. In another form, the predetermined second lower level is 11mmol / L. In another form, the predetermined second lower level is 10mmol / L. In another form, the predetermined second lower level is 9mmol / L. In another form, the predetermined second lower level is 8mmol / L. In another form, the predetermined second lower level is 7mmol / L. In another form, the predetermined second lower level is 6mmol / L. In another form, the predetermined second lower level is 5mmol / L. In another form, the predetermined second lower level is 4mmol / L. In another form, the predetermined second lower level is 3mmol / L. In another form, the predetermined second lower level is 2mmol / L. In another form, the predetermined second lower level is 1mmol / L. In another form, the predetermined second lower level is less than 1mmol / L.

[0227] In one form, the predetermined second lower level is a 10% reduction in POV. In another form, the predetermined second lower level is a 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 or 100% reduction in POV.

[0228] Without intending to be bound by any particular theory, the reduction, prevention and / or inhibition of oxidation increases, enhances and / or improves the stability and / or shelf life of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material.

[0229] Without intending to be bound by any particular theory, reducing the POV of the seasoned product, nutritional supplement or food raw material prevents, reduces or inhibits the formation of intermediate glycerol hydroperoxides in the seasoned product, nutritional supplement or food raw material. Reducing or inhibiting or preventing the formation of intermediate glycerol hydroperoxides in the seasoned product, nutritional supplement or food raw material can prevent, reduce or delay the occurrence of rancidity in the seasoned product, nutritional supplement or food raw material.

[0230] Without intending to be bound by any particular theory, the at least one restorative agent may react with and consume lipid hydroperoxides formed by auto-oxidation and / or react with and consume rancid aldehydes generated by decomposition of lipid hydroperoxides.

[0231] Without intending to be limited to any particular theory, and by way of illustration, the reaction of at least one α-oxocarboxylic acid with autoxidative triglycerides appears to occur via two different and independent pathways. The first pathway is the reductive decarboxylation of lipid hydroperoxides by at least one α-oxocarboxylic acid. This may result in the formation of the corresponding lipid alcohols and a reduction in POV (peroxide value). In addition, this may also prevent further development of sensory rancidity, since lipid hydroperoxides are no longer available for decomposition into aldehydes that cause rancidity. Without intending to be limited to any particular theory, it is these aldehydes that are perceived as rancid odors. Lipid hydroperoxides themselves have no perceptible odor and therefore do not directly contribute to rancid, unpleasant aromas.

[0232] Thus, the development of rancidity is a two-step process; first, the auto-oxidation of unsaturated lipids to odorless lipid hydroperoxides, followed by a second step in which the lipid hydroperoxides decompose to form rancid aldehydes. The development of rancidity can be prevented by consuming the intermediate lipid hydroperoxides before they decompose into rancid aldehydes.

[0233] The second approach is to reduce the concentration of rancid aldehydes. The at least one α-oxocarboxylic acid can also react directly with the rancid aldehyde to form a less smelling adduct, thereby consuming the aldehyde and reducing its concentration. The result is a reduction in rancid odor in the treated oil, constituting a remedy for oils that have gone rancid. The treatment of triglycerides with at least one α-oxocarboxylic acid is described in detail in Example 36 below.

[0234] Flavored products, nutritional supplements include, for example, food products (e.g., beverages), sweeteners such as natural sweeteners or artificial sweeteners, pharmaceutical compositions, dietary supplements, nutraceuticals, dental hygiene compositions and cosmetics. Flavored products, nutritional supplements may further comprise at least one flavoring agent.

[0235] In some forms, the at least one flavoring agent can further alter the taste profile or taste attributes of the flavored product, nutritional supplement.

[0236] In some forms, the flavored preparations, nutritional supplements are foods, including, for example, but not limited to, fruits, vegetables, juices, meat products such as ham, bacon and sausage, egg products, fruit concentrates, gelatin and gelatin-like products such as jams, jellies, preserved fruits, etc., dairy products such as ice cream, sour cream and sherbet, frostings, syrups (including molasses), corn, wheat, rye, soy, oat, rice and barley products, nut meats and nut products, cakes, cookies, sugars such as candies, gummies, fruit-flavored hard candies (drops) and chocolate, chewing gum, mints, cream, pies and bread.

[0237] In some forms, the food product is a beverage, including but not limited to, for example, juice, juice-containing beverages, coffee, tea, carbonated soft drinks (such as COKE and PEPSI), non-carbonated soft drinks and other juices, sports drinks (such as GATORADE) and alcoholic beverages (such as beer, wine and spirits).

[0238] Flavored products and nutritional supplements may also include ready-to-use packaged products, such as granulated flavoring mixes (which, when reconstituted with water, provide non-carbonated beverages), instant pudding mixes, instant coffee and tea, coffee whiteners, malted milk mixes, pet food, livestock feed, tobacco, and materials for baking, such as powdered baking mixes for preparing bread, cookies, cakes, pancakes, donuts, and the like.

[0239] Flavored products, nutritional supplements can also include diet or low-calorie foods and beverages that contain little or no sucrose. Flavored products, nutritional supplements can also include condiments, such as herbs, spices and seasonings, flavor enhancers (such as monosodium glutamate), dietary sweeteners and liquid sweeteners.

[0240] In some aspects, the flavored product, nutritional supplement is a pharmaceutical composition, a dietary supplement, a nutraceutical, a dental hygiene composition or a cosmetic.

[0241] Dental hygiene compositions are known in the art and include, for example, but not limited to, toothpaste, mouthwash, plaque rinse, dental floss, toothache relievers (e.g., ANBESOL), etc. In some forms, the dental hygiene composition comprises a natural sweetener. In some forms, the dental hygiene composition comprises more than one natural sweetener. In some forms, the dental hygiene composition comprises sucrose and corn syrup, or sucrose and aspartame.

[0242] In some forms, cosmetics include, for example, but not limited to, face creams, lipsticks, lip glosses, etc. Other suitable cosmetics for use in the present disclosure include lip balms, such as CHAPSTICK or BURT'S BEESWAX lip balms.

[0243] In another aspect presented herein, a method for increasing the shelf life of a food material is provided, comprising the steps of: adding at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid to a food material having a first POV level; and mixing or contacting the at least one restorative agent with the food material for a sufficient period of time to reduce the first POV level to a predetermined second lower level. Without intending to be limited to any particular theory, reducing the first POV level to the predetermined second lower level can prevent, reduce or inhibit the formation of intermediate glycerol hydroperoxides in the food material, thereby preventing, reducing or inhibiting the development of rancidity in the food material.

[0244] In another aspect presented herein, a method for increasing the shelf life of a food material is provided, comprising the steps of: adding an α-oxocarboxylic acid to a food material having a first POV level; and mixing or contacting the α-oxocarboxylic acid with the food material for a sufficient period of time to reduce the first POV level to a predetermined second lower level. Without intending to be limited to any particular theory, reducing the first POV level to the predetermined second lower level can prevent, reduce or inhibit the formation of an intermediate glycerol hydroperoxide in the food material, thereby preventing, reducing or inhibiting the development of rancidity in the food material.

[0245] Without intending to be bound by any particular theory, the food material may be used as a solvent for the flavoring ingredient, or alternatively, the food material itself may be the flavoring ingredient.

[0246] In another aspect provided herein, a method for increasing the shelf life of a flavored product or nutritional supplement is provided, comprising the steps of: adding at least one restorative agent selected from the group consisting of: α-oxocarboxylic acids, organic ammonium salts of α-oxocarboxylic acids, inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides, diesters of oxaloacetic acid, salts of diesters of oxaloacetic acid, glyoxylic acid and salts of glyoxylic acid to the flavored product or nutritional supplement having a first POV level; and mixing or contacting the at least one restorative agent with the flavored product or nutritional supplement for a sufficient period of time to reduce the first POV level to a predetermined second lower level. Without intending to be limited to any particular theory, reducing the first POV level to the predetermined second lower level can prevent, reduce or inhibit the formation of intermediate glycerol hydroperoxide in the flavored product or nutritional supplement, thereby preventing, reducing or inhibiting the development of rancidity in the flavored product or nutritional supplement.

[0247] In another aspect provided herein, a method for increasing the shelf life of a seasoned product or nutritional supplement is provided, comprising the steps of: adding an α-oxocarboxylic acid to a seasoned product or nutritional supplement having a first POV level; and mixing or contacting the α-oxocarboxylic acid with the seasoned product or nutritional supplement for a sufficient period of time to reduce the first POV level to a predetermined second lower level. Without intending to be limited to any particular theory, reducing the first POV level to the predetermined second lower level can prevent, reduce or inhibit the formation of an intermediate glycerol hydroperoxide in the seasoned product or nutritional supplement, thereby preventing, reducing or inhibiting the development of rancidity in the seasoned product or nutritional supplement.

[0248] In one embodiment, the food material is selected from fats, oils or their derivatives. In one embodiment, the derivatives thereof are selected from monoglycerides, diglycerides and phospholipids. In one embodiment, the phospholipids are selected from lecithin, phosphatidylethanolamine and modified triglycerides.

[0249] In one embodiment, the food material is processed before being incorporated into a seasoned product or nutritional supplement. In another embodiment, the food material is processed after being incorporated into a seasoned product or nutritional supplement.

[0250] In one embodiment, the food material is an edible oil. Examples of edible oils suitable for processing according to the embodiments described herein include, but are not limited to, olive oil, palm oil, soybean oil, canola oil, corn oil, peanut oil, other vegetable oils, and animal oils, such as butter or lard, for example.

[0251] In one embodiment, the method is performed at room temperature. In one embodiment, the method is performed at a temperature of -20 degrees Celsius to 78 degrees Celsius.

[0252] In one form, the predetermined second lower level is 0 to 6 mmol / L. In another form, the predetermined second lower level is 0 to 5 mmol / L. In another form, the predetermined second lower level is 0 to 4 mmol / L. In another form, the predetermined second lower level is 0 and 3 mmol / L. In another form, the predetermined second lower level is 0 to 2 mmol / L. In another form, the predetermined second lower level is 0 to 1 mmol / L.

[0253] In one form, the predetermined second lower level is 1 to 6 mmol / L. In another form, the predetermined second lower level is 2 to 5 mmol / L. In another form, the predetermined second lower level is 3 to 5 mmol / L. In another form, the predetermined second lower level is 4 to 5 mmol / L.

[0254] In one form, the predetermined second lower level is 5mmol / L. In another form, the predetermined second lower level is 4mmol / L. In another form, the predetermined second lower level is 3mmol / L. In another form, the predetermined second lower level is 2mmol / L. In another form, the predetermined second lower level is 1mmol / L. In another form, the predetermined second lower level is 0.9mmol / L. In another form, the predetermined second lower level is 0.8mmol / L. In another form, the predetermined second lower level is 0.7mmol / L. In another form, the predetermined second lower level is 0.6mmol / L. In another form, the predetermined second lower level is 0.5mmol / L. In another form, the predetermined second lower level is 0.4mmol / L. In another form, the predetermined second lower level is 0.3mmol / L. In another form, the predetermined second lower level is 0.2mmol / L. In another form, the predetermined second lower level is 0.1mmol / L. In another form, the predetermined second lower level is 0mmol / L.

[0255] In one form, the predetermined second lower level is a 10% reduction in POV. In another form, the predetermined second lower level is a 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 or 100% reduction in POV.

[0256] In one aspect, at least one of the remedial agents has FEMA-GRAS status.

[0257] In one embodiment, the α-oxocarboxylic acid has FEMA-GRAS status. In one embodiment, the α-oxocarboxylic acid is selected from the group consisting of pyruvic acid, 2-oxopentanoic acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid, 2-oxoglutaric acid, indole-3-pyruvic acid, 2-thiophene glyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.

[0258] As used herein, the term "salt" applied to the anion of 2-oxo acid, oxalic acid, oxalic acid monoester, glyoxylic acid, etc., can represent any cationic moiety, including but not limited to: inorganic salts containing metal cations, such as lithium, sodium, potassium, magnesium, calcium, iron, copper, zinc, ammonium cation (NH4+), etc. Cations derived from protonation of organic amines, including but not limited to N-monoalkyl, N,N-dialkyl, N,N,N-trialkyl, N-monoaryl, N,N-diaryl, N,N,N-triarylamines, or any combination thereof, including N-aryl and / or N-alkyl substituents containing further substituents, such as triethanolamine, N-methyldiethanolamine, etc. Cations derived from complete substitution of amines, including but not limited to N,N,N,N-tetraalkyl, N,N,N,N-tetraaryl, or any combination thereof, including N-aryl and / or N-alkyl substituents containing further substituents, such as tetraethanolamine, N-methyltriethanolamine, etc. Cations derived from amino acids such as arginine, ornithine, or proteins or peptides containing basic amino acids, or metabolites such as creatine, uric acid, etc. Cations derived from synthetic or natural nitrogen-containing polymers (e.g., chitosan). Nitrogen-containing heterocycles, wherein the nitrogen is contained within the ring, or wherein the nitrogen is contained on a ring substituent, including any nitrogen-containing alkaloids, such as caffeine, etc., or any combination of the above moieties.

[0259] In some forms, at least one α-oxocarboxylic acid is added as a salt to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material. The salt can be formed by reacting at least one α-oxocarboxylic acid with an organic base.

[0260] In the form where at least one α-oxocarboxylic acid is a monoacid, the resulting salt may be a monosalt. In the form where at least one α-oxocarboxylic acid is a diacid, the resulting salt may be a monosalt or a disalt.

[0261] Examples of suitable organic bases include, but are not limited to, the organic bases described in Examples 7 to 11 below, polymeric amines, polyethyleneimine, and the like.

[0262] Alternatively, the salt comprises at least one anion of an α-oxocarboxylic acid and a + , K + Mg 2+ and Ca 2+ of cations.

[0263] Examples of the ammonium salt include ammonium salts formed by reacting at least one α-oxocarboxylic acid with N-methyldiethanolamine.

[0264] In some forms, the molar ratio of at least one α-oxocarboxylic acid to N-methyldiethanolamine can be 1:2 or 1:1 or 2:1.

[0265] In some forms, the ammonium salt of at least one α-oxocarboxylic acid has surfactant properties. Without intending to be bound by any particular theory, surfactant properties generally occur in molecules that contain ionic and / or highly polar functional groups and one or more spatially separated long hydrophobic moieties. If a hydrophobic moiety, such as an alkyl group with a sufficient carbon number (e.g., C-8 to C-24), is attached to the ammonium salt of at least one α-oxocarboxylic acid, the resulting molecule can exhibit surfactant properties.

[0266] Without intending to be bound by any particular theory, the ammonium salt of at least one alpha-oxocarboxylic acid having surfactant properties or ionicity and high polarity can be used in a variety of home care and body care consumer products that come into contact with the user's skin during use.

[0267] Examples of ammonium salts of at least one α-oxocarboxylic acid having surfactant properties include, but are not limited to, diammonium salts formed from α-ketoglutaric acid and N,N-dimethyldodecylamine in a molar ratio of 1:2, and monoammonium salts formed from α-ketoglutaric acid and N,N-dimethyldodecylamine in a molar ratio of 1:1.

[0268] In some forms, the ammonium salt of at least one α-oxocarboxylic acid has emollient properties. Without intending to be limited to any particular theory, emollient properties are generally found in molecules that are primarily hydrophobic and inert with a low melting point (relative to body temperature) and can be used as emollients. Useful emollients have oily or greasy physical properties and act as softeners and / or moisture barriers when applied to the skin. Although the ammonium salt of at least one α-oxocarboxylic acid listed above is ionic and highly polar, if a sufficient amount of a hydrophobic portion can be incorporated into the ammonium salt of at least one α-oxocarboxylic acid, the resulting molecule may display emollient properties.

[0269] One approach is to use an amine with three long, hydrophobic or oily substituents as the base component of the ammonium salt of at least one alpha-oxocarboxylic acid. Such a molecule can have hydrogen peroxide consuming / POV reducing qualities as well as emollient properties, thus providing additional benefits to the user. These products can be used in a variety of body care consumer products that are placed on the skin during use and left on for extended periods of time to moisturize, protect or soften the user's skin.

[0270] Examples of ammonium salts of at least one α-oxocarboxylic acid having emollient properties include, but are not limited to, diammonium salts formed from α-ketoglutaric acid and tri[2(2(methoxyethoxy)ethyl]amine in a 1:2 molar ratio.

[0271] In some forms, at least one alpha-oxocarboxylic acid can be reacted with N-methyldiethanolamine by dissolving at least one alpha-oxocarboxylic acid in a solvent, for example, acetone, and adding N-methyldiethanolamine to the solution. The resulting opaque white emulsion can then be vortexed, during which the second phase will coalesce. The mixture can then be placed in a freezer for at least 30 minutes to thicken the bottom phase into a waxy solid. When still very cold, the top layer can be easily removed and discarded by decantation. Residual acetone can be removed from the bottom product layer by a stream of nitrogen gas, then treated in a vacuum oven at room temperature, thereby obtaining a light yellow high viscosity oil at room temperature comprising the diammonium salt.

[0272] Other compounds suitable for forming ammonium salts by reaction with at least one α-oxocarboxylic acid include 2-(dimethylamino)ethanol and N,N-dimethyldodecylamine.

[0273] In one form, the salt is an ammonium salt formed by reacting an α-oxocarboxylic acid with a compound selected from the group consisting of 2-(dimethylamino)ethanol, N,N-dimethyldodecylamine, tri[2(2(methoxyethoxy))ethyl]amine and N-methyldiethanolamine.

[0274] Without intending to be bound by any particular theory, the ammonium salt of at least one α-oxocarboxylic acid can prevent acid-catalyzed chemical reactions that can harm and / or degrade the treated formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. Alternatively, the ammonium salt of at least one α-oxocarboxylic acid can improve the solubility of the at least one α-oxocarboxylic acid. Alternatively, the ammonium salt of at least one α-oxocarboxylic acid can provide emulsification.

[0275] Without intending to be bound by any particular theory, at least one salt of an α-oxocarboxylic acid can be an emulsifier when added to an aqueous system comprising a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned preparation, nutritional supplement or food raw material. Such a composition can be used in dressings, marinades, sauces, etc.

[0276] In one aspect, the at least one ammonium salt of an α-oxocarboxylic acid can be further combined with at least one other agent. In one aspect, the at least one other agent is chitosan.

[0277] In one form, alpha-ketoglutaric acid is added to a mixture of palmitic acid and chitosan. Such a composition can be an emulsifier for edible oils in aqueous systems and can be used in salad dressings, marinades, sauces, and the like.

[0278] In one aspect, the at least one salt of an α-oxocarboxylic acid is ornithine or creatine.

[0279] In one embodiment, the thiol is selected from the group consisting of glutathione, N-acetylcysteine ​​methyl ester and cysteine ​​ethyl ester hydrochloride.

[0280] In one embodiment, the ascorbyl ester may be ascorbyl palmitate.

[0281] In one embodiment, the ascorbate salt may be triethanolammonium ascorbate.

[0282] In one embodiment, the salt of oxaloacetate diester may be diethyl oxaloacetate sodium salt.

[0283] In one embodiment, the salt of glyoxylic acid may be triethanolamine glyoxylate.

[0284] In one form, the time sufficient to reduce POV to a predetermined second lower level is 30 or 29 or 28 or 27 or 26 or 25 or 24 or 23 or 22 or 21 or 20 or 19 or 18 or 17 or 16 or 15 or 14 or 13 or 12 or 11 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 day.

[0285] In one form, the time sufficient to reduce POV to the predetermined second lower level is greater than 24 hours. In one form, the time sufficient to reduce POV to the predetermined second lower level is 48 or 47 or 46 or 45 or 44 or 43 or 43 or 42 or 41 or 40 or 39 or 38 or 37 or 36 or 35 or 34 or 33 or 32 or 31 or 30 or 29 or 28 or 27 or 26 or 25 or 24 or 23 or 22 or 21 or 20 or 19 or 18 or 17 or 16 or 15 or 14 or 13 or 12 or 11 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 hour.

[0286] In one form, the time sufficient to reduce the POV to the predetermined second lower level is 60 minutes or less. In one form, the time sufficient to reduce the POV to the predetermined second lower level is 60 or 50 or 40 or 30 or 20 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 minutes.

[0287] Without intending to be bound by any particular theory, the amount of α-oxocarboxylic acid and / or the ratio of α-oxocarboxylic acid added to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material is controlled to ensure that excess α-oxocarboxylic acid does not accumulate. Excessive accumulation of α-oxocarboxylic acid can lead to, for example, acid-catalyzed damage to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material.

[0288] The amount of α-oxocarboxylic acid added to a formulated fragrance, body care product, fragrance raw material, flavored preparation, nutritional supplement or food material depends on several factors, including but not limited to the stability of the α-oxocarboxylic acid in solution, the solubility of the α-oxocarboxylic acid in the formulated fragrance, body care product, fragrance raw material, flavored preparation, nutritional supplement or food material, the pKa of the α-oxocarboxylic acid, the reduction ratio of POV, the effect of the α-oxocarboxylic acid on the olfactory properties and / or taste of the formulated fragrance, body care product, fragrance raw material, flavored preparation, nutritional supplement or food material.

[0289] As an illustration, pyruvic acid, phenylpyruvic acid and 2-oxopentanoic acid have strong aromas and are used as FEMA-GRAS flavoring ingredients. In these forms, the inherent odor of α-oxocarboxylic acids may be altered or incompatible with the organoleptic qualities of, for example, formulated fragrances.

[0290] An alternative to using an odorless α-oxocarboxylic acid in the forms described herein is to use an α-oxocarboxylic acid that is compatible with the aroma of the fragrance and that, when consumed by reaction with the hydroperoxide, also releases an aroma-compatible carboxylic acid. As an illustration, indole-3-pyruvic acid can be used to reduce the POV of a fragrance having an indole character (i.e., containing appreciable amounts of indole and / or skatole).

[0291] Examples of odorless α-oxocarboxylic acids include α-ketoglutaric acid. Without intending to be bound by any particular theory, odorless α-oxocarboxylic acids can reduce the POV of formulated fragrances, body care products, cosmetics, home care products, fragrance raw materials, flavored products, nutritional supplements, or food raw materials, and have less impact on the sensory properties of formulated fragrances, body care products, cosmetics, home care products, fragrance raw materials, flavored products, nutritional supplements, or food raw materials than odorous α-oxocarboxylic acids.

[0292] If the composition comprising an α-oxocarboxylic acid is formulated in a different manner, the solubility of the α-oxocarboxylic acid may change. Taking α-ketoglutaric acid as an example, the solubility of the α-oxocarboxylic acid may be low in a flavor raw material such as citrus oil. However, if the flavor raw material is added to a hydroalcoholic flavor base (a solution containing 80% to 90% ethanol in water), the solubility of the α-oxocarboxylic acid may increase. In these forms, if the α-oxocarboxylic acid is a strong acid, the amount of the α-oxocarboxylic acid in the solution in the hydroalcoholic flavor base must be limited to prevent the sensory properties of the flavor raw material or the formulated flavor from being changed due to acid-catalyzed degradation of the flavor raw material.

[0293] Examples of forms in which α-oxocarboxylic acids may be unstable in solution include oxaloacetic acid, which is unstable in aqueous solution. In these forms, oxaloacetic acid decomposes into pyruvic acid and carbon dioxide. In these forms, the POV of a formulated fragrance, body care product, fragrance raw material, flavored product, nutritional supplement, or food raw material can be reduced by oxaloacetic acid, pyruvic acid, or any combination thereof.

[0294] In some forms, the α-oxocarboxylic acid has low solubility in a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. As an illustration, at the lower limit of solubility, the α-oxocarboxylic acid may be virtually insoluble in a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. Conversely, at the upper limit of solubility, the α-oxocarboxylic acid may be completely miscible with a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material.

[0295] Examples of low solubility forms of α-oxocarboxylic acids in formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials include, but are not limited to, pyruvic acid in citrus oils. In these forms, α-oxocarboxylic acids can be added at a concentration exceeding solubility to form a two-phase system, in which one phase is composed of α-oxocarboxylic acids. It is not intended to be limited to any particular theory, and the ingredients of formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials can be distributed into the phase composed of α-oxocarboxylic acids. The ingredients of formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials are exposed to the phase composed of α-oxocarboxylic acids and may cause chemical changes / damage to the acid-sensitive compounds in the formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials.

[0296] As an illustration, essential oils are primarily composed of terpene compounds. As a class, terpenes are generally subject to acid-catalyzed rearrangements. Therefore, exposure of ingredients of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material to a phase composed of α-oxocarboxylic acids may cause chemical changes / damage to acid-sensitive compounds in the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material, thereby altering the sensory properties of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material.

[0297] Therefore, in some forms proposed herein, the α-oxocarboxylic acid is added at a rate that minimizes or prevents the formation of the second phase composed of the α-oxocarboxylic acid. Such an addition rate can be equal to the rate of the chemical reaction that reduces the POV of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material. It is not intended to be limited to any particular theory, adding the α-oxocarboxylic acid at the same rate as the chemical reaction can prevent the accumulation of the α-oxocarboxylic acid, thereby minimizing the volume of the second phase, which will reduce the distribution of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material into the highly acidic phase composed of the α-oxocarboxylic acid.

[0298] Alternatively, effective dispersion of the α-oxocarboxylic acid in a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material can increase the rate of chemical reaction by increasing the contact surface area between the two phases in a two-phase system, which reduces the POV of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material.

[0299] The example of the form of the non-low solubility of alpha-oxocarboxylic acid in the spices, body care products, cosmetics, home care products, spice raw materials, seasoned products, nutritional supplements or food raw materials of preparation includes but is not limited to 2-oxopentanoic acid. It is not intended to be limited to any particular theory, and the non-low solubility of alpha-oxocarboxylic acid in the spices, body care products, cosmetics, home care products, spice raw materials, seasoned products, nutritional supplements or food raw materials of preparation may cause the formation of a single phase. Here, the added alpha-oxocarboxylic acid can be dissolved in the spices, body care products, cosmetics, home care products, spice raw materials, seasoned products or food raw materials of preparation, so it will be diluted immediately after addition. In this case, if the addition rate is close to the reaction rate, the alpha-oxocarboxylic acid will also be consumed when added. The concentration of the alpha-oxocarboxylic acid will remain low, and the change caused by the acid will be minimized.

[0300] In another aspect, the concentration of unreacted α-oxocarboxylic acid is minimized by using a buffer, wherein the α-oxocarboxylic acid is present as a deprotonated anion.

[0301] The anionic form of the α-oxocarboxylic acid may be unreactive to the hydroperoxide relative to the protonated acidic form. However, since the acidic form is consumed by reaction with the hydroperoxide, the equilibrium of the α-oxocarboxylic acid-base pair will be rapidly reestablished according to the pKa of the α-oxocarboxylic acid; the anionic form will immediately capture a proton from the medium, thereby producing more of the hydroperoxide-reactive acidic form of the α-oxocarboxylic acid. In this way, the overall acidity of the medium can be maintained at a moderate pH without causing acid damage to the ingredients of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material. But at the same time, there will be a relatively low but fixed level of the reactive protonated form of the α-oxocarboxylic acid, which will be immediately replenished once it is consumed from the relatively inert anionic form of the sink.

[0302] For example, using pyruvate for illustration purposes only, which has a pKa of 2.50, buffering a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material to pH 5.5 (a difference of 3 log units) will result in a pyruvate anion concentration of 10 compared to pyruvate (according to the Henderson-Hasselbalch equation). 3 times (or 1000 times) higher.

[0303] In one embodiment, the concentration of the α-oxocarboxylic acid is 0.001 to 10% by weight after addition to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material. In one embodiment, the concentration of the α-oxocarboxylic acid is 10% by weight after addition to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material. Alternatively, the concentration of the α-oxocarboxylic acid after addition to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material is 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 or 0.9 or 0.8 or 0.7 or 0.6 or 0.5 or 0.4 or 0.3 or 0.2 or 0.1 or 0.09 or 0.08 or 0.07 or 0.06 or 0.05 or 0.04 or 0.03 or 0.02 or 0.01 or 0.009 or 0.008 or 0.007 or 0.006 or 0.005 or 0.004 or 0.003 or 0.002 or 0.001 weight percent.

[0304] The α-oxocarboxylic acid can be added directly to the formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials, or the α-oxocarboxylic acid can be diluted before being added to the formulated spices, body care products, cosmetics, home care products, spice raw materials, flavored products, nutritional supplements or food raw materials. Any diluent that can be used in spices can be used. Suitable diluents include but are not limited to isopropyl alcohol, ethanol, diethylene glycol dimethyl ether, triethylene glycol, etc. The α-oxocarboxylic acid can be diluted with a diluent to 1:1 or 1:2 or 1:3 or 1:4 or higher.

[0305] Without intending to be limited to any particular theory, the selection of diluents may also affect the amount of α-oxocarboxylic acids that can be added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. In addition, the selection of diluents may also affect the rate at which the α-oxocarboxylic acid is added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. For example, as an illustration, using pyruvic acid as the α-oxocarboxylic acid and using ethanol as the solvent, the pyruvic acid must be added in a certain amount and / or at a certain rate to minimize the formation of esters with ethanol.

[0306] The α-oxocarboxylic acid can be added to any volume of a formulated perfume, body care product, cosmetic, home care product, perfume raw material, flavored product, nutritional supplement or food raw material. For example, the α-oxocarboxylic acid can be added to 1000 ml of a formulated perfume, body care product or perfume raw material, or to 900 or 800 or 700 or 600 or 500 or 400 or 300 or 200 or 100 or 90 or 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 ml of a formulated perfume, body care product, cosmetic, home care product, perfume raw material, flavored product, nutritional supplement or food raw material.

[0307] In one embodiment, the α-oxocarboxylic acid can be added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material for 80 minutes. Alternatively, the α-oxocarboxylic acid can be added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material for 70 or 60 or 50 or 40 or 30 or 20 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 minute.

[0308] In one embodiment, the α-oxocarboxylic acid is added to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material at a rate of 0.25 ml per minute. In some embodiments, the addition rate is greater than 0.25 ml per minute. In some embodiments, the addition rate is less than 0.25 ml per minute.

[0309] In some embodiments, the rate at which an α-oxocarboxylic acid is added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material is constant. In some embodiments, the rate at which an α-oxocarboxylic acid is added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material may vary. In one embodiment, an α-oxocarboxylic acid is added to a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material at a rate equal to the rate at which the α-oxocarboxylic acid is oxidized. In some embodiments, the rate at which an α-oxocarboxylic acid is oxidized can be determined by measuring the POV in a treated formulated fragrance, body care product, or fragrance raw material. Reference Figures 2 to 4 As an illustration, the rate of decrease of the POV may have a first rate that is greater than a second rate. In the illustrated form, the duration of the first rate is less than the duration of the second rate.

[0310] In another embodiment, the α-oxocarboxylic acid can be added and then quenched after a period of time. The α-oxocarboxylic acid can be quenched 80 minutes after being added to the material. Alternatively, the α-oxocarboxylic acid can be quenched 70 or 60 or 50 or 40 or 30 or 20 or 10 or 9 or 8 or 7 or 6 or 5 or 4 or 3 or 2 or 1 minute after being added to the material.

[0311] In one form, the method further comprises removing excess at least one restorative agent from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material having a predetermined second, lower level of POV.

[0312] In one aspect, excess at least one restorative agent is removed from a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material by liquid-liquid extraction.

[0313] In one embodiment, the method further comprises treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material after removing the at least one restorative agent to reduce the acidity of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0314] In one form, the method further comprises removing excess alpha-oxocarboxylic acid from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material having a predetermined second lower level of POV.

[0315] In one aspect, excess alpha-oxocarboxylic acid is removed from a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material by liquid-liquid extraction.

[0316] In one aspect, excess alpha-oxocarboxylic acid is removed from a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material by liquid-liquid extraction with water.

[0317] In one form, other byproducts of the reaction that reduce the POV of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material to a predetermined second lower level are also removed by liquid-liquid extraction. All byproducts or a portion of the byproducts may be removed.

[0318] In one embodiment, the method further comprises treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material to reduce the acidity of the material after removing the excess α-oxocarboxylic acid. In some embodiments, the treatment comprises adding a buffer, such as triethanolamine or N-methyldiethanolamine, for example.

[0319] In one form, the material is treated with a carbonate salt to reduce the acidity of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material.

[0320] In one aspect, a method for reducing the POV of a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material comprises the following steps:

[0321] a) introducing a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material into a reaction vessel, wherein the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material is in an inert gas such as, for example, argon;

[0322] b) introducing the α-oxocarboxylic acid into the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material at a rate of 0.25 ml per minute, wherein the α-oxocarboxylic acid is diluted with a diluent at a ratio of 1:4, wherein the α-oxocarboxylic acid introduced into the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, seasoned product, nutritional supplement or food raw material is continuously stirred during the introduction process;

[0323] c) introducing water and anhydrous sodium carbonate into the mixture and allowing the reaction to continue until no further carbon dioxide evolution is observed; and

[0324] d) discarding the aqueous layer, thereby obtaining a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material having a predetermined second, lower level of POV.

[0325] Examples of methods according to the above aspects can be found in Examples 1 to 4 below.

[0326] In some forms, the second phase of α-oxocarboxylic acid in the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material is a "leave-in" composition of the α-oxocarboxylic acid. Without intending to be limited to any particular theory, the amount of α-oxocarboxylic acid present in the two phases is in equilibrium, and the reduction of POV can cause the α-oxocarboxylic acid to move from the phase composed of the α-oxocarboxylic acid to the phase containing the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material. An example of this form is described in Example 5 below.

[0327] In some forms, the "leave-on" composition of an alpha-oxocarboxylic acid includes a single-phase composition having a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement, or food raw material. In these forms, the composition also includes a buffer, wherein the pH is configured to maintain a majority of the alpha-oxocarboxylic acid in an unprotonated form, wherein the unprotonated form cannot react with chemicals (including peroxides, organic hydroperoxides, peroxy hemiacetals) that contribute to the POV of the composition. Without intending to be limited to any particular theory, the amount of the alpha-oxocarboxylic acid in the unprotonated form is in balance with the amount of the alpha-oxocarboxylic acid in the protonated form, and a reduction in the POV may cause the alpha-oxocarboxylic acid to move from the unprotonated form to the protonated form. An example of this form is described in Example 4 below.

[0328] In these cases, a "leave-on" composition of an alpha-oxocarboxylic acid can provide prolonged reduction in POV.

[0329] Thus, one aspect presented herein provides a composition comprising: (a) a formulated fragrance, a body care product, a cosmetic, a home care product, a fragrance raw material, a flavored preparation, a nutritional supplement or a food raw material, and (b) an α-oxocarboxylic acid, wherein the α-oxocarboxylic acid is present in the composition in an amount sufficient to reduce POV from a first level to a predetermined second, lower level.

[0330] In one aspect, the α-oxocarboxylic acid is present in the composition in an amount sufficient to prevent the predetermined second lower level from changing over time. The time period may be hours, days, weeks or longer.

[0331] One embodiment presented herein provides a composition comprising: (a) a formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material, and (b) an α-oxocarboxylic acid, wherein the α-oxocarboxylic acid is present in the composition in an amount sufficient to reduce, prevent or ameliorate an increase in POV of the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

[0332] In one form, the at least one α-oxocarboxylic acid is present in the composition at a concentration of 0.001 to 10 wt %.

[0333] In one embodiment, the thiol is selected from the group consisting of glutathione, N-acetylcysteine ​​methyl ester and cysteine ​​ethyl ester hydrochloride.

[0334] In one embodiment, the ascorbyl ester may be ascorbyl palmitate.

[0335] In one embodiment, the ascorbate salt may be triethanolammonium ascorbate.

[0336] In one embodiment, the salt of oxaloacetate diester may be diethyl oxaloacetate sodium salt.

[0337] In one embodiment, the salt of glyoxylic acid may be triethanolamine glyoxylate.

[0338] In one aspect, the at least one salt of an α-oxocarboxylic acid is ornithine or creatine.

[0339] In one embodiment, the at least one α-oxocarboxylic acid is selected from the group consisting of pyruvic acid, 2-oxopentanoic acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid, 2-oxoglutaric acid, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid and mixtures thereof.

[0340] In one aspect, the flavor raw material is a citrus oil.

[0341] Examples of compositions according to the above described morphology can be found in Example 5 below.

[0342] In some forms, at least one restorative agent may be applied to or incorporated into or covalently bonded to a solid matrix, wherein the solid matrix comprising at least one restorative agent is used to treat the formulated fragrance, body care product, cosmetic, fragrance raw material, flavored preparation, nutritional supplement, or food raw material.

[0343] In some forms, at least one α-oxocarboxylic acid or salt thereof can be applied to or incorporated into or covalently bonded to a solid matrix, wherein the solid matrix comprising at least one α-oxocarboxylic acid or salt thereof is used to treat the formulated fragrance, body care product, cosmetic, fragrance raw material, flavored preparation, nutritional supplement, or food raw material.

[0344] Any inert, finely divided or high surface area material can be used as a solid support. Examples include, but are not limited to, metals, glass, expanded ceramics, plastics, or inorganic solids. In addition, the solid support can comprise the bottom and / or walls of a container containing a formulated fragrance, body care product, cosmetic, fragrance raw material, flavored product, nutritional supplement, or food raw material.

[0345] In some configurations, the solid support has a high surface area: volume ratio. Examples of such solid supports include, but are not limited to, steel wool. Examples of compositions treated with a solid support as described above according to the above configurations can be found in Example 24 below.

[0346] Reference Fig.17 and Examples 27 to 34 below, in some forms, the salt of at least one α-oxocarboxylic acid is insoluble, wherein the salt comprises a linear series of at least one α-oxocarboxylic acid ionically bonded to a polydentate amine compound. As used herein, the term "polydentate amine compound" refers to an amine compound having more than one free amine group capable of forming an ionic bond with a carboxyl group of at least one α-oxocarboxylic acid.

[0347] In some forms, the linear series comprises a "bidentate" amine compound. As used herein, the term "bidentate amine compound" refers to an amine compound having two free amine groups capable of forming ionic bonds with the carboxyl groups of at least one α-oxocarboxylic acid.

[0348] refer to Fig.17 and Fig.18 In some forms, a branched chain can be introduced into the linear series of at least one α-oxocarboxylic acid bonded to an amine compound by introducing a tridentate amine compound, a bidentate acid, or a mixture thereof. As used herein, the term "tridentate amine compound" refers to an amine compound having three free amine groups capable of forming ionic bonds with the carboxyl group of at least one α-oxocarboxylic acid. As used herein, the term "bidentate acid" refers to an acid having two carboxyl groups capable of forming ionic bonds with the amide group of an amide compound. Examples of tridentate acids include, but are not limited to, citric acid.

[0349] In some embodiments, the at least one α-oxocarboxylic acid is selected from the group consisting of pyruvate, 2-oxopentanoate, phenylglyoxylate, 2-oxobutyrate, 2-oxo-2-furanacetate, oxaloacetate, α-ketoglutarate, 2-oxoglutarate, indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof.

[0350] In some aspects, the polydentate amine compound is selected from the group consisting of N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, and mixtures thereof.

[0351] Other examples of polydentate amine compounds suitable for use in the present disclosure include amino acids, polyimines, chitosan, and the like.

[0352] In some forms, reference Fig.19 and Fig. 20 The linear and / or branched series of at least one α-oxocarboxylic acid ionically bonded to the polydentate amine compound also includes polyacrylic acid, polyethyleneimine, or a mixture thereof.

[0353] In some forms, the linear and / or branched series may include a polydentate amine compound ionically bonded to at least one α-oxocarboxylic acid with other moieties, such as phosphate or sulfate moieties.

[0354] In some forms, the at least one α-oxocarboxylic acid is incorporated into an aqueous phase of a gel comprising a polymer selected from the group consisting of gelatin, agarose, alginate, polyacrylamide, acrylate, and combinations thereof.

[0355] In some forms, the gel can be configured to exclude molecules above or below a certain molecular weight. Examples of such configurations include, but are not limited to, the formation of branches configured to act as size exclusion filters.

[0356] In some forms, the at least one α-oxocarboxylic acid further comprises an ammonium salt.

[0357] In some embodiments, the linear and / or branched series of at least one α-oxocarboxylic acid bonded to the amine compound via an ionic bond further comprises a polymer selected from the group consisting of gelatin, agarose, alginate, polyacrylamide, acrylate, and combinations thereof. In some embodiments, the linear and / or branched series of at least one α-oxocarboxylic acid bonded to the amine compound via an ionic bond comprises a network associated with an aqueous phase. In some embodiments, the aqueous phase may comprise at least one α-oxocarboxylic acid.

[0358] In one aspect, the amine compound may be a polydentate amine compound.

[0359] In some forms, the linear and / or branched series of at least one α-oxocarboxylic acid bonded to the amine compound by an ionic bond can be configured to exclude molecules above or below a certain molecular weight. Examples of such configurations include, but are not limited to, the formation of branches configured to act as size exclusion filters.

[0360] In one aspect, the amine compound may be a polydentate amine compound.

[0361] Without intending to be bound by any particular theory, the linear and / or branched series of at least one α-oxocarboxylic acid bonded to the polydentate amine compound via an ionic bond is insoluble, has increased viscosity, viscoelasticity, or gel-like properties. In some forms, the linear and / or branched series of at least one α-oxocarboxylic acid bonded to the polydentate amine compound via an ionic bond is free of water.

[0362] In some aspects, the increased viscosity, viscoelasticity, or gel-like properties of the linear and / or branched series of at least one α-oxocarboxylic acid ionically bonded to the polydentate amine compound can be configured to enhance, improve, or promote adhesion of the linear and / or branched series of at least one α-oxocarboxylic acid ionically bonded to the polydentate amine compound to a solid substrate.

[0363] Referring to Example 32, in some forms, the rate of reduction of POV can be increased by increasing the hydrophobicity of at least one α-oxocarboxylic acid bonded to the polydentate amine compound via an ionic bond.

[0364] The POV repair compounds described herein may be used in combination with known antioxidants.Any antioxidant that has been conventionally used and / or is suitable for a particular application may be combined with the POV repair compounds of the present invention.

[0365] Other antioxidants include, but are not limited to, synthetic compounds such as BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tert-butylhydroquinone), propyl gallate, antioxidants described in U.S. Pat. No. 7,247,658B2, etc. Naturally occurring antioxidants may also be used in conjunction with the POV repair agent, including, but not limited to, tocopherols, tocotrienols, ascorbic acid, carotenoids, flavonoids, anthocyanins, stilbenoids, isoflavones, and catechins.

[0366] The present invention is best illustrated by, but not limited to, the following examples.

[0367] Example

[0368] Example 1: Reduction of POV in citrus oil using pyruvic acid according to one embodiment of the invention

[0369] 50 mL of mixed citrus oils (orange, lemon, lime, mandarins, bergamot and tangerines) were placed in a 100 cm round bottom flask at room temperature along with a stir bar and an argon blanket.

[0370] A 4:1 v / v isopropanol / pyruvic acid solution was prepared and 20 mL of the pyruvic acid solution was dripped into the stirred citrus oil at a rate of 0.25 mL / min by using a syringe pump.

[0371] When the addition is complete, add 10 mL of water and 100 mg of anhydrous sodium carbonate to the flask and keep stirring. 2 When evolution ceased (approximately 2-4 minutes), the aqueous layer was removed with a pipette and discarded.POV measurements were performed on the mixed citrus oils before and after pyruvic acid treatment.

[0372] The POV before treatment was 27.261 mEq / L, and the POV after treatment was 4.786 mEq. / L. The reduction rate of POV was about 82%.

[0373] Example 2: Reduction of POV in limonene using 2-oxopentanoic acid according to one embodiment proposed herein

[0374] 10 mL of autoxidized limonene was placed in a 30 mL glass vial at room temperature along with a stir bar and argon blanket. 100 μL of 2-oxopentanoic acid was added. The vial was shaken once and allowed to sit for 50 minutes. No further treatment was done prior to POV testing. POV measurements were taken on limonene before and after 2-oxopentanoic acid treatment. The POV before treatment was 65.97 mEq. / L and the POV after treatment was 17.21 mEq. / L. The reduction in POV was approximately 74%.

[0375] Example 3: Reduction of POV in limonene using 2-oxobutyric acid according to one embodiment proposed herein

[0376] 20 mL of self-oxidized limonene was placed in a 30 mL glass vial at room temperature along with a stir bar and an argon blanket. 250 μL of 2-oxobutyric acid was added. The vial was shaken once and allowed to stand while monitoring the POV value over time. The collected data is shown in the table below.

[0377]

[0378] The results show an initial rapid decrease in POV followed by a decrease in the rate of POV decrease. This may be due to reagent consumption, but the loss of POV is not sufficient to fully account for all of the added 2-oxobutyric acid on a molar basis. It is possible that some hydroperoxides are destroyed very quickly, while other oxidants are destroyed more slowly. When an additional 500 μL of 2-oxobutyric acid was added and the sample was allowed to stand for an additional 24 hours, the measured POV was 8.577 mEq. / L (total reduction of 87.1%).

[0379] Example 4: Reduction of POV in limonene using 2-phenylglyoxylic acid according to one embodiment proposed herein

[0380] 20 mL of self-oxidized limonene was placed in a 30 mL glass vial at room temperature along with a stir bar and an argon blanket. 200 mg of phenylglyoxylic acid was added and allowed to dissolve. The vial was shaken once and allowed to stand while monitoring the POV value over time. The data collected is shown in the table below.

[0381]

[0382] Example 5: Reduction of POV in limonene using 2-oxo-2-furanacetic acid according to one embodiment proposed herein

[0383] 20 mL of mixed citrus oil was placed in a 30 mL glass vial with a stir bar and argon blanket at room temperature. 400 mg of α-oxo-2-furanacetic acid was added. The vial was shaken once and allowed to stand while monitoring the POV value over time. Most of the added α-oxo-2-furanacetic acid was insoluble, so the limited solubility of the acid may act as a mechanism for controlled release. As the α-oxo-2-furanacetic acid in solution is consumed by the hydroperoxide, it is more likely to dissolve based on the solubility constant. In this way, the undissolved solids act as a sink to maintain a stable, low concentration of α-oxo-2-furanacetic acid dissolved in the mixed citrus oil.

[0384] In this case, because the time between measurements was relatively long (days rather than minutes), it is possible that the untreated blended citrus oil had further oxidized during the experiment. Therefore, the POV of the treated oil was still compared to the POV of the untreated oil, but the measurement of the untreated oil was re-determined at each time point (rather than using just one initial value). The data collected is shown in the table below.

[0385]

[0386] Example 6: According to one embodiment proposed herein, 2-oxopentanoic acid or phenylglyoxylic acid is used to reduce POV in a skin cream formulation.

[0387] According to the German Pharmacopoeia DAB 2008, a skin cream formulation containing 0.5 parts of cetyl stearyl alcohol, 6.0 parts of lanolin alcohol and 93.5 parts of white petroleum jelly was prepared.

[0388] The skin cream was divided into two separate formulations. A highly oxidized limonene sample was added to both formulations, with the first formulation receiving approximately one-third the concentration of oxidized limonene in the second formulation. Analysis of the oxidized limonene sample indicated that the sample contained a mixture of limonene hydroperoxide isomers.

[0389] The initial POV of the first and second skin cream formulations, followed by treatment with 2-oxopentanoic acid or phenylglyoxylic acid, was performed as follows: 2-oxopentanoic acid (second formulation) or phenylglyoxylic acid (first formulation) was thoroughly mixed into the skin cream formulation. The POV of the formulation was measured during the addition of 2-oxopentanoic acid. After the addition of 2-oxopentanoic acid or phenylglyoxylic acid, the treated formulation was allowed to stand at room temperature. The POV data obtained were corrected to the exact weight of the cream aliquot titrated at each individual time point and normalized as a percentage relative to the initial POV.

[0390] The second formulation, which contained the highest amount of oxidized limonene sample, was treated with about 2.3% w / w 2-oxopentanoic acid. The results are as follows Figure 3 shown.

[0391] The first formulation, which contained the lowest amount of oxidized limonene sample, was treated with about 3.9% w / w 2-phenylglyoxylic acid. The results are as follows Figure 4 shown.

[0392] Example 7: The diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 1:2.

[0393] 1.461 g (0.01 mole) of α-ketoglutaric acid was dissolved in 10 mL of anhydrous acetone to give a clear solution. This solution was added as a portion to 2.384 g (0.02 mole) of pure NMDEA. The opaque white emulsion was vortexed vigorously for 3-4 minutes, during which the second phase had coalesced. The mixture was placed in a freezer for at least 30 minutes to thicken the bottom phase into a waxy solid. When still very cold, the top layer can be easily removed by decantation or a pipette and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen and then processed in a vacuum oven at room temperature. This produced a transparent, light yellow, high viscosity oil at room temperature containing diammonium salt (AKG-DiNMDEA salt).

[0394] Model fragrances were made using 90 / 10 v / v ethanol / water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as fragrance oil. The mixed citrus oil was loaded into the solvent in an amount of approximately 19.4% v / v (6 mL oil was added to 25 mL solvent). About 400 mg (2.0% w / v) of AKG-DiNMDEA salt was dissolved in 20 mL of mixed citrus fragrances and POV was measured based on the change in time after addition. Untreated fragrance samples were operated in a similar manner to the treated fragrances and were also tested because POV would rise rapidly with the operation of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0395] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 12.39mmol / L 12.39mmol / L 70 8.07 --- 90 6.16 --- 1150 1.38 --- 1165 1.06 --- 1180 0.85 --- 1195,1210 --- 12.31,13.60 1220 0.78 --- 1400 --- 13.38 1420 0.77 --- 1440(24 hours) 0.79 ---

[0396] These data show that 24 hours after the addition of AKG-DiNMDEA salt, the reduction in POV was approximately 94%.

[0397] In addition to the treatments performed in the model fragrance as described above, similar experiments were performed in mixed citrus oils. A mixed citrus oil sample was prepared by mixing lime oil, orange oil, grapefruit oil, lemon oil, tangerine oil, mandarin oil, and bergamot oil so that a variety of terpene hydroperoxides were present in the treated mixture to be tested. About 200 mg (1.0% w / v) of AKG-DiNMDEA salt was added to 20 mL of mixed citrus oil. Even with vigorous mixing, the salt did not seem to be completely dissolved. However, POV measurements were performed based on the change in time after addition. Untreated mixed citrus oil samples were handled in a similar manner to the treated oils and were also tested because POV increases rapidly with the handling of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0398] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 10.37mmol / L 10.37mmol / L 90 5.42 --- 110 5.36 --- 135 --- 11.28 150(2.5 hours) 4.87 --- 1240 3.91 --- 1250 4.40 --- 1280 3.96 --- 1505 (25 hours & 5 minutes) 4.52 --- 1545 4.25 ---

[0399] This represents only a moderate to good improvement in the POV status of the oil; after one day of treatment, the POV reduction was 59%. This may be due to the poor solubility of 2-oxo acid salts in citrus oils.

[0400] Example 8: A diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and N,N-dimethyldodecylamine (DiMeC12A, CAS#112-18-5) in a molar ratio of 1:2.

[0401] 1.461 g (0.01 mole) of α-ketoglutaric acid was dissolved in 6 mL of anhydrous acetone. The solution was added dropwise to a separate solution of 4.268 g (0.02 mole) of N,N-dimethyldodecylamine in 6 mL of anhydrous acetone under stirring over a period of 1 to 2 minutes. No obvious signs of reaction were observed except that the combined solution was warmed to about 35 to 40°C. The mixture was shaken briefly but vigorously and then cooled in a freezer for 30 minutes. Even in the cold state, no precipitation of the product occurred, but when the mixture was shaken again, the entire mass solidified almost immediately into a solid white waxy substance. The solid was warmed to 30 to 35°C to reliquefy the product so that the trapped acetone could be removed by a nitrogen stream and then processed in a vacuum oven at room temperature. A white waxy solid containing the diammonium salt (AKG-DiMeC12A salt) was obtained.

[0402] Model fragrances were made using 90 / 10 v / v ethanol / water as solvent and a mixture of orange oil, grapefruit oil, and bergamot oil as fragrance oils. The mixed citrus oil was loaded into the solvent at approximately 19.4% v / v (6 mL of oil was added to 25 mL of solvent). Approximately 400 mg (2.0% w / v) of AKG-DiMeC12A salt was dissolved in 20 mL of mixed citrus fragrances and POV was measured based on the change in time after addition. Untreated fragrance samples were operated in a similar manner to the treated fragrances and were also tested because POV would rise rapidly with the operation of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0403] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 12.74mmol / L 12.74mmol / L 35 8.31 --- 45 8.35 --- 70 6.77 --- 130 6.54 --- 145 5.82 --- 180 4.89 --- 210 4.51 --- 240(4 hours) 4.15 --- 270 3.49 --- 4320 (3 days, 72 hours) 0.0 is indistinguishable from blank 14.43

[0404] In addition to the treatments performed in the model fragrance as described above, similar experiments were performed in mixed citrus oils. A mixed citrus oil sample was prepared by mixing lime oil, orange oil, grapefruit oil, lemon oil, tangerine oil, mandarin oil, and bergamot oil so that a variety of terpene hydroperoxides were present in the treated mixture to be tested. About 200 mg (1.0% w / v) of AKG-DiMeC12A salt was dissolved in 20 mL of the mixed citrus oil and POV measurements were performed as a function of time after addition. Untreated mixed citrus oil samples were handled in a similar manner to the treated oils and were also tested because POV increases rapidly with handling of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0405] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 9.53mmol / L 9.53mmol / L 90 3.32 --- 95 2.32 --- 105 2.63 --- 130 2.68 --- 150(2.5 hours) 2.28 --- 250 1.81 --- 260 1.41 --- 4320 (3 days, 72 hours) 1.50 13.58

[0406] These data represent an 89.0% reduction in POV within 72 hours (3 days) after the addition of AKG-DiMeC12A. It appears that the AKG-DiMeC12A may have been exhausted after the 260 minute time point, as no further reaction occurred even after such a long period of time.

[0407] Surface tension measurements of aqueous solutions of AKG-DiMeC12A: To evaluate the surfactant properties of AKG-DiMeC12A, the reduction in surface tension caused by it in aqueous solution relative to pure water was measured. The measurements were performed on a Kruss DSA100S tensiometer by the pendant method. A 0.14 wt % solution of AKG-DiMeC12A in water was used for the measurements. This concentration was chosen so that the results could be compared with literature values ​​for the known surfactant sodium dodecyl sulfate (SDS) at 5 mM, which is approximately 0.15 wt %. The results show that AKG-DiMeC12A has significant surfactant properties:

[0408] Pure water – 71.57 mN / m

[0409] AKG-DiMeC12A – 32.08mN / m

[0410] For comparison, SDS at a concentration of 5 mM at 273 K (approximately 0.15 wt %, very close to the 0.14 wt % used here) has an air-water surface tension of 33.5 to 35.5 mN / m, depending on the pH (see Hernainz, F. et al., Colloids Surf. A, 2002, 196, 19-24).

[0411] Example 9: The diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and 2-(dimethylamino)ethanol (Deanol, CAS#108-01-0) in a molar ratio of 1:2.

[0412] 1.461 g (0.01 mole) of α-ketoglutaric acid was dissolved in 10 mL of anhydrous acetone to give a clear solution. The solution was added to 1.783 g (0.02 mole) of pure 2-dimethylaminoethanol ("Deanol") under stirring over a period of 1 to 2 minutes. The opaque white emulsion was vortexed vigorously for one minute, during which the second phase had coalesced. The mixture was placed in a freezer overnight to thicken the bottom phase into an extremely viscous, turbid oil. When still very cold, the top layer can be easily removed by decantation or a pipette and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen and then processed in a vacuum oven at room temperature. This produced a transparent, colorless viscous oil at room temperature containing diammonium salt (AKGDiDeanol salt).

[0413] Model fragrances were made using 90 / 10 v / v ethanol / water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as fragrance oils. The mixed citrus oil was loaded into the solvent at approximately 19.4% v / v (6 mL of oil was added to 25 mL of solvent). Approximately 200 mg (1.0% w / v) of AKG DiDeanol salt was dissolved in 20 mL of mixed citrus fragrances and POV was measured based on the change in time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because POV increases rapidly with the handling of the samples (opening bottles, stirring, etc.). The results are shown in the table below.

[0414] Time in minutes Processed Spice's POV Unprocessed Spice's POV 45 --- 11.73mmol / L 60 5.95mmol / L --- 75 5.66 --- 115 4.96 --- 195 3.20 --- 210 3.08 --- 270 --- 12.25 300(5 hours) 2.31 --- 370 1.73 --- 380 1.72 --- 390 --- 11.70 1440(24 hours) 0.0 is indistinguishable from blank 11.79

[0415] Example 10: An ammonium salt was formed by reacting pyruvic acid (CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 1:1.

[0416] 2.642 g (0.03 mole) of pyruvic acid was dissolved in 5 mL of anhydrous acetone to give a clear solution. The solution was added dropwise to a second solution made of 3.575 g (0.03 mole) of NMDEA and 5 mL of anhydrous acetone under stirring over a period of 1 to 2 minutes. Due to the addition of the acidic solution, the resulting mixture became warm (about 35 to 45 ° C) and turbid. The milky emulsion was vortexed vigorously for one minute, during which the second phase had coalesced. The mixture was placed in a freezer for at least 1 hour, causing a significant increase in the viscosity of the bottom phase, but it did not solidify. When it was still very cold, the top layer could be easily removed by decantation or a pipette and discarded. The residual acetone was removed from the bottom product layer by a nitrogen stream and then processed in a vacuum oven at room temperature. This produced a clear golden, high-viscosity oil at room temperature containing diammonium salt (PA-NMDEA salt).

[0417] Model fragrances were prepared using 90 / 10 v / v ethanol / water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as fragrance oil. Mixed citrus oil was loaded into the solvent in an amount of approximately 16.7% v / v (40 mL oil dissolved in 200 mL solvent, 240 mL fragrance in total). About 150 mg (1.0% w / v) of PA-NMDEA salt was dissolved in 15 mL of mixed citrus fragrance and POV was measured based on the change in time after addition. Untreated fragrance samples were operated in a similar manner to the treated fragrances and were also tested because POV would rise rapidly with the operation of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0418] Time in hours Processed Spice's POV Unprocessed Spice's POV 0.0 --- 5.55mmol / L 1.8 3.48mmol / L --- 71.5 1.01 --- 72.5 --- 6.66 73.3 0.58 --- 74.7 --- 6.58

[0419] These data indicate that PA-NMDEA was depleted at the 73.3 hour mark, as the POV of the sample never decreased after that, even at extended reaction times. This represents a >90% reduction in POV; the average untreated oil after 3 days was (6.66+6.58) / 2=6.62 mmol / L, so 0.58 / 6.62 x 100=8.76% remaining, or a 91.2% reduction in POV).

[0420] Example 11: Ammonium salt was formed by reacting phenylglyoxylic acid (PhGA, CAS#611-73-4) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 1:1.

[0421] 1.501 g (0.01 mole) of PhGA was dissolved in 5 mL of anhydrous acetone to give a clear solution. This solution was added as a portion to a second solution made from 1.192 g (0.01 mole) of NMDEA and 5 mL of anhydrous acetone. The resulting mixture became warm (about 30-35° C.) and turned light yellow, but no turbidity or precipitation was formed. The solution was vortexed vigorously for one minute and placed in a freezer for 30 minutes. There was still no precipitate or second layer formed, but the solution was clearly supersaturated. An attempt was made to remove the solvent acetone by a nitrogen stream, but a thick paste of white crystalline material formed almost immediately when the nitrogen stream contacted the solution. As the mixture warmed to room temperature, the crystals began to dissolve back into the acetone. The product was refrozen, resulting in reprecipitation of a highly crystalline product, and the supernatant acetone was removed by pipette as much as possible while still cold. The residual acetone was then removed under a nitrogen stream to give pure white needle-shaped crystals. The crystalline product containing the diammonium salt (PhGA-NMDEA salt) is extremely hygroscopic and will liquefy quickly if exposed to the environment. The needle-shaped white masses must be kept under vacuum or strict nitrogen protection to maintain the crystalline state. Due to hygroscopicity, no weight / yield was obtained.

[0422] Model fragrances were prepared using 90 / 10 v / v ethanol / water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as fragrance oil. Mixed citrus oil was loaded into the solvent with an amount of approximately 16.7% v / v (40 mL oil was dissolved in 200 mL solvent, 240 mL fragrance in total). About 150 mg (1.0% w / v) of PhGA-NMDEA salt was dissolved in 15 mL mixed citrus fragrances and POV was measured according to the change in time after addition. Untreated fragrance samples were operated in a similar manner to treated fragrances and were also tested because POV would rise rapidly with the operation of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0423] Time in hours Processed Spice's POV Unprocessed Spice's POV 0.0 --- 5.55mmol / L 1.8 4.87mmol / L --- 71.5 (~3 days) 4.61 --- 72.5 --- 6.66 73.3 4.18 --- 74.7 --- 6.58 243 (~10 days) 2.62 8.37

[0424] These data suggest that while the phenylglyoxylate moiety does play a role in reducing POV in the model fragrance, it is less active than the non-aryl pyruvates studied. This difference in reactivity may be useful in certain circumstances.

[0425] Example 12: Reduction of POV in sunflower oil using 2-oxopentanoic acid according to one embodiment presented herein.

[0426] 25 mL of sunflower oil (from an off-the-shelf opened 1 quart container with approximately 25% atmospheric headspace; unknown storage time) was placed in a 30 mL vial at room temperature. 250 μL of 2-oxopentanoic acid was added. The vial was shaken and allowed to sit on the bench at ambient temperature under laboratory lighting. No further processing was done prior to POV testing.

[0427] POV measurements were taken on sunflower oil before and after treatment with 2-oxopentanoic acid. The untreated oil was also remeasured regularly for comparison, since opening the bottle replenishes the atmospheric headspace and may result in an increase in the POV of the bottle contents. The percentage reduction relative to the most recent POV value of the untreated oil was always calculated, and if multiple measurements were made, the average value (shown in brackets) was used for the calculation. The results are shown in the table below.

[0428]

[0429] N / A = Not Applicable

[0430] Untreated sunflower oil increased POV by nearly 40% (12.30 / 8.81 mmol / L x 100 = 139.6%) after only 15 days in the bottle at room temperature, and the headspace was already filled with ambient atmosphere during the brief open period required for each sampling.

[0431] In contrast, treatment of sunflower oil with 0.83% v / v 2-oxopentanoic acid resulted in a 82.9% reduction in POV after 15 days compared to untreated oil.

[0432] Example 13: An ammonium salt was formed by reacting phenylpyruvic acid (CAS#156-06-9) and N,N-dimethyldecylamine (DiMeC10A, CAS#1120-24-7) in a molar ratio of 1:1.

[0433] 3.707 g (0.02 mole) of phenylpyruvic acid was dissolved in 10 mL of anhydrous acetone to give a clear solution. A separate solution was made from 3.283 g (0.02 mole) of N,N-dimethyldecylamine in 10 mL of anhydrous acetone. The amine solution was added dropwise to the phenylpyruvic acid solution over a period of 2-3 minutes with stirring; no obvious signs of reaction were seen and no significant exotherm was observed. The mixture was shaken briefly but vigorously and cooled in a freezer for 30 minutes. A thick network of white flocculent fine crystals formed and a small amount of acetone was decanted from the solid while still cold and discarded. Most of the solvent acetone appeared to be entrapped in the crystalline network and was removed by a stream of nitrogen and then worked up in a vacuum oven at room temperature. An off-white, fluffy, crystalline solid was obtained in quantitative yield.

[0434] According to one embodiment proposed herein, the POV in sunflower oil was reduced using a diammonium salt formed by the reaction of phenylpyruvic acid and N,N-dimethyldecylamine (referred to herein as DiMeC10A-PhPA): 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial and 0.3032 g of DiMeC10A-PhPA was added thereto. Most of the salt dissolved, but some undissolved solids remained. The mixture was placed on a bench under ambient light in the laboratory at room temperature and POV measurements were taken periodically. The results are shown in the table below.

[0435]

[0436] (*) – indistinguishable from whitespace

[0437] This phenyl pyruvate salt can reduce the POV of sunflower oil very quickly.

[0438] According to one embodiment proposed herein, the diammonium salt formed by the reaction of phenylpyruvic acid with N,N-dimethyldecylamine (referred to herein as DiMeC10A-PhPA) was used to reduce the POV in a model fragrance: A model fragrance was made using 90 / 10 v / v ethanol / water as the solvent and a mixture of lime oil, orange oil, grapefruit oil, and bergamot oil as the fragrance oil. The mixed citrus oil was loaded into the solvent at an amount of approximately 16.7% v / v (40 mL of oil dissolved in 200 mL of solvent, a total of 240 mL of fragrance). Approximately 164 mg (1.1% w / v) of PhPA-DiMeC10A salt was dissolved in 15 mL of the mixed citrus fragrance and POV measurements were taken as a function of time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because the POV increases rapidly with the handling of the sample (opening the bottle, stirring, etc.).

[0439] The results are shown in the following table.

[0440] Time in hours / days Processed Spice's POV Unprocessed Spice's POV 0.0 9.44mmol / L 9.44mmol / L 0.5 hours 5.7 --- 1 hour --- 9.8 4 hours 4.58 9.8 1 day 3.1 9.66 2 days 2.38 10.60 4 days 1.98 10.12 7 days 1.33 10.38

[0441] The results shown above indicate that after 7 days of adding PhPA DiMeC10A, there was an 87.2% reduction in POV relative to the untreated material.

[0442] Example 14: An ammonium salt was formed by reacting α-oxo-2-furanacetic acid (CAS#1467-70-5) and N,N-dimethyldecylamine (DiMeC10A, CAS#1120-24-7) in a molar ratio of 1:1.

[0443] 2.114 g (0.015 mole) of α-oxo-2-furanacetic acid was dissolved in 10 mL of anhydrous acetone. α-oxo-2-furanacetic acid (grey-brown crystalline solid) was used as received from the supplier to give a dark brown solution containing a small amount of undissolved flocculent material. It was decided to continue with the initial screening of the material "as received" and if the screening results indicated so, the purified starting material could be prepared at a later time.

[0444] A separate solution was made from 2.780 g (0.015 mole) of N,N-dimethyldecylamine in 10 mL of anhydrous acetone. The amine solution was added dropwise to the crude α-oxo-2-furanacetic acid solution under stirring over a period of 5 minutes; no obvious signs of reaction were observed, nor was there a noticeable temperature rise. The mixture was shaken briefly but vigorously and cooled in the freezer for 30 minutes. Even in the cold state, no precipitation of the product occurred, so the acetone was removed by a stream of nitrogen and then processed in a vacuum oven at room temperature. A quantitative yield of a brown viscous oil was obtained, which crystallized to a brown solid after a few days at freezer temperature.

[0445] According to one embodiment proposed herein, the POV in sunflower oil is reduced using a diammonium salt formed by the reaction of α-oxo-2-furanacetic acid with N,N-dimethyldecylamine (referred to herein as FAA-DiMeC10A): 15 mL of sunflower oil that has been stored in a plastic bottle at room temperature for 1 year but has never been opened during this storage period is placed in a 30 mL glass vial and 0.3358 g of FAA-DiMeC10A is added thereto. Most of the salt dissolves, but a small amount of dark brown insoluble droplets remain. The mixture is placed on a workbench at room temperature under laboratory ambient light, and POV measurements are performed periodically. The results are shown in the following table.

[0446]

[0447] (*) – indistinguishable from whitespace

[0448] According to one embodiment proposed herein, the diammonium salt formed by the reaction of α-oxo-2-furanacetic acid with N,N-dimethyldecylamine (referred to herein as FAA-DiMeC10A) was used to reduce the POV in a model fragrance: A model fragrance was made using 90 / 10 v / v ethanol / water as a solvent and a mixture of lime oil, orange oil, grapefruit oil, and bergamot oil as fragrance oils. The mixed citrus oil was loaded into the solvent in an amount of approximately 16.7% v / v (40 mL of oil dissolved in 200 mL of solvent, a total of 240 mL of fragrance). About 150 mg (1.0% w / v) of FAA-DiMeC10A salt was dissolved in 15 mL of mixed citrus fragrance, and POV measurements were performed as a function of time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because POV increases rapidly with the handling of the sample (opening the bottle, stirring, etc.). The results are shown in the following table.

[0449] Time in days Processed Spice's POV Unprocessed Spice's POV 0.0 --- 5.15mmol / L 1 5.06mmol / L 6.31 2 4.89 6.77 4 4.68 7.14 7 4.28 7.13

[0450] The results shown above indicate a 40.0% reduction in POV relative to the untreated material after 7 days of addition of FAA DiMeC10A. It appears that while the α-oxo-2-furanacetic acid moiety does play a role in reducing POV in the model fragrance, it is less active / slower than the non-aromatic α-oxo carboxylic acids studied.

[0451] Example 15: The diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and tri[2-(2-(methoxyethoxy)ethyl]amine (CAS#70384-51-9) in a molar ratio of 1:2.

[0452] 2.922 g (0.02 mole) of α-ketoglutaric acid was dissolved in 10 mL of anhydrous acetone. A separate solution of 12.937 g (0.04 mole) of tri[2-(2-(methoxyethoxy)ethyl]amine (TMEEA) was made in 5 mL of anhydrous acetone, and the amine solution was added dropwise to the AKG solution over a period of 2 minutes with stirring; no obvious signs of reaction were observed, but the resulting mixture became slightly warm (about 35-45°C). The mixture was shaken briefly but vigorously and cooled in a freezer for 30 minutes. Even in the cold state, no precipitation of the product occurred, so the acetone was removed by a stream of nitrogen and then processed in a vacuum oven at room temperature. A clear golden brown, slightly viscous oil was obtained in quantitative yield.

[0453] According to one embodiment presented herein, the POV in sunflower oil was reduced using a diammonium salt formed by the reaction of α-ketoglutaric acid and tri[2-(2-(methoxyethoxy)ethyl]amine (referred to herein as AKG-diTMEEA): 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial and 0.5081 g of AKG-diTMEEA was added thereto. Due to the very high molecular weight of this compound (792.96 g / mole), a higher weight than usual was used. The salt dissolved completely to give a clear golden brown oil. The solution was placed on a bench under ambient light in the laboratory at room temperature and POV measurements were taken periodically, with the results shown in the table below.

[0454]

[0455] Example 16: The diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and N,N-dimethyldodecylamine (CAS#112-18-5) in a molar ratio of 1:2.

[0456] 1.461 g (0.01 mole) of α-ketoglutaric acid was dissolved in 6 mL of anhydrous acetone. This solution was added dropwise to a separate solution of 4.268 g (0.02 mole) of N,N-dimethyldodecylamine in 6 mL of anhydrous acetone under stirring over a period of 1 to 2 minutes. No obvious signs of reaction were observed except that the combined solution was warmed to about 35 to 40°C. The mixture was shaken briefly but vigorously and then cooled in a freezer for 30 minutes. Even in the cold state, no precipitation of the product occurred, but when the mixture was shaken again, the entire mass solidified almost immediately into a solid white waxy substance. The solid was warmed to 30 to 35°C to reliquefy the product so that the trapped acetone could be removed by a stream of nitrogen and then processed in a vacuum oven at room temperature. A white waxy solid was obtained in quantitative yield.

[0457] According to one embodiment proposed herein, the POV in sunflower oil is reduced using a diammonium salt formed by the reaction of α-ketoglutaric acid and N,N-dimethyldodecylamine (referred to herein as AKG-DiMeC12A): 15 mL of sunflower oil that has been stored in a plastic bottle at room temperature for 1 year but has never been opened during this storage period is placed in a 30 mL glass vial and 0.3062 g of AKG-DiMeC12A is added thereto. The salt does not completely dissolve but forms a turbid gel-like suspension with the sunflower oil. The mixture is placed on a bench under ambient light in the laboratory at room temperature and POV measurements are performed periodically. The results are shown in the table below.

[0458]

[0459] Example 17: An ammonium salt was formed by reacting pyruvic acid (CAS#127-17-3) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 1:1.

[0460] 2.642 g (0.03 mole) of pyruvic acid was dissolved in 5 mL of anhydrous acetone to give a clear solution. The solution was added dropwise to a second solution made of 3.575 g (0.03 mole) of NMDEA and 5 mL of anhydrous acetone under stirring for 1 to 2 minutes. Due to the addition of the acidic solution, the resulting mixture became warm (about 35 to 45 ° C) and turbid. The milky emulsion was vortexed vigorously for one minute, during which the second phase had coalesced. The mixture was placed in a freezer for at least 1 hour, causing a significant increase in the viscosity of the bottom phase, but it did not solidify. When it was still very cold, the top layer could be easily removed by decantation or a pipette and discarded. The residual acetone was removed from the bottom product layer by a nitrogen stream and then processed in a vacuum oven at room temperature. A golden, high-viscosity oil that was clear at room temperature was obtained in quantitative yield.

[0461] According to one embodiment proposed herein, POV in sunflower oil was reduced using a diammonium salt formed by the reaction of pyruvic acid and N-methyldiethanolamine (referred to herein as PA-NMDEA): 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial and 0.2988 g of PA-NMDEA was added thereto. The salt appeared to dissolve and / or disperse, but the resulting mixture was not completely clear; it had a translucent colloidal appearance. The mixture was placed on a bench at room temperature under ambient laboratory light and POV measurements were taken periodically. The results are shown in the table below.

[0462]

[0463] Example 18: Reduction of POV in a model flavor using α-ketoglutarate according to one embodiment proposed herein

[0464] Alpha-ketoglutaric acid is a strong acid, with a solution of 0.114 g of alpha-ketoglutaric acid in 10 mL of water having a measured pH of 1.75. Therefore, it may be necessary to limit the amount of alpha-ketoglutaric acid in solution in a hydroalcoholic flavor base to prevent changes to the sensory properties of the flavor raw material.

[0465] A model fragrance was made using 90 / 10 v / v ethanol / water as solvent, to which a mixture of orange oil, grapefruit oil, and bergamot oil was added. The mixed citrus oil was loaded into the solvent at approximately 19.4% v / v (6 mL oil was added to 25 mL solvent). Approximately 240 mg (1.2% w / v) of alpha-ketoglutaric acid was dissolved in 20 mL of the mixed citrus fragrance and POV measurements were performed the next day. The results are shown in the table below.

[0466] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 11.99mmol / L 11.99mmol / L 1440(24 hours) 0.0 is indistinguishable from blank ---

[0467] These data show that the POV of the formulated fragrance was completely reduced after 24 hours of treatment of the formulated fragrance with alpha-ketoglutarate.

[0468] Example 19: Reduction of POV in a model fragrance using oxaloacetic acid according to one embodiment proposed herein

[0469] Oxaloacetate is known to be unstable in aqueous solution (see HA Krebs, Biochemistry (1942) 36, 303-305), resulting in the release of carbon dioxide and pyruvic acid. However, oxaloacetate is effective in reducing POV in solutions in which it is dissolved (e.g., hydroalcoholic fragrances). However, it is not clear whether the reduction in POV occurs directly through oxaloacetate or through the released pyruvic acid, or through both. Analysis of the reaction products (acetic acid and malonic acid) can distinguish between these two pathways, but this is not studied here.

[0470] A model fragrance was made using 90 / 10 v / v ethanol / water as solvent, to which a mixture of orange oil, grapefruit oil, and bergamot oil was added. The mixed citrus oil was loaded into the solvent at approximately 19.4% v / v (6 mL oil added to 25 mL solvent). Approximately 166 mg (0.83% w / v) of oxaloacetic acid was dissolved in 20 mL of the mixed citrus fragrance and POV measurements were taken at the times shown in the table below.

[0471] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 9.44mmol / L 9.44mmol / L 27 5.90 --- 245 1.91 --- 1440(24 hours) 0.0 is indistinguishable from blank ---

[0472] These data show that the POV of the formulated fragrance was completely reduced 24 hours after treatment of the formulated fragrance with oxaloacetic acid.

[0473] Example 20: An ammonium salt was formed by reacting phenylglyoxylic acid (CAS#611-73-4) and 1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS#3699-54-5) in a molar ratio of 1:1.

[0474] 3.003 g (0.02 mole) of phenylglyoxylic acid was dissolved in 10 mL of anhydrous acetone to give a clear solution. A separate solution was made from 2.603 g (0.02 mole) of 1-(2-hydroxyethyl)-2-imidazolidinone in 10 mL of anhydrous acetone. Since 1-(2-hydroxyethyl)-2-imidazolidinone was provided as a 75% w / w aqueous solution, the actual amount of 75% reagent used was 3.471 g to compensate for the weight of the solvent water. The 1-(2-hydroxyethyl)-2-imidazolidinone amine solution was added dropwise to the phenylglyoxylic acid solution under stirring over a period of 3 minutes; no obvious signs of reaction were observed, nor was there any noticeable warming. The mixture was shaken briefly but vigorously and cooled in a freezer for 30 minutes. Even in the cold state, no precipitation of the product occurred, so the acetone solvent was removed by a stream of nitrogen and then processed in a vacuum oven at room temperature. A clear, light yellow, high viscosity oil was obtained in quantitative yield.

[0475] According to one embodiment proposed herein, the diammonium salt formed by the reaction of phenylglyoxylic acid with 1-(2-hydroxyethyl)-2-imidazolidinone (referred to herein as PhGA-HEI) was used to reduce the POV in a model fragrance: A model fragrance was made using 90 / 10 v / v ethanol / water as the solvent and a mixture of lime oil, orange oil, grapefruit oil, and bergamot oil as the fragrance oil. The mixed citrus oil was added to the solvent in an amount of approximately 16.7% v / v (40 mL of oil dissolved in 200 mL of solvent, a total of 240 mL of fragrance). About 150 mg (1.0% w / v) of PhGA-HEI salt was dissolved in 15 mL of the mixed citrus fragrance and POV was measured as a function of time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because the POV increases rapidly with the handling of the sample (opening the bottle, stirring, etc.). The results are shown in the following table.

[0476] Time in days Processed Spice's POV Unprocessed Spice's POV 0.0 --- 5.15mmol / L 1 3.51mmol / L 6.31 2 3.18 6.77 4 3.06 7.14 7 2.94 7.13

[0477] The results shown above indicate that after 7 days of PhGA HEI addition, there was a 58.8% reduction in POV relative to the untreated material. It appears that while the phenylglyoxylic acid moiety does play a role in reducing POV in the model fragrance, it is less active / slower than the non-aromatic α-oxocarboxylic acids studied. This difference in reactivity may be useful in certain circumstances.

[0478] Example 21: The diammonium salt was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and 1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS#3699-54-5) in a molar ratio of 1:2.

[0479] 2.922 g (0.02 mole) of α-ketoglutaric acid (AKG) was dissolved in 10 mL of anhydrous acetone to give a clear solution. A separate solution was made from 5.206 g (0.04 mole) of 1-(2-hydroxyethyl)-2-imidazolidinone (HEI) in 10 mL of anhydrous acetone. Since HEI was provided as a 75% w / w aqueous solution, the actual amount of 75% reagent used was 6.942 g to compensate for the weight of the solvent water. The HEI amine solution was added dropwise to the AKG solution over a period of 3 minutes with stirring; no obvious signs of reaction were observed and no warming was evident. The mixture was shaken briefly but vigorously and cooled in a freezer for 1 hour. Even in the cold state, no precipitation of the product occurred, so the acetone solvent was removed by a stream of nitrogen and then worked up in a vacuum oven at room temperature. A clear, water-white, very viscous oil was obtained in quantitative yield.

[0480] According to one embodiment proposed herein, the diammonium salt formed by the reaction of α-ketoglutaric acid with 1-(2-hydroxyethyl)-2-imidazolidinone (referred to herein as AKG-HEI) was used to reduce the POV in a model fragrance: A model fragrance was prepared using 90 / 10 v / v ethanol / water as the solvent and a mixture of lime oil, orange oil, grapefruit oil, and bergamot oil as the fragrance oil. The mixed citrus oil was loaded into the solvent at approximately 16.7% v / v (40 mL of oil dissolved in 200 mL of solvent, a total of 240 mL of fragrance). About 150 mg (1.0% w / v) of AKG-HEI salt was dissolved in 15 mL of the mixed citrus fragrance and POV was measured as a function of time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because the POV increases rapidly with the handling of the sample (opening the bottle, stirring, etc.). The results are shown in the following table.

[0481] Time in days Processed Spice's POV Unprocessed Spice's POV 0.0 --- 5.15mmol / L 1 1.12mmol / L 6.31 2 0.72 6.77 4 0.70 7.14 7 0.56 7.13

[0482] The results shown above indicate that after 7 days of adding AKG DiHEI, there was a 92.1% reduction in POV relative to the untreated material.

[0483] Example 22: An ammonium salt (referred to herein as AKG-mono(DiMeC12A)) was formed by reacting α-ketoglutaric acid (CAS#328-50-7) and N,N-dimethyldodecylamine (DiMeC12A, CAS#112-18-5) in a molar ratio of 1:1.

[0484] 2.922 g (0.02 mole) of α-ketoglutaric acid was dissolved in 12 mL of anhydrous acetone. This solution was added dropwise to a separate solution of 4.268 g (0.02 mole) of N,N-dimethyldodecylamine in 6 mL of anhydrous acetone under stirring over a period of 1 to 2 minutes. The mixture was shaken, but no visible signs of reaction were seen, except that the temperature of the mixed solution warmed to about 35 to 40°C. The mixture remained clear for several minutes, but upon further shaking, the entire mass immediately solidified into a solid white crystalline mass. The solid was warmed to 30 to 35°C to reliquefy the product so that the trapped acetone could be removed by a stream of nitrogen and then processed in a vacuum oven at room temperature. A white waxy solid was obtained in quantitative yield.

[0485] Model fragrances were made using 90 / 10 v / v ethanol / water as solvent and a mixture of orange oil, grapefruit oil, and bergamot oil as fragrance oils. The mixed citrus oil was loaded into the solvent at approximately 19.4% v / v (6 mL of oil was added to 25 mL of solvent). Approximately 200 mg (1.0% w / v) of AKG-monoMeC12A salt was dissolved in 20 mL of mixed citrus fragrance and POV was measured as a function of time after addition. Untreated fragrance samples were handled in a similar manner to the treated fragrances and were also tested because POV increases rapidly with handling of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0486] Time in minutes (hours) Processed Spice's POV Unprocessed Spice's POV 0.0 11.99mmol / L 11.99mmol / L 30(0.5) 7.01 --- 45(0.75) 6.97 --- 60(1.0) 7.02 --- 180(3.0) 4.89 --- 210(3.5) 4.54 --- 240(4.0) 3.78 --- 270(4.5) 3.77 --- 300(5.0) 3.05 --- 340(5.67) 2.52 --- 1440(24 hours) 0.76 11.66 1470 (24.5 hours) 0.67 --- 1560(26 hours) 0.0 is indistinguishable from blank ---

[0487] These data represent a total and complete reduction in POV within 26 hours following the addition of AKG-mono (DiMeC12A).

[0488] In addition to the treatments performed in the model fragrance as described above, similar experiments were performed in mixed citrus oils. A mixed citrus oil sample was prepared by mixing lime oil, orange oil, grapefruit oil, lemon oil, tangerine oil, mandarin oil, and bergamot oil so that a variety of terpene hydroperoxides were present in the treated mixture to be tested. About 200 mg (1.0% w / v) of AKG-mono (DiMeC12A) salt was added to 20 mL of the mixed citrus oil, but most of it did not dissolve. POV measurements were performed as a function of time after addition. Untreated mixed citrus oil samples were handled in a similar manner to the treated oils and were also tested because POV increases rapidly with handling of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0489] Time in minutes (hours) Processed Spice's POV Unprocessed Spice's POV 0.0 9.45mmol / L 9.45mmol / L 90(1.5) 2.09 --- 100(1.67) 2.00 --- 120(2.0) --- 10.12 135(2.25) 1.63 --- 180(3.0) 1.79 --- 1320(22.0) 0.96 10.56 1345(22.42) 0.91 --- 1620(27.0) --- 10.42 1660(27.67) 0.80 --- 1680(28.0) 0.60 ---

[0490] These data represent a 94.2% reduction in POV relative to the untreated material 28.0 hours after addition of the AKG-mono (DiMeC12A) salt.

[0491] Surface tension measurements of aqueous solutions of AKG-monoDiMeC12A: To evaluate the surfactant properties of AKG-Mono (DiMeC12A), the reduction in surface tension caused by it in aqueous solution relative to pure water was measured. The measurements were performed on a Kruss DSA100S tensiometer by the pendant method. A 0.14 wt % solution of AKG-Mono (DiMeC12A) in water was used for the measurements. This concentration was chosen so that the results could be compared with the literature value of the known surfactant sodium dodecyl sulfate (SDS) at 5 mM, which is approximately 0.15 wt %. The results show that AKG-Mono (DiMeC12A) has significant surfactant properties:

[0492] Pure water – 71.57 mN / m

[0493] AKG-monoDiMeC12A – 32.93mN / m

[0494] For comparison, SDS at a concentration of 5 mM at 273 K (-0.15 wt %, very close to the 0.14 wt % used here) has an air-water surface tension of 33.5 to 35.5 mN / m depending on the pH (see Hernainz, F. et al., Colloids Surf. A, 2002, 196, 19-24).

[0495] Example 23: An ammonium salt was formed by reacting indole-3-pyruvic acid (I-3-PA, CAS#392-12-1) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 1:1.

[0496] 0.61g (0.003 mole) of I-3-PA-NMDEA was placed in 4mL methanol, but it was only partially dissolved. A separate mixture was made in 2mL acetone by 0.357g (0.003 mole) of NMDEA, which formed a clear solution. The amine solution was added to indole-3-pyruvic acid as a portion and vortexed vigorously for 1 minute. Some solids remained insoluble, so the mixture was placed in a 40°C water bath. As it became warm, all substances dissolved to form a dark orange clear solution. The mixture was cooled to room temperature, but no precipitation was formed. The solution was placed in a freezer for 30 minutes, during which light pink needle-shaped crystals fell off. The mother liquor was removed with a pipette. It was shown that it contained a large amount of lower purity substances, which could be further recovered to obtain a dark orange solid by blowing the solvent dry under a nitrogen stream. In order to conduct preliminary experiments, the two parts of the product were re-merged, waiting for the development of a more effective crystallization procedure. The yield is quantitative.

[0497] Model fragrances were prepared using 90 / 10 v / v ethanol / water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as fragrance oil. Mixed citrus oil was loaded into the solvent in an amount of approximately 19.4% v / v (6 mL oil was added to 25 mL solvent). About 244 mg (1.2% w / v) of 1-3-PA-NMDEA salt was dissolved in 20 mL of mixed citrus fragrances and POV was measured based on the change in time after addition. Untreated fragrance samples were operated in a similar manner to treated fragrances and were also tested because POV would rise rapidly with the operation of the sample (opening the bottle, stirring, etc.). The results are shown in the table below.

[0498] Time in minutes Processed Spice's POV Unprocessed Spice's POV 0.0 11.09mmol / L 11.09mmol / L 60 0.0 is indistinguishable from blank ---

[0499] These data show that 60 minutes after addition of the 1-3-PA-NMDEA salt, there is a rapid decrease in POV relative to the untreated material.

[0500] Example 24: According to one embodiment proposed herein, POV was reduced in a model fragrance using a diammonium salt prepared from α-ketoglutaric acid (CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) at a molar ratio of 1:2 incorporated into a solid support.

[0501] It has been observed that POV can be reduced in citrus oils even with α-oxocarboxylates that are virtually insoluble in the citrus oil being treated. This finding appears to hold true for both solid and liquid salts (which tend to have high viscosities), although the rate and efficiency of reduction is not as high as with soluble salts. It is speculated that the contact surface area between the α-oxocarboxylate phase and the citrus oil phase may be a limiting factor, so if this is the case, any method of increasing the contact area should promote a faster and more facile reaction.

[0502] To this end, an attempt was made to spread a thin, highly dispersed layer of the diammonium salt formed from α-ketoglutaric acid and two equivalents of N-methyldiethanolamine (AKG-DiNMDEA) onto a chemically inert, high surface area solid support. In this example, a commercially available household scrubbing pad made of very thin stainless steel (Scotch-Brite manufactured by 3M Company) was used. pad).

[0503] Preparation of AKG-DiNMDEA coated pads: A single pad was cleaned as follows: The pad was placed in a 250 mL glass beaker and completely covered with pentane. The beaker was sonicated for three minutes, the pentane was drained, and the process was repeated with acetone. The acetone was also drained and the pad was dried in a vacuum oven at room temperature for one hour. The weight of the pad was 19.229 g before and after cleaning, so no significant weight loss was observed after cleaning.

[0504] A solution was made of 3.0 g of AKG-DiNMDEA and 10 mL of fragrance grade ethanol. The pad was loaded by spreading the solution through a pipette onto a stainless steel pad and removing the ethanol by vacuum drying at room temperature. The best method is to divide the solution into about three portions with a drying step between each portion. There will be some spillage when trying as one full portion because the pad will not be able to fully hold that much solution. After all the ethanol has been removed, the viscous AKG-DiNMDEA seems to stick tightly to the pad so that the pad can be transferred between containers without losing the liquid coating.

[0505] Treatment of Mixed Citrus Oil: A sample of mixed citrus oil was prepared by mixing lime oil, orange oil, grapefruit oil, and bergamot oil so that a variety of terpene hydroperoxides were present in the mixture treated for testing. In two separate 250 mL glass bottles, 150 mL of the mixed citrus oil was placed. This allowed for a significant atmospheric headspace in the closed bottles, which was replenished by fresh atmosphere / oxygen each time the bottle was opened to remove an aliquot for testing. This arrangement was intended to mimic the oxygen exposure caused by typical operations in the production of a barrel of citrus oil stock and should result in realistic levels of autoxidation in the contained oils.

[0506] The AKG-DiNMDEA coated pad was placed in one of the bottles (treated sample) and completely submerged under the mixed citrus oil therein. In the second bottle, nothing was placed except the mixed citrus oil (untreated sample). The bottles were placed on a laboratory bench under ambient temperature and light conditions throughout the testing period. Aliquots were removed from each bottle periodically for POV testing. The downward flow of coating shedding, as evidenced by the appearance of puddles of AKG-DiNMDEA collecting at the bottom of the container, took several weeks to appear to a noticeable extent. It is speculated that as this flow proceeds, the contact area between the phases becomes smaller, which may reduce the efficiency of the reduction reaction. However, as shown in the following tables and Figure 5 and Figure 6 As shown, effective protection of the treated citrus oils from an increase in POV caused by auto-oxidation occurred.

[0507] Recharge of pads: After 26 days, a slight increase in POV was observed for the treated samples (see Figure 5 ). At the same time, the percentage reduction in POV for the treated samples began to decrease slightly relative to the untreated samples (see Figure 6 ). This is interpreted to mean that the coated pad has stopped working effectively, perhaps because the AKG-DiNMDEA has been chemically consumed. Alternatively, it may be that the viscous liquid AKG-DiNMDEA is slowly flowing down from the stainless steel coil of the pad. This will create a puddle with low surface area, so the reagent will become ineffective due to insufficient contact with the citrus oil.

[0508] The pad was removed from the mixed citrus oil and washed sequentially with 100 mL each of acetone, then 95% ethanol, and then acetone again. The clean pad was dried under vacuum at room temperature and then reloaded with AKG-DiNMDEA. This time a simpler process was attempted to replenish / reactivate / reload Instead of applying a solution and evaporating the solvent, simply rub the viscous AKG-DiNMDEA oil into the steel coil. Place approximately 3.2 g of AKG-DiNMDEA on the surface of the steel pad and knead with gloved hands to distribute the oil as evenly as possible. Then, apply the supplied Return to container of treated citrus oil and continue POV monitoring as before. Figure 5 and Figure 6 The vertical purple lines in the graph show the time points corresponding to recharge.

[0509] Raw POV titration data:

[0510]

[0511]

[0512]

[0513] Example 25: Reducing POV in a selected consumer product according to one aspect presented herein.

[0514] This example reports the treatment of exemplary consumer product formulations. As shown in the table below, the consumer product formulations had a measurable degree of oxidation as-is, but with the exception of the general purpose cleaner, the POV content was low. All samples were unperfumed, so the POV was related to the base component that was self-oxidized. Highly oxidized limonene generated in a photoreactor was spiked into five consumer product formulations as a source of mixed limonene hydroperoxide isomers (POV of 1434 mmol / L). The oxidized limonene was spiked into each solution at 10 μL per gram, so that approximately 14.3 mmol / L of POV was added to the existing as-is POV as received.

[0515] In all cases, treatment with the ammonium salt of an α-oxocarboxylate resulted in a rapid and extensive reduction in the POV of the samples; the hydroperoxide present in the samples was consumed / destroyed by a defined, controlled reaction with the α-oxocarboxylic acid, resulting in a harmless and predictable byproduct. In some cases, the untreated samples showed a much slower but steady reduction in POV. This is likely due to the limonene hydroperoxide reacting with the base component and oxidizing it, resulting in the formation of unknown byproducts. In many cases, this could have a detrimental effect on the formulation, such as malodor formation, discoloration, changes in physical properties, etc. This uncontrolled, undirected POV reduction is likely to reduce the skin sensitization of the samples due to the consumption of the sensitizing hydroperoxide, but may not necessarily be beneficial to the formulation in all forms.

[0516]

[0517] Sample Preparation: 40 mL (Sample #3) or 40 g (Sample #1, 2, 4, and 5) were added to 0.4 mL of oxidized limonene and mixed until homogeneous. Half of each spiked consumer product sample was transferred to a second container and treated with 0.5-1% (w / w) 2-oxocarboxylic acid ammonium salt as described in the table below and mixed until homogeneous. Each of the five pairs of two treated and untreated samples was placed on the bench at room temperature under laboratory ambient light and POV measurements were taken periodically. The results are described below.

[0518]

[0519] Sample 1, Hand Dishwashing Liquid Soap (HDLS) – see Figure 7 and Figure 8 :

[0520]

[0521] Sample 2, Shampoo – see Fig. 9 and Fig.10 :

[0522]

[0523] Sample 3, All-Purpose Cleaner (APC) – See Fig.11 and Fig.12 :

[0524]

[0525] Sample 4, Skin Cream – see Fig.13 and Fig.14 :

[0526]

[0527] Sample 5, Antiperspirant Stick (APS) – see Fig.15 and Fig.16 :

[0528]

[0529] Example 26: Reducing POV in selected essential oils obtained from non-citrus sources according to one embodiment presented herein.

[0530] In this example, a series of essential oils from non-citrus sources were treated with AKG-DiTMEEA (a diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) and tri[2-(2-(methoxyethoxy)ethyl]amine (TMEEA, CAS#70384-51-9) in a molar ratio of 1:2) as described below. The results show that the claimed treatment method is broadly effective for a wide range of essential oils, which contain a wide range of terpenes and other small organic molecules such as aromas. Thus, in these other types of oils, a wide range of organic hydroperoxides will be present as autoxidation products, all of which appear to be reduced by 2-oxo acids (particularly in this case, α-ketoglutarate ammonium salt).

[0531] The data below shows nine oils and the POV each oil obtained as received from production stock. For each oil, 20 mL was placed into a 30 mL glass vial and the following procedure was followed daily for 8 days; the vial was opened to refresh the atmospheric headspace, then resealed and shaken to maximize gas / liquid contact, and then stored on the bench at ambient laboratory temperature and light conditions. This procedure was designed to mimic typical handling of the container in a production environment, where the oil would be consumed in many small aliquots rather than the entire container at once.

[0532] On day 4, each oil sample was split in half, so two 10 mL aliquots were placed in separate vials, making "treated" and "untreated" samples. AKG-DiTMEEA was added to the treated samples of each oil according to the dosage table below. Pine oil has an extremely high POV, so the dosage and measurement protocol was somewhat different from the other oils. The daily opening, shaking, and standing procedure continued for another four days until the POV measurement was taken. It can be seen that this 8-day treatment of the untreated oil caused a significant increase in the POV measurement.

[0533] Even as is, the POV of Siberian pine oil was so unusually high that stoichiometric depletion of AKG-DiTMEEA was likely occurring. Therefore, two levels of AKG-DiTMEEA treatment were tried, x2 and x4 of the treatment used on the other oils. The results suggest that even larger amounts may be required to fully remediate this pine oil sample, since AKG-DiTMEEA has a higher molecular weight due to the larger amine groups and a lower stoichiometric capacity per unit weight to scavenge hydroperoxides. A different, lower molecular weight 2-oxoacid salt may be a better choice.

[0534] POV of untreated oil before and after operation:

[0535]

[0536] Metering / Processing of Non-Citrus Essential Oils with AKG-DiTMEEA

[0537]

[0538] AKG-DiTMEEA treatment of non-citrus essential oils (4 days)

[0539]

[0540] Example 27: Preparation and testing of high viscosity 2-oxoacid-containing materials; AKG amine disalt-containing materials prepared using polydentate amines and / or polydentate carboxylic acids.

[0541] In this example, the following amines were used to prepare salts of α-ketoglutaric acid:

[0542]

[0543] Seven substituted ammonium salts of α-ketoglutaric acid (“AKG”) were prepared using the following general procedure: AKG (about 0.01 mole, about 1.461 g) was dissolved in 10 mL of anhydrous acetone to give a clear solution. This solution was added in one portion to a solution of mixed amines in 5 mL of acetone. Each amine mixture provided a total of 0.02 moles of basic N atoms. This completely neutralized the two carboxylic acid moieties present in 0.01 mole of AKG. The resulting opaque white emulsion was vortexed vigorously for 2 to 3 minutes, during which time a second phase coalesced and separated from the milky mixture. The mixture was placed in a freezer overnight, allowing the bottom phase to thicken to a waxy solid. While still cold, the top layer was removed by decantation and discarded. Residual acetone was removed from the bottom product layer via a stream of nitrogen and then treated in a vacuum oven at room temperature for at least 2 hours. In each case, a highly viscous colorless or yellow oil was produced at room temperature. This process was repeated to make 7 different AKG cross-linked disalts, as shown below:

[0544]

[0545] A mixed citrus oil was prepared for testing with AKG salts as follows: Approximately equal parts of cold-pressed orange oil, lemon oil, lime oil, bergamot oil, and grapefruit oil were mixed into a mixed oil. These citrus oils have been used extensively in the laboratory for other purposes and have been autoxidized to varying degrees, but each has a high POV value. The POV value of the mixed oil used at the beginning of the experiment was approximately equal to 18 mmol / L, but treatment during the experiment caused the POV of the untreated oil to increase. The treated oils were subjected to the same treatment (during sampling at each time point, the vials were opened and the headspace was replenished from the ambient atmosphere). The percent reduction in POV was calculated for each time point, which was relative to the POV of the untreated oil at that time, rather than the initial POV value.

[0546] Preparation of samples for testing / treatment: To a series of vials containing approximately 0.2 g of one of the seven AKG ionically cross-linked di-salts (#1 to #7 prepared as described above), 5 mL of mixed citrus oil was added. Each mixture was vortexed for 1 to 2 minutes and then allowed to sit on the bench under laboratory ambient light and temperature conditions. This process was repeated for each salt, with a total of seven samples prepared. POV measurements were taken as a function of time after addition. Untreated citrus oil (also 5 mL) was treated similarly to the treated oil and tested because the POV increased rapidly as the samples were treated. Formulations #1 to #7 were virtually insoluble and all formed a second phase in the mixed citrus oil.

[0547] POV measurements were taken periodically over 3 and 4 days for 7 treated citrus oil samples and 1 untreated citrus oil sample. The results are shown below and Figures 21 to 34 middle:

[0548] #1.AKG-NMDEA (90%) + THED (10%) [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (90%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140 07 8) in a molar ratio of 1:1.8:0.1] was used to reduce the POV of mixed citrus oils. POV measurements were performed over four days. The results are shown in the table below and Fig.21 and Fig. 22 middle.

[0549]

[0550]

[0551] #2. AKG-NMDEA (80%) + THED (20%) [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140 07-8) in a molar ratio of 1:1.6:0.2] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over four days. The results are shown in the table below and Fig.23 and Fig.24 middle.

[0552]

[0553]

[0554] #3. AKG-NMDEA (80%) + THED (10%) + BDMPP (10%) [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (80%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (10%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (10%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.6:0.1:0.067] was used to reduce the POV of the mixed citrus oils. The POV measurements were performed over four days. The results are shown in the table below and Fig.25 and Fig.26 middle.

[0555]

[0556]

[0557] #4. AKG-NMDEA (60%) + THED (20%) + BDMPP (20%) [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) with N-methyldiethanolamine (60%, NMDEA, CAS#105-59-9), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:1.2:0.2:0.134] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over three days. The results are shown in the table below and Fig. 27 and Fig.28 middle.

[0558]

[0559]

[0560] #5. AKG-THED [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (20%, THED, CAS#140 07-8) in a 1:1 molar ratio] was used to reduce the POV of the mixed citrus oil. POV measurements were performed over three days. The results are shown in the table below and Fig.29 and Fig.30 middle.

[0561]

[0562]

[0563] #6. AKG-THED (80%) + BDMPP (20%) [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 1:0.8:0.13] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over four days. The results are shown in the table below and Fig.31 and Fig.32 middle.

[0564]

[0565]

[0566] #7. AKG-BDMPP [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328 50-7) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151 63-7) in a molar ratio of 1:0.67] was used to reduce the POV of mixed citrus oils. POV measurements were performed over four days. The results are shown in the table below and Fig.33 and Fig.34 middle.

[0567]

[0568]

[0569] Example 28: AKG-Ammonium Citrate Treatment of Mixed Citrus Model Flavor.

[0570] Citric acid is a tridentate carboxylic acid capable of forming three ionic bonds with amine compounds. Without intending to be bound by any particular theory, citric acid allows branching to occur in the ionic bonding network formed in these formulations, which is expected to increase viscosity. The formulations were tested in mixed citrus oil raw materials and in hydroalcoholic model fragrances made from mixed citrus oils. The prepared AKG salts were insoluble in pure citrus oil raw materials, but still worked as shown below. They were completely soluble in the hydroalcoholic model fragrances and worked faster after dissolution.

[0571] Preparation of citrus model flavor: 180 mL of ethanol (seasoning grade), 20 mL of distilled water and 40 mL of mixed citrus oils were mixed and vortexed. The amount of oil produced was 40 mL of oil / 240 mL of total = 16.67% v / v, resulting in a slightly turbid yellow solution.

[0572] The list of amines and acids used to prepare the AKG salt formulations is as follows:

[0573]

[0574]

[0575] Four AKG ion-crosslinked substituted ammonium salts containing citric acid were prepared using the following general procedure: AKG (about 0.009 mole, about 1.314 g) and citric acid (0.001 mole X 2 / 3 = 0.000667 mole, 0.128 g) were dissolved in 10 mL of anhydrous acetone by vigorous vortexing. The solution was added in one portion to a solution of mixed amines in 5 mL of acetone. Each amine mixture provided a total of 0.02 moles of basic N atoms. This completely neutralized the carboxylic acid moieties present in 0.009 moles of AKG and 0.000667 moles of citric acid (CA). The resulting opaque white emulsion was vortexed vigorously for 2 to 3 minutes, during which time the second phase coalesced and separated from the milky mixture. The mixture was placed in a freezer overnight to thicken the bottom phase into a waxy solid. While still very cold, the top layer was removed by decantation and discarded. Residual acetone was removed from the bottom product layer via a nitrogen stream and then treated in a vacuum oven at room temperature for at least 4 hours. In each case, a highly viscous colorless or yellow oil was produced at room temperature. This process was repeated to prepare four different AKG / CA cross-linked disalts, as shown in the table below:

[0576]

[0577]

[0578] Preparation of Samples for Testing / Treatment: Model citrus flavor (15 mL of each in four separate 16 mL vials) was treated with one of the four AKG-CA salts (~0.2 g each, see table below). All AKG-CA salts were dissolved in the model citrus flavor to give yellow solutions with minimal turbidity and no color change, indistinguishable from the untreated sample. These treated and untreated solutions were placed on the bench under ambient laboratory light at room temperature and POV measurements were taken periodically. For all treated samples, no color change occurred over the entire study period. The results are shown in the table below and Figures 35 to 42 middle.

[0579]

[0580] A. AKG-CA + NMDEA [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a molar ratio of 9:0.67:20] was used to reduce the POV of a mixed citrus model flavor. POV measurements were performed over five days. The results are shown in the table below and Fig.35 and Fig.36 middle.

[0581]

[0582]

[0583] B. AKG-CA-THED [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9:0.67:10] was used to reduce the POV of a mixed citrus model flavor. POV measurements were performed over five days. The results are shown in the table below and Fig.37 and Fig.38 middle.

[0584]

[0585]

[0586] C: AKG-CA-THED (80%) + BDMPP (20%): [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3] was used to reduce the POV of a mixed citrus model flavor. The POV measurements were performed over five days. The results are shown in the table below and Fig.39 and Fig.40 middle.

[0587]

[0588]

[0589] D. AKG-CA + BDMPP [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with 1-[bis[3-[dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7] was used to reduce the POV of a mixed citrus model flavor. POV measurements were performed over four days. The results are shown in the table below and Fig.41 and Fig.42 middle.

[0590]

[0591]

[0592] Example 29: AKG-ammonium citrate treatment of mixed citrus oils.

[0593] The compounds used were prepared as described above in Examples 27 and 28. A notable difference between the two experiments is that AKG-citrate salts were fully soluble in the hydroalcoholic model fragrance, but they were not soluble in the mixed citrus oil itself.

[0594] Treatment of mixed citrus oil: 5 mL of mixed citrus oil was added to each of two vials containing approximately 0.2 g of AKG di-salt (C: AKG (90%)-CA (10%)-THED (80%) + BDMPP (20%) or D: AKG (90%)-CA (10%) + BDMPP). The vials were vortexed for 2 minutes and allowed to sit on the bench under laboratory ambient light and temperature conditions. POV measurements were taken periodically as a function of time after addition. The results are shown in the following table and Figure 43 to Figure 46 middle.

[0595] C: AKG (90%)-CA (10%) + THED (80%)-BDMPP (20%): [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (80%, THED, CAS#140-07-8) and 1-bis[3-(dimethylamino)propyl]amino]-2-propanol (20%, BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:8:1.3] was used to reduce the POV of mixed citrus oils. POV measurements were performed over 12 days. The results are shown in the table below and Fig.43 and Fig.44 middle.

[0596]

[0597]

[0598] D. AKG (90%)-CA (10%) + BDMPP [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and citric acid (10%, CA, CAS#77-92-9) with 1[bis[3-[dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9:0.67:6.7] was used to reduce the POV of mixed citrus oils. POV measurements were performed over 12 days. The results are shown in the table below and Fig.45 and Fig.46 middle.

[0599]

[0600]

[0601] Example 30: 2-oxoacid salt containing materials prepared using polydentate / polyacid and / or polydentate / polyamine / base.

[0602] Without intending to be bound by any particular theory, the concept of forming an ionically linked network that will increase the viscosity of the material containing the 2-oxo acid salt, or produce a gel-type rheological behavior in the 2-oxo acid salt phase, can be extended beyond bidentate or tridentate acids or bases. For example, if a polyacid (e.g., polyacrylic acid) or a polyamine (e.g., chitosan) is used as a component, the ionic network formed may be complex and extensive. Such an extensive network may produce a large number of physical properties in an extremely viscous or gel-like material (or even a solid / particle in some cases). As shown below, the materials so prepared do show these physical properties, but still show their ability to react with the hydroperoxide terpenes contained in a unique separated phase consisting of mixed citrus oils.

[0603] AKG amine salt prepared with polyacrylic acid component:

[0604]

[0605] Preparation of AKG PAA-linked salts:

[0606]

[0607]

[0608] Procedure for preparing salts: Four vials were charged with AKG (0.0099 or 0.0095 moles, 1.446 or 1.388 g) and polyacrylic acid (0.0002 or 0.001 moles, 0.0144 or 0.072 g) according to the table above, and anhydrous acetone was added to each solution (10 mL for #1 and #3, 14 to 15 mL for #2 and #4; additional acetone was required to dissolve the PAA). The vials were vortexed for 30 seconds each. A very small amount of white solid (which appeared to be an impurity from AKG) did not completely dissolve and precipitated at the bottom of the vial, so the top clear solution was added as a portion to the amine in 5 mL acetone (0.02 moles of total N groups, THED: 2.363 g or BDMPP: 1.636 g, see table above). The opaque white emulsion was vortexed vigorously for 2 minutes, during which time the second phase coalesced. The mixture was placed in the freezer over the weekend, allowing the bottom phase to thicken to a waxy solid. While still cold, the top layer was removed by decantation and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen and then treated in a vacuum oven at room temperature for 7 days.

[0609] #1P and #4P were used in POV reduction testing in mixed citrus oils as shown below.

[0610] Treatment of mixed citrus oil: To a vial containing approximately 0.2 g of the AKG-PAA salt formulation (described above) was added 5 mL of the mixed citrus oil. The mixture was vortexed for 2 minutes and then allowed to sit on the bench under laboratory ambient light and temperature conditions. POV measurements were taken periodically as a function of time after addition. None of the AKG-PAA salt formulations were soluble in the oil. The results are shown in the table below and Figures 47 to 50 middle.

[0611] #1P: AKG (99%)-PAA1 (%) + THED: [a cross-linked diammonium salt made of α-ketoglutaric acid (99%, AKG, CAS#328-50-7) and polyacrylic acid (1%, PAA, CAS#: 9003-01-4) and N,N,N',N'-tetrakis (2-hydroxyethyl) ethylenediamine (THED, CAS#140-07-8) in a molar ratio of 9.9:0.2:10] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over 12 days. The results are shown in the table below and Fig.47 and Fig.48 middle.

[0612]

[0613]

[0614] #4P: AKG (95%)-PAA (5%) + BDMPP [a cross-linked diammonium salt made of α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#:9003-01-4) and 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151-63-7) in a molar ratio of 9.5:1:6.7] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over 12 days. The results are shown in the table below and Fig.49 and Fig.50 middle.

[0615]

[0616]

[0617] Example 31: AKG amine salt prepared with polyacrylic acid and polyamine components.

[0618]

[0619] General procedure for preparing AKG-PAA-PEI ammonium salt: Four vials were charged with AKG (0.0095 or 0.01 mole, 1.388 g or 1.484 g) and poly(acrylic acid) (0.001 mole, 0.072 g) according to the table above (the actual mass used is shown in the table), and 14 mL of anhydrous acetone was added to each of them. The vials were vortexed for 30 seconds. A very small amount of white solid (which appeared to be an impurity from AKG) did not completely dissolve and precipitated at the bottom of the vial, so the top transparent solution was added as part to the amine mixture dissolved in 10 mL of acetone (0.02 mole of total N groups, see the table below). The opaque white emulsion was vortexed vigorously for 2 minutes, during which time the second phase coalesced. The mixture was placed in a freezer over the weekend to thicken the bottom phase into a waxy solid. While still very cold, the top layer was removed by decantation and discarded. The residual acetone was removed from the bottom product layer via a nitrogen stream and then treated in a vacuum oven at room temperature for 7 days.

[0620]

[0621] Treatment of mixed citrus oil: To a vial containing approximately 0.2 g of the AKG-PAA-PEI salt formulation (described above) was added 5 mL of mixed citrus oil. The mixture was vortexed for 2 minutes and then allowed to sit on the bench under laboratory ambient light and temperature conditions. POV measurements were taken periodically. The results are shown in the table below and Figure 51 to Figure 58 middle.

[0622] APP1: AKG (95%)-PAA (5%) + THED (95%)-PEI (5%): [a cross-linked diammonium salt made from α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (95%, THED, CAS#140 07-8) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:9.5:1] was used to reduce the POV of mixed citrus oils. POV measurements were performed over 12 days.

[0623] The results are shown in the table below and Fig.51 and Fig.52 middle.

[0624]

[0625]

[0626] APP2: AKG (95%)-PAA (5%) + BDMPP (95%)-PEI (5%): [a cross-linked diammonium salt made from α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#9003-01-4) with 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (BDMPP, CAS#67151 63-7) and polyethyleneimine (5%, PEI, CAS#:9002-98-6) in a molar ratio of 9.5:1:6.3:1] was used to reduce the POV of the mixed citrus oils. The POV measurements were performed over 12 days. The results are shown in the table below and Fig.53 and Fig.54 middle.

[0627]

[0628]

[0629] APP3: AKG (95%)-PAA (5%) + PEI: [a cross-linked diammonium salt made of α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyacrylic acid (5%, PAA, CAS#: 9003-01-4) with polyethyleneimine (PEI, CAS#: 9002-98-6) in a molar ratio of 9.5:1:20] was used to reduce the POV of the mixed citrus oils. The POV measurements were performed over 12 days. The results are shown in the table below and Fig.55 and Fig.56 middle.

[0630]

[0631]

[0632] APP4: AKG+PEI: [a cross-linked diammonium salt of α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and polyethyleneimine (PEI, CAS#:9002-98-6) in a molar ratio of 1:2] was used to reduce the POV of mixed citrus oils. POV measurements were performed over 12 days. The results are shown in the table below and Fig.57 and Fig.58 middle.

[0633]

[0634]

[0635] Example 32: Materials comprising polydentate acids and amines with increasing hydrophobicity to produce a more hydrophobic 2-oxoacid salt phase.

[0636] Due to the highly ionic nature of the 2-oxoacid ammonium salt phases made from α-ketoglutaric acid and amines (e.g., NMDEA, THED, and BDMPP), terpene hydroperoxides likely do not partition into these phases to any great extent. This would be expected to slow the rate of reduction of the hydroperoxides to the corresponding alcohols and cause POV repair to occur more slowly.

[0637] If the 2-oxoacid phase can be made more hydrophobic, the partitioning of terpene hydroperoxides can be increased, and higher concentrations can lead to faster reduction. However, if the character of the 2-oxoacid phase becomes too hydrophobic, it will dissolve in the material being treated (e.g., citrus oil) and will no longer remain as a second phase. Fine-tuning the hydrophobic properties of the 2-oxoacid phase may allow for more effective POV repair while still maintaining the repair material as a separate, distinct second phase.

[0638] For this reason, a portion of the active 2-oxo acid can be replaced with a bidentate, tridentate or multidentate acid that is more hydrophobic than the 2-oxo acid. For this reason, we used sebacic acid. It contains two carboxylic acid moieties linked together by a straight eight-carbon chain. This unfunctionalized eight-carbon moiety makes sebacic acid more hydrophobic than AKG, and by changing the percentage of sebacic acid in the mixture, the overall hydrophobicity of the 2-oxo acid salt phase should be adjustable.

[0639] In addition, we used the bidentate amine THPED, which is more hydrophobic than THED; compared with THED, THPED (also known as Neutrol ) has four additional methyl groups. These four methyl groups also impart greater hydrophobicity to the amine component.

[0640]

[0641]

[0642] Procedure for preparing salts: Anhydrous acetone (approximately 13 mL for AST-1 and 2 and approximately 25 mL for AST-3, as SA is less soluble in acetone than AKG) was added to each vial containing AKG and sebacic acid ("SA"). The mixture was vortexed. A very small amount of white solid (which appeared to be an impurity in AKG) did not completely dissolve and precipitated at the bottom of the vial. The top clear solution was added as a portion to the amine solution (0.01 mole in 5 mL acetone). The opaque white emulsion was vortexed vigorously for approximately 1 minute, during which time the second phase coalesced. The mixture was placed in a freezer overnight to thicken the bottom phase into a waxy solid. While still very cold, the top layer was removed by decantation and discarded. Residual acetone was removed from the bottom product layer via a stream of nitrogen and then treated in a vacuum oven at room temperature for approximately 10 days.

[0643] Treatment of mixed citrus oil: To a vial containing approximately 0.2 g of AKG disalt (AST 1 to AST 3 listed above) was added 5 mL of mixed citrus oil. The mixture was vortexed for 1 minute and placed on the bench under ambient light and temperature in the laboratory. POV measurements were taken as a function of time after addition. The salt did not dissolve in the oil, but settled as a mobile liquid at the bottom of the vial. The results are shown in the table below and Figure 59 to Figure 64 middle.

[0644] AST-1: AKG (95%)-SA (5%) + THPED: [a cross-linked diammonium salt made from α-ketoglutaric acid (95%, AKG, CAS#328-50-7) and sebacic acid (5%, SA, CAS#: 111-20-6) and N,N,N',N'-tetrakis (2-hydroxy-propyl) ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9.5:0.5:10] was used to reduce the POV of mixed citrus oils. POV measurements were performed over six days.

[0645] The results are shown in the table below and Fig.59 and Fig.60 middle.

[0646]

[0647]

[0648] AST-2: AKG (90%)-SA (10%) + THPED: [a cross-linked diammonium salt made from α-ketoglutaric acid (90%, AKG, CAS#328-50-7) and sebacic acid (10%, SA, CAS#:111-20-6) with N,N,N',N'-tetrakis (2-hydroxy-propyl) ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 9:1:10] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over six days. The results are shown in the table below and Fig.61 and Fig.62 middle.

[0649]

[0650]

[0651] AST-3: AKG (80%)-SA (20%) + THPED: [a cross-linked diammonium salt made from α-ketoglutaric acid (80%, AKG, CAS#328-50-7) and sebacic acid (20%, SA, CAS#:111-20-6) with N,N,N',N'-tetrakis (2-hydroxy-propyl) ethylenediamine (THPED, CAS#102-60-3) in a molar ratio of 8:2:10] was used to reduce the POV of the mixed citrus oil. The POV measurements were performed over six days. The results are shown in the table below and Fig.63 and Fig.64 middle.

[0652]

[0653]

[0654] Comparing the results of #5AKG-THED or #6AKG-THED (80%) + BDMPP (20%) above with each of the three materials containing sebacic acid / THPED shows that the more hydrophobic, the more active salt phase does provide faster hydroperoxide reduction / POV repair. This was especially true at the earliest time points in the experiment, with the average difference being most pronounced at the shortest time point of approximately 0.1 days. As expected, the difference caused by sebacic acid was less pronounced compared to #7AKG-BDMPP (BDMPP is more hydrophobic than THED, so the benefit of sebacic acid / THPED should be less). This data suggests that including a hydrophobic component in the active salt phase can result in faster, and in some cases more complete, reduction of hydroperoxides. The hydrophobic component does not have to be a polydentate compound with all acid groups or all amine / base groups. It can have a mixture of acid and basic moieties, such as an amino acid or a derivative thereof, such as N,N-dimethylphenylalanine or a hydrophobic protein.

[0655] Example 33: Rheological measurements.

[0656] Rheological simple shear flow measurements were performed on several of the reported 2-oxoacid samples using an Anton Paar modular compact rheometer MCR 302 using a parallel plate geometry (25 mm). All samples were analyzed at 25 °C ± 0.2 °C. Viscosity η curves were generated using a shear rate (γ·) sweep ranging from 0.001 to 10 1 / s. The results are shown in Figure 65 to Figure 67 .

[0657] We measured the moisture content before and after a series of rheological measurements using the Karl Fischer titration method. The 2-oxoacid was loaded onto the rheological table, the parallel plates were lowered to a measurement distance of 1 mm, the samples were trimmed to remove any excess sample that was not in contact with the table and plates, and the experiment was started. Multiple analyses were performed on each sample. The sample was measured 5 times in a row without lifting the parallel plates. After these 5 measurements, the parallel plates were lifted and the samples were exposed to the laboratory ambient air, humidity and temperature for 15 minute intervals until 90 minutes. After each 15 minute interval, the samples were reanalyzed using the same rheological method. During the 90 minute exposure time, the viscosity of all samples decreased as the sample absorbed more water. After 90 minutes, the samples were collected into plastic cuvettes, capped and sealed with parafilm (to prevent further moisture absorption) for future Karl Fischer titration analysis. The Karl Fischer titration table in the table below records the moisture content before and after the rheological measurements. Obviously, these materials are extremely hygroscopic and dry samples must be used to obtain meaningful comparative viscosity measurements.

[0658] The results are shown in the following table.

[0659]

[0660] Clearly, all of these samples exhibit Newtonian behavior in the range of shear rates studied. The small changes in viscosity are minor, which may be due to the low number of crystals in the samples. Clearly, the different formulations aimed at increasing viscosity were successful, showing a significant increase in viscosity (e.g., 2 orders of magnitude) at all shear rates studied.

[0661] Example 34: Preparation and testing of a hydrogel phase containing dissolved 2-oxoacid salts.

[0662] In this form, there is no need to use bidentate 2-oxo acids such as α-ketoglutaric acid, since no gel or molecular association will be formed by the 2-oxo acid component incorporated into the ionic network. Monodentate 2-oxo acids (those containing only one acidic part in the molecule) such as pyruvic acid or 2-oxopentanoic acid may also work, since they only need to be soluble in the aqueous gel formed by water and any gelling agent / thickener used. Even water-insoluble 2-oxo acids should be possible, but emulsions of active droplets will be formed that are encapsulated in a hard hydrogel.

[0663] In this case, the gel is formed from materials that are inactive for POV repair, but serve the sole purpose of producing a semi-solid aqueous phase in which the 2-oxoacid component can be dissolved, emulsified or suspended. Any material that forms a gel in an aqueous phase is a possible use. Gelatin, various gums such as xanthan gum, alginates, agar, synthetic polymers such as polyacrylic acid etc. are all ingredients that form the gel.

[0664] Two examples are shown below; one based on gelatin and the other based on xanthan gum.

[0665] Porcine skin gelatin with AKG-NMDEA salt [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9): Approximately 500 mg of Type A gelatin from porcine skin, gel strength 300 (product #G2500 from Sigma-Aldrich Chemical Co.) was added to 20 mL of distilled water and the mixture was heated until a clear solution was produced. When the gelatin solution cooled to 48°C, 2 mL was placed in a 15 mL vial and 105 mg of AKG-NMDEA salt was dissolved therein. The solution was placed in a freezer to place the gel at the bottom of the vial. Next, 10 mL of mixed citrus oil was added to the sample vial to form a second phase mobile liquid above the solidified gelatin water layer. A blank sample vial was also prepared with 10 mL of mixed citrus oil. Both the treated and blank vials were stored on the laboratory bench for 7 days while the POV measurements were performed. The results are as follows, showing a 39.6% POV reduction:

[0666] Blank – 31.67 mmol / L

[0667] Treated – 19.13 mmol / L

[0668] Xanthan Gum with AKG-NMDEA Salt [diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9): Approximately 700 mg of xanthan gum was added to 20 mL of distilled water and the mixture was stirred with a spatula until a uniform thick gel was produced. 2 mL of gel was placed in a 15 mL vial and 110 mg of AKG-NMDEA salt was stirred into it until dissolved. Next, 10 mL of mixed citrus oil was added to the sample vial, forming a second phase mobile liquid above the thick aqueous gel layer. A blank sample vial was also made with 10 mL of mixed citrus oil. When performing POV measurements, both the treated and blank vials were stored on the laboratory bench for 7 days. The results are as follows, showing a POV reduction of 45.8%:

[0669] Blank – 31.67 mmol / L

[0670] Treated – 17.17 mmol / L

[0671] Example 35: Stabilization of model fragrance using diammonium salt made from α-ketoglutaric acid (AKG, CAS#328-50-7) and N-methyldiethanolamine (90%, NMDEA, CAS#105-59-9) according to one embodiment proposed herein

[0672] In this example, the ability of alpha-ketoglutarate to replace the traditional antioxidant butylated hydroxytoluene (BHT) as a stabilizer for fine gragrance was investigated.

[0673] BHT was used as a control and compared with alpha-ketoglutarate. BHT and alpha-ketoglutarate were added to the fragrance oil at three different concentrations (0.05, 0.10 and 0.25%) and mixed with a magnetic stirrer during 30 minutes.

[0674] Next, eau de toilette ("EDT") formulations containing the test and control formulations were prepared as follows: 10% (wt) fragrance oil concentrate, 10% (wt) deionized water, 80% (wt) BHT or α-ketoglutarate in the EDT at final concentrations of 0.005%, 0.010%, and 0.025%.

[0675] The resulting EDT formulation was stored at 45°C for 2 months. After storage, a sample of the EDT formulation was taken and analyzed by gas chromatography to determine the concentration of acetaldehyde diethyl acetal. The amount of acetaldehyde diethyl acetal is directly related to the general oxidation reaction of EDT, since it is formed by oxidation of ethanol according to the reaction described below:

[0676] Then

[0677] The results are shown in the table below.

[0678]

[0679] The EDT formulation lacking BHT or α-ketoglutarate contained 150 ppm of acetaldehyde diethyl acetal and its odor was observed to have been oxidatively modified during stability testing. The odor was typical of oxidized fragrances.

[0680] The EDT formulation containing BHT (0.005% to 0.025% in EDT) was less oxidized, with acetaldehyde diethyl acetal at 85 ppm and 0.025% BHT in EDT.

[0681] The EDT formulation containing alpha-ketoglutarate was further stabilized because the concentration of acetaldehyde diethyl acetal was 10 ppm, 0.025% in EDT, and acetaldehyde diethyl acetal was 33 ppm, 0.010% in EDT.

[0682] Example 36: Measurement of rancid aldehydes in triglycerides after treatment with at least one α-oxocarboxylic acid

[0683] Blank Sample : In all the following experiments, the untreated oil (blank) sample was kept. The packaging, storage, handling and sampling of the blank sample were always exactly the same as the treated sample, except that the 2-oxo acid salt was added. In this way, the effect of atmospheric oxygen on the headspace volume will be similar. For example, the ratio of headspace volume to oil volume and the contact area between the headspace and the oil surface will be the same for the treated and untreated samples.

[0684] Sensory evaluation : Phenylpyruvic acid and pyruvic acid and their salts each have an aroma that is somewhat acidic in itself. In contrast, alpha-ketoglutaric acid or its salts do not have this aroma. The flavorists who performed the sensory evaluation here noticed that this acidic aroma was somewhat confused with the assessment of rancidity in the oil, especially when the rancidity was not very severe. As a result of this, the effect of rancidity in oils containing phenylpyruvic acid or pyruvic acid salts may be overestimated, especially in the early stages of research before flavorists have gained the ability to distinguish oxo-acid aromas from rancidity through experience. This overestimation did not occur with the odorless alpha-ketoglutaric acid salt. This overestimation phenomenon may play a role in some examples, where the sensory ratings of these examples did not correlate well with the HPLC aldehyde data. For the examples with alpha-ketoglutaric acid, the sensory-HPLC data correlation was much stronger.

[0685] Low oleic sunflower oil: Low oleic sunflower oil was treated with PhPA-DiMeC10A [ammonium salt made from phenylpyruvic acid and N,N-dimethyldecylamine in a 1:1 molar ratio]:

[0686]

[0687] 15 mL of low oleic sunflower oil was placed in a 30 mL glass vial, which was newly purchased from a local supermarket, opened 44 days ago and kept at room temperature. 0.3001 g of PhPA-DiMeC10A was added to the vial. Most of the salt dissolved, but some undissolved solids were retained. The mixture was placed on a workbench under laboratory ambient light at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see method below), and sensory evaluation were recorded regularly. The results are as follows:

[0688] POV Data:

[0689]

[0690] The data show that treatment was very rapid and effective, but somewhere between the 35-day time point and the 76-day time point, the PhPA-DiMeC10A appeared to be consumed. When consumed, both the treated and untreated samples began to auto-oxidize. Still, the improvement was dramatic.

[0691] HPLC data:

[0692] Sample preparation (dinitrophenylhydrazine [DNPH] derivatization): The synthesis of DNPH derivatives of aldehyde / ketone products in oxidized oils and treated oxidized oils is as follows:

[0693] Approximately 0.500 g of triglycerides were diluted to 12 mL by adding propan-2-ol (IPA). 1 mL of the diluted oil mixture was added to 1 mL of a diluted DNPH solution, which was prepared separately by mixing DNPH (3 g / L in IPA) and 3% HCL and diluted to 12 mL with propan-2-ol (IPA). The reaction vial was stirred and kept at 40°C for 1 hour to accelerate the derivatization reaction. The reaction mixture was then cooled to room temperature, neutralized with 20% trimethylamine in IPA, and centrifuged at 5000 rpm for 5 minutes. The supernatant was then injected for HPLC analysis as follows:

[0694] HPLC analysis method: An Agilent 1100 series HPLC system equipped with a diode array detector was used.

[0695] Chromatographic column: Phenomenex Luna C18(2) column (250x 4.6mm, 5um).

[0696] Column temperature: 30℃.

[0697] Flow rate: 0.8 mL / min

[0698] Injection volume: 5 μL

[0699] Detection: UV absorption at 250, 300, 366 and 385 nm

[0700] Mobile phase gradient:

[0701] step Time (minutes) % Acetonitrile %water 1 0 70 30 2 10 80 20 3 20 100 0 4 40 100 0

[0702] HPLC Results - Untreated (Blank)

[0703]

[0704] HPLC results - treatment with PhPA-DiMeC10A

[0705]

[0706] Sensory Data: A Guide to Sensory Evaluation

[0707] describe grade Extremely fresh, with no detectable rancidity 1 Fresh, very slightly rancid 2 Useable / average; slightly but noticeably rancid 3 bad; rancid and unpleasant 4 Totally unpalatable; extremely unpleasantly rancid. 5

[0708] Sensory evaluation results:

[0709]

[0710]

[0711] Treatment of low oleic sunflower oil with PA-NMDEA [ammonium salt made from pyruvic acid and N-methyldiethanolamine in a 1:1 molar ratio]:

[0712]

[0713] 10 mL of low oleic sunflower oil was placed in a 30 mL glass vial, which was newly purchased from a local supermarket, opened 50 days ago and kept at room temperature. 0.2002 g of PA NMDEA was added to the vial. Most of the salt was dissolved. The mixture was placed on a workbench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above method), and sensory evaluation were recorded regularly. The results are shown below:

[0714] POV Data:

[0715]

[0716] HPLC data: Sample preparation (DNPH derivatization): As described above.

[0717] HPLC Results - Untreated (Blank):

[0718]

[0719] HPLC results - treatment with PA-NMDEA

[0720]

[0721] Sensory Data: Sensory Evaluation Guidelines: As above

[0722]

[0723] Treatment of low oleic sunflower oil with AKG-DiMeC12A [ammonium salt made from α-ketoglutaric acid and N,N-dimethyldodecylamine in a 1:2 molar ratio]

[0724]

[0725] In a 30 mL glass vial was placed 10 mL of low oleic sunflower oil, newly purchased from a local supermarket, opened 50 days ago and kept at room temperature. To this vial was added 0.2400 g of AKG-DiMeC12A. The salt was not completely dissolved, but a turbid, gelatinous suspension was produced. The mixture was placed on a workbench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above method), and sensory evaluation were recorded regularly. The results are shown below:

[0726] POV Data:

[0727]

[0728] The data show that treatment was rapid and effective, but sometime between the 29-day time point and the 76-day time point, the AKG-DiMeC12A appeared to be consumed. When consumed, both the treated and untreated samples began to auto-oxidize. Nonetheless, the improvement was substantial.

[0729] HPLC data: Sample preparation (DNPH derivatization): As described above.

[0730] HPLC Results - Untreated (Blank):

[0731]

[0732] HPLC results - treated with AKG-DiMeC12A:

[0733]

[0734] Sensory Data: Sensory Evaluation Guidelines: As above

[0735]

[0736] High Oleic Sunflower Oil:

[0737] Treatment of high oleic sunflower oil with PhPA-DiMeC10A [ammonium salt made from phenylpyruvic acid and N,N-dimethyldecylamine in a 1:1 molar ratio]:

[0738]

[0739] In a 30 mL glass vial was placed 15 mL of high oleic sunflower oil that had been stored in a plastic bottle at room temperature but had never been opened. To this vial was added 0.301 g of PhPA-DiMeC10A. Most of the salt dissolved, but some undissolved solids remained. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0740] POV Data:

[0741]

[0742] HPLC data:

[0743] Sample preparation (DNPH derivatization): As described above.

[0744] HPLC Results - Untreated (Blank):

[0745]

[0746] HPLC results - treated with PhPA-DiMeC10A:

[0747]

[0748] Sensory Data: Sensory Evaluation Guidelines: As above

[0749]

[0750] Treatment of high oleic sunflower oil with PA-NMDEA [ammonium salt made from pyruvic acid and N-methyldiethanolamine in a 1:1 molar ratio]:

[0751]

[0752] 15 mL of high oleic sunflower oil was placed in a 30 mL glass vial, which had been stored in a plastic bottle at room temperature but had never been opened. 0.3002 g of PA-NMDEA was added to the vial. Most of the salt dissolved. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0753] POV Data:

[0754]

[0755] HPLC data:

[0756] Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0757]

[0758] HPLC Results - Treatment with PA-NMDEA:

[0759]

[0760] Sensory Data: Sensory Evaluation Guidelines: As above

[0761]

[0762] Treatment of high oleic sunflower oil with AKG-DiMeC12A [ammonium salt made from α-ketoglutaric acid and N,N-dimethyldodecylamine in a 1:2 molar ratio]

[0763]

[0764] In a 30 mL glass vial was placed 15 mL of high oleic sunflower oil that had been stored in a plastic bottle at room temperature but had never been opened. To this bottle was added 0.302 g of AKG-DiMeC12A. The salt did not completely dissolve, but a cloudy, gelatinous suspension was produced. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0765] POV Data:

[0766]

[0767] HPLC data:

[0768] Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0769]

[0770] HPLC results - treated with AKG-DiMeC12A:

[0771]

[0772] Sensory Data:

[0773] Sensory Evaluation Guidelines: As above

[0774]

[0775] Soybean Oil:

[0776] Treatment of soybean oil with PhPA-DiMeC10A [ammonium salt made from phenylpyruvic acid and N,N-dimethyldecylamine in a 1:1 molar ratio]:

[0777]

[0778] In a 30 mL glass vial was placed 15 mL of soybean oil that had been stored in a plastic bottle at room temperature but had never been opened. 0.301 g of PhPA-DiMeC10A was added to the vial. Most of the salt dissolved, but some undissolved solids remained. The mixture was placed on a workbench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above method), and sensory evaluation were recorded regularly. The results are shown below:

[0779] POV Data:

[0780]

[0781] HPLC data:

[0782] Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0783]

[0784] HPLC results - treated with PhPA-DiMeC10A:

[0785]

[0786] Sensory Data: Sensory Evaluation Guidelines: As above

[0787]

[0788] Treatment of soybean oil with PA-NMDEA [ammonium salt made from pyruvic acid and N-methyldiethanolamine in a 1:1 molar ratio]:

[0789]

[0790] 15 mL of soybean oil was placed in a 30 mL glass vial, which had been stored in a plastic bottle at room temperature, but had never been opened. 0.3002 g of PA-NMDEA was added to the vial. Most of the salt was dissolved. The mixture was placed on a workbench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above method), and sensory evaluation were recorded regularly. The results are shown below:

[0791] POV Data:

[0792]

[0793] HPLC data: Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0794]

[0795] HPLC Results - Treatment with PA-NMDEA:

[0796]

[0797] Sensory Data: Sensory Evaluation Guidelines: As above

[0798]

[0799] Treatment of soybean oil with AKG-DiMeC12A [ammonium salt made from α-ketoglutaric acid and N,N-dimethyldodecylamine in a 1:2 molar ratio]

[0800]

[0801] In a 30 mL glass vial was placed 15 mL of soybean oil that had been stored in a plastic bottle at room temperature but had never been opened. To this bottle was added 0.302 g of AKG-DiMeC12A. The salt was not completely dissolved, but a turbid, gelatinous suspension was produced. The mixture was placed on a workbench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0802] POV Data:

[0803]

[0804] HPLC data:

[0805] Sample preparation (DNPH derivatization): As described above.

[0806] HPLC Results - Untreated (Blank):

[0807]

[0808] HPLC results - treated with AKG-DiMeC12A:

[0809]

[0810] Sensory Data: Sensory Evaluation Guidelines: As above

[0811]

[0812] Extra virgin olive oil: Treatment of extra virgin olive oil with PhPA-DiMeC10A [ammonium salt made from phenylpyruvic acid and N,N-dimethyldecylamine in a 1:1 molar ratio]:

[0813]

[0814] In a 30 mL glass vial was placed 15 mL of extra virgin olive oil that had been stored in a brown glass bottle at room temperature but had never been opened. To this vial was added 0.301 g of PhPA-DiMeC10A. Most of the salt dissolved, but some undissolved solids remained. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0815] POV Data:

[0816]

[0817] HPLC data:

[0818] Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0819]

[0820] HPLC results - treated with PhPA-DiMeC10A:

[0821]

[0822] Sensory Data: Sensory Evaluation Guidelines: As above

[0823]

[0824] Treatment of extra virgin olive oil with AKG-DiMeC12A [ammonium salt made from α-ketoglutaric acid and N,N-dimethyldodecylamine in a 1:2 molar ratio]

[0825]

[0826] In a 30 mL glass vial was placed 15 mL of extra virgin olive oil that had been stored at room temperature in a brown glass bottle but had never been opened. To this bottle was added 0.302 g of AKG-DiMeC12A. The salt did not completely dissolve, but a cloudy, gelatinous suspension was produced. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC with DNPH derivatization (see Methods above), and the sensory evaluation were recorded regularly. The results are shown below:

[0827] POV Data:

[0828]

[0829] HPLC data:

[0830] Sample preparation (DNPH derivatization): As described above. HPLC results - untreated (blank):

[0831]

[0832] HPLC results - treated with AKG-DiMeC12A:

[0833]

[0834] Sensory Data: Sensory Evaluation Guidelines: As above

[0835]

[0836] Treatment of formulated ranch dressing: Treatment of the dressing with PhPA-DiMeC10A [ammonium salt made from phenylpyruvic acid and N,N-dimethyldecylamine in a 1:1 molar ratio]:

[0837] In a 30 mL glass vial was placed 15 g of commercial salad dressing that had been stored in the laboratory at room temperature for an unknown but long time after opening. To this vial was added 0.4002 g of PhPA-DiMeC10A and mixed thoroughly. The mixture was placed on a bench under ambient light in the laboratory at room temperature. The POV measured by titration, the measurement of rancid odor aldehydes by HPLC derived from DNPH (see above), and sensory evaluation were recorded regularly. The results are shown below:

[0838] POV Data:

[0839]

[0840] HPLC data:

[0841] Sample preparation (DNPH derivatization): As described above.

[0842] HPLC Results - Untreated (Blank):

[0843]

[0844] HPLC results - treated with PhPA-DiMeC10A:

[0845]

[0846] Sensory Data: Sensory Evaluation Guidelines: As above

[0847]

[0848] Example 37: According to one embodiment proposed herein, the diammonium salt formed by the reaction of phenylpyruvic acid and N,N-dimethyldecylamine (referred to herein as DiMeC10A-PhPA) is used to reduce POV and rancidity in soap formulations.

[0849] The degree of rancidity in the tested soap formulations was determined by measuring the content of the aldehyde and ketone reaction products of the proposed soap oils. The synthesis of the DNPH derivatives of the aldehyde / ketone products in the soaps and treated soaps was as follows:

[0850] 0.1000 g of soap formulation treated or untreated with DiMeC10A-PhPA was measured separately and diluted to 12 mL by adding propan-2-ol. 1 mL of this prepared diluted mixture was added to 1 mL of diluted DNPH solution, which was prepared separately by mixing DNPH (3 g / L) and 3% HCl and diluted to 12 mL by adding propan-2-ol. The reaction vial was stirred and kept at 40°C for 1 hour to accelerate the derivatization reaction. It was then cooled to room temperature and neutralized with 20% triethylamine and centrifuged at 5000 rpm for 5 minutes. The sample was then injected into an HPLC column. The results are shown in the following table:

[0851]

[0852] These data indicate that treatment of the soap formulations with DiMeC10A-PhPA reduced the amount of aldehyde and ketone reaction products of the soap oil, thereby remediating or reducing rancidity. The sensory properties of the treated and untreated soap formulations are shown below.

[0853]

[0854] Example 38: Reduction of POV of a model citrus flavor using L-cysteine ​​ethyl ester hydrochloride, N-acetylcysteine ​​methyl ester or glutathione according to one embodiment of the invention

[0855] Without intending to be bound by any particular theory, reduced sulfur compounds such as mercaptans can readily react with hydroperoxides, resulting in their reduction, most likely to the corresponding alcohols. Many low molecular weight mercaptans (such as ethanethiol) are extremely unpleasant to the sense and therefore may not be suitable for use in aromatized products or food products. However, certain mercaptan compounds are not malodorous and can be used in a satisfactory manner. Such compounds include amino acid and / or peptide derived mercaptans, such as cysteine ​​derivatives (e.g., cysteine ​​ethyl ester hydrochloride, N-acetyl cysteine ​​methyl ester and glutathione).

[0856] Treatment of Model Flavors: Model mixed citrus flavors (15 mL in each of three 16 mL vials) were treated with sulfur-containing compounds (approximately 0.15 g each, see list below). The vials were placed on a bench at room temperature under ambient laboratory light and POV measurements were taken periodically. Some brown discoloration was observed for the samples treated with L-cysteine ​​ethyl ester hydrochloride.

[0857] The results are shown in the following table: The POV of the untreated model fragrance was 5.55 mmol / L.

[0858]

[0859] Example 39: Reduction of POV of model citrus flavors or mixed citrus oils using trisodium 2-phospho-L-ascorbic acid (Vc-PTNa) or L-ascorbic acid 2-phosphate sesquimagnesium salt hydrate (Vc-PSeMg) according to one embodiment proposed herein

[0860] Without intending to be bound by any particular theory, ascorbic acid and its esters (e.g., ascorbyl palmitate) are widely used antioxidants in many applications. However, in fine fragrances, home and skin care products, and other cosmetics, it has a tendency to cause discoloration problems. Phosphorylated versions of ascorbic acid are used in skin care products to provide the cosmeceutical benefits of topical vitamin C without causing discoloration problems. Herein, we used phosphorylated ascorbic acid analogs to reduce the POV of mixed citrus oils and model citrus flavors.

[0861] Treatment of Model Flavors: Model citrus flavors (15 mL each in a 16 mL vial, YIWA-1702, pg61) were treated with ascorbate (approximately 0.15 g each, see list below) and measured by POV titration. All ascorbate was dissolved in the model citrus flavor to give a yellow solution with minimal turbidity, identical to the untreated. These treated and untreated solutions were placed on a bench under ambient laboratory light at room temperature and POV measurements were taken periodically. For all treated samples, no color change occurred over the entire study period.

[0862] Treatment of mixed citrus oils: Mixed citrus oils (9 mL each in separate vials) were treated with the above-described phosphorylated ascorbate salts (approximately 0.35 g each). The treated and untreated oils were placed on a bench at room temperature under ambient laboratory light and POV measurements were taken periodically. For all treated samples, no color change was observed throughout the experimental period.

[0863]

[0864] The results are shown in the following table and Figures 68 to 75 middle.

[0865]

[0866] Citrus flavor treated with Vc-PTNa (0.1611 g)

[0867]

[0868] Citrus oil treated with Vc-PSeMg (0.3585 g)

[0869]

[0870] Citrus flavor treated with Vc-PSeMg (0.1544 g)

[0871]

[0872] Example 40: Reduction of POV of a model citrus flavor or mixed citrus oil using dimethylethylsilane (DMESi), pentamethyldisiloxane (PMDSi), methylhydrogensiloxane polymer (PMHS) or methylhydrogensiloxane polymer (PMHS) according to one embodiment of the present invention

[0873] Treatment of Model Flavors: Model citrus flavors (15 mL in each of four 16 mL vials) were treated with the test compounds (approximately 0.3 g each, only PMDSiH was miscible with the flavors; the other three were immiscible). Treated and untreated flavors were placed on a bench under ambient laboratory light at room temperature and POV measurements were taken periodically. For all treated samples, no color change was observed during the test period.

[0874] Treatment of mixed citrus oil: Mixed citrus oil (6 mL in each of four separate 9 mL vials) was treated with the test compounds (approximately 0.2 g each; all miscible with citrus oil). The treated and untreated oils were placed on a bench at room temperature under ambient laboratory light and POV measurements were taken periodically. For all treated samples, no color change was observed during the treatment period.

[0875] Test compound

[0876]

[0877] For mixed citrus oil, use 5mL + about 200mg of Si compound, about 40mg / mL. For model citrus flavor, use 15mL + about 300mg of Si compound, about 20mg / mL. The results are shown in the table below and Figure 76 to Figure 91 middle.

[0878] Citrus oil treated with DMESi (0.2614 g)

[0879]

[0880] Citrus oil treated with PMDSi (0.2511 g)

[0881]

[0882] Citrus oil treated with PMHSi-a (0.2525 g)

[0883]

[0884] Citrus oil treated with PMHSi-b (0.2482 g)

[0885]

[0886] Citrus flavor treated with DMESi (0.3247 g)

[0887]

[0888] Citrus flavor treated with PMDSi (0 0.3302 g)

[0889]

[0890] Citrus flavor treated with PMHSi-a (0.3185 g)

[0891]

[0892] Citrus flavor treated with PMHSi-b (0.3123 g)

[0893]

[0894] Example 41: Reduction of POV of a model citrus flavor using glyoxylic acid or diethyl oxaloacetic acid sodium salt according to one embodiment presented herein

[0895] Treatment of Model Flavors: Model citrus flavors (15 mL in each of four 16 mL vials) were treated with the test compounds. The treated and untreated flavors were placed on a bench under ambient laboratory light at room temperature and POV measurements were taken periodically. For all treated samples, no color change was observed during the test. The results are shown in the table below. The starting POV of the untreated model flavor was 5.55 mmol / L.

[0896]

[0897] Example 42: Reducing the POV of a mixed citrus oil using monobutyl oxalate (2-butoxy-2-oxoacetic acid) or monobenzyl oxalate (2-(benzyloxy)-2-oxoacetic acid) according to one embodiment of the present invention

[0898] Treatment of mixed citrus oil: Mixed citrus oil (6 mL in each of two 8 mL vials) was treated with oxalic acid monoester (approximately 0.12 g). The treated and untreated oils were placed on the bench under ambient laboratory light at room temperature and POV measurements were taken periodically. Both compounds were dissolved in the mixed citrus oil. Since the POV of the untreated oil was high, 0.5 mL of oil was used for each titration instead of the usual 1 mL sample amount. The results are shown in the table below and Figure 92 to Figure 95 middle.

[0899] Oxalic acid monoester:

[0900]

[0901] Citrus oil treated with monobutyl oxalate (0.1243 g):

[0902]

[0903] Citrus oil treated with benzyl oxalate (0.1234 g):

[0904]

[0905] Example 43: Reduction of POV of auto-oxidized limonene oil using N(3),N(3),N(5),N(5),2,6-hexamethyl-1,4-dihydro-3,5-pyridinedicarboxamide (HDPA, C13H21N3O2, MW=251.331) according to one embodiment proposed herein

[0906] Without intending to be bound by any particular theory, 1,4-dihydropyridines are known to act as reducing agents in biological systems (eg, NADH; the reduced form of nicotinamide adenine dinucleotide).This example demonstrates that the heterocyclic system non-enzymatically prevents the increase in the POV of limonene auto-oxidation.

[0907] HDPA: N(3),N(3),N(5),N(5),2,6-hexamethyl-1,4-dihydro-3,5-pyridinedicarboxamide (HDPA, C13H21N3O2, MW=251.331)

[0908]

[0909] Preparation of treated samples: Oxidized limonene (100 μL, starting POV about 38 mmol / L) was treated with 2 mg of HDPA (about 2 eq of HP). The treated and untreated limonene samples were placed on the bench at room temperature under laboratory ambient light and HPLC chemiluminescence measurements were performed periodically. The same amount of untreated limonene was prepared in a second vial and monitored similarly to the treated samples for comparison. The results are shown in the following table and Fig.96 middle.

[0910]

[0911] Example 44: Hydrolyzable esters of 2-oxoacids and / or oxalic acid, which cause a reduction in POV by hydrolysis of the ester moiety, thereby producing a controlled and / or prolonged in situ release of 2-oxoacids, oxalate monoesters or oxalic acid

[0912] This experiment shows the use of hydrolyzable esters of 2-oxo acids and / or oxalic acid, which cause a reduction in POV by hydrolysis of the ester moiety, resulting in a controlled and / or prolonged in situ release of 2-oxo acids, oxalic acid monoesters or oxalic acid itself. 2-oxo acids and oxalic acid are very strong acids that can damage aroma and / or formulation ingredients if added all at once in high concentrations without buffering. Controlled release can prevent such damage.

[0913] 2-oxo acid ester or oxalate serves as the non-acidic source of parent 2-oxo acid, oxalic acid monoester or oxalic acid itself. The ester releases 2-oxo acid, oxalic acid monoester or oxalic acid at a controlled rate by the hydrolysis caused by the water in the treated material. For this reason, some water must be present in the treated material. The released 2-oxo acid, oxalic acid monoester or oxalic acid react with the harmful hydroperoxides present in the treated material usually due to autoxidation, and consume them chemically by oxidative decarboxylation. Hydroperoxides eventually become the corresponding alcohols in the structure relatively harmless.

[0914] The following compounds were tested as described below:

[0915]

[0916] Preparation of citrus model flavor (mixed citrus oils in 90 / 10 v / v EtOH / water):

[0917] 360 mL EtOH (seasoning grade or HPLC grade) + 40 mL DI water + 80 mL mixed citrus oils. Concentration: 80 mL / 480 mL = 16.67% v / v. A yellow solution was obtained with slight turbidity.

[0918] Treatment of citrus flavor (10 mg / mL):

[0919] Model citrus flavors (40 mL aliquots, each in a separate 40 mL vial) were treated with compounds 1-6 (~0.4 g each) by simply mixing and dissolving the treatment compounds. Treated and untreated solutions were placed on a bench under ambient laboratory light at room temperature and POV measurements were taken regularly. Samples were also monitored for color change throughout the study.

[0920] For AKG-diEtO (Compound 7), a separate experiment was performed: Model citrus flavor (22 mL in a 36 mL vial) was treated with AKG-diEtO (-0.23 g) and monitored for POV measurements as described above.

[0921] It shows that α-ketoglutarate di-n-butyl ester ( Fig.97 ), di-tert-butyl α-ketoglutarate ( Fig.99 ), α-ketoglutarate dibenzyl ester ( Fig.100 ), dimethyl oxalate ( Fig.101 ), dibutyl oxalopropionate ( Fig.105 )’s POV plotted against time.

[0922] It shows that α-ketoglutarate di-n-butyl ester ( Fig.98 ), dimethyl oxalate ( Fig.102 ), dibutyl oxalate ( Fig.104 ), diethyl oxalopropionate ( Fig.106 ) and diethyl α-ketoglutarate ( Fig.108 ) is a graph of the percentage reduction in POV versus time.

[0923] Publications cited throughout this article are incorporated herein by reference in their entirety. Although various aspects of the present invention have been described above with reference to examples and preferred embodiments, it should be understood that the scope of the present invention is not limited by the foregoing description, but is defined by the appended claims appropriately interpreted under the principles of patent law.

Claims

1. A method of reducing, preventing or improving POV of a fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material, the method comprising: a. adding at least one repair agent selected from the group consisting of: inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides to the fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material having a first POV level; as well as b. mixing or contacting the at least one restorative agent with the fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a sufficient period of time to reduce the first POV level to a predetermined second lower level.

2. A method of reducing, preventing or ameliorating skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material to a subject in need thereof, the method comprising: a. adding to the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level at least one repair agent selected from the group consisting of: inorganic salts of α-oxocarboxylic acids, thiols, sulfur-containing peptides, sulfur-containing proteins, phosphorylated ascorbic acid analogs, ascorbic acid esters, ascorbic acid salts, oxalic acid monoesters, oxalic acid monoester salts, silane hydrides; as well as b. mixing the at least one restorative agent into the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material for a sufficient period of time to reduce the first POV level to a predetermined second, lower level, wherein the predetermined second, lower level is sufficient to reduce, prevent or ameliorate skin irritation of the subject caused by the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material.

3. The method of claim 1, wherein the fragrance raw material is treated prior to incorporation into the fragrance.

4. The method of claim 1, wherein the fragrance raw material is treated after incorporation into the fragrance.

5. The method of claim 1, wherein the food material is processed before being incorporated into a seasoning product, a nutritional supplement.

6. The method according to claim 1, wherein the food material is treated after being incorporated into a seasoning product, a nutritional supplement.

7. The method of claim 1, wherein the at least one restorative agent is present in a concentration of 0.001 to 10 weight percent after addition to the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

8. The method of claim 1, wherein the thiol is selected from the group consisting of glutathione, N-acetylcysteine ​​methyl ester and cysteine ​​ethyl ester hydrochloride.

9. The method of claim 1, wherein the ascorbyl ester is ascorbyl palmitate.

10. The method of claim 1, wherein the ascorbate is triethanolammonium ascorbate.

11. The method according to claim 1, wherein the salt of the diester of oxaloacetic acid is diethyl oxaloacetate sodium salt.

12. The method according to claim 1, wherein the α-oxocarboxylic acid is selected from the group consisting of pyruvic acid, 2-oxopentanoic acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid, 2-oxoglutaric acid, indole-3-pyruvic acid, 2-thiophene glyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid and mixtures thereof.

13. The method according to claim 1, wherein the predetermined second lower level is 5 to 20 mmol / L.

14. The method according to claim 1, wherein the predetermined second lower level is 0 to 6 mmol / L.

15. The method of claim 1 further comprising removing the alpha-oxocarboxylic acid from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement, or food raw material having a predetermined second lower level.

16. The method of claim 15, wherein the step of removing the alpha-oxocarboxylic acid from the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material comprises liquid-liquid extraction.

17. The method of claim 1 further comprising treating the formulated fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material with a carbonate salt after removing the α-oxocarboxylic acid to reduce the acidity of the formulated fragrance, body care product, fragrance raw material, flavored product, nutritional supplement or food raw material.

18. A method, wherein the method reduces the POV of a fragrance, a body care product, a cosmetic, a home care product, a fragrance raw material, a flavored preparation, a nutritional supplement, or a food raw material, the method comprising: a. adding at least one hydrolyzable ester of oxalic acid to a fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored product, nutritional supplement or food raw material having a first POV level; as well as b. mixing the at least one hydrolyzable ester of oxalic acid into the fragrance, body care product, cosmetic, home care product, fragrance raw material, flavored preparation, nutritional supplement or food raw material for a sufficient time to reduce the first POV level to a predetermined second lower level.

19. A method of reducing, preventing or ameliorating skin irritation caused by a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material to a subject in need thereof, the method comprising: a. adding at least one hydrolyzable ester of oxalic acid to a formulated fragrance, body care product, home care product, cosmetic or fragrance raw material having a first POV level; and b. mixing the at least one hydrolyzable ester of oxalic acid into the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material for a sufficient period of time to reduce the first POV level to a predetermined second lower level, wherein the predetermined second lower level is sufficient to reduce, prevent or ameliorate skin irritation of the subject caused by the formulated fragrance, body care product, home care product, cosmetic or fragrance raw material.

20. The method according to claim 18 or 19, wherein the at least one hydrolyzable ester of oxalic acid is an aryl or alkyl ester.

21. The method of claim 18 or 19, wherein the at least one hydrolyzable ester of oxalic acid is selected from the group consisting of dimethyl oxalate, dibutyl oxalate, diethyl oxalopropionate, diethyl oxalopropionate, and combinations thereof.

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