Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/22—Peroxides; Oxygen; Ozone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/08—Anti-ageing preparations
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent

Definitions

• perfumes, body care products, home care products, perfumery raw materials (such as, for example, essential oils, natural extracts, and synthetic ingredients), and food raw materials (such as, for example, fats and oils derived from animal or plant sources, and derivatives thereof, including monoglycerides, diglycerides, lecithins, phosphatidyl ethanolamines, or other phospholipids, and modified triglycerides) can undergo oxidation, resulting in the formation of chemical species including peroxides, organic hydroperoxides, peroxyhemiacetals.
• the peroxide value defined as the amount of equivalents of oxidizing potential per 1 kilogram of material is an indication of the extent of the oxidation.
• the POV of formulated perfumes, body care products, and perfumery raw materials is, or may be subject to regulatory limits, due to skin sensitization issues, such as, for example, contact dermatitis.
• an unacceptably high POV can result in a perfumery raw material failing quality control testing, and therefore being deemed unusable.
• an unacceptably high POV can result in a food raw material having an unpleasant rancid taste.
• One aspect presented herein provides a method for reducing the POV of a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, comprising the steps of: adding an a-oxocarboxylic acid to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material having a first POV level; and mixing the a-oxocarboxylic acid into the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• One aspect presented herein provides a method for reducing, preventing, or ameliorating formulated perfume, body care product, homecare product, cosmetic product, or perfumery raw material-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an ⁇ -oxocarboxylic acid to the formulated perfume, body care product, homecare product, cosmetic product, or perfumery raw material having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the formulated perfume, body care product, homecare product, cosmetic product, or perfumery raw material for a time sufficient to reduce the first POV level to a pre-determined second lower level, wherein the predetermined second lower level is sufficient to reduce, prevent, or ameliorate the formulated perfume, body care product, homecare product, cosmetic product, or perfumery raw material- induced skin irritation of the subject.
• the perfumery raw material is selected from the group consisting of a synthetic ingredient, a natural product, an essential oil, and a natural extract.
• the body care product is a skin cream.
• the food raw material is selected from the group consisting of a fat, an oil, or a derivative thereof.
• the derivative thereof is selected from the group consisting of a monoglyceride, a diglyceride, and a phospholipid.
• the phospholipid is selected from the group consisting of a lecithin, a phosphatidyl ethanolamine, and a modified triglyceride.
• the perfumery raw material is treated prior to the incorporation into a perfume.
• the perfumery raw material is treated after the incorporation into a perfume.
• the food raw material is treated prior to the incorporation into a flavored article.
• the food raw material is incorporated after the incorporation into a flavored article.
• the concentration of the a-oxocarboxylic acid ranges from 0.001 to 10 weight percent, after the addition to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the a-oxocarboxylic acid is selected from the group consisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, a-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.
• the perfumery raw material is citrus oil.
• the food raw material is a cooking oil.
• the pre-determined second lower level is between 5 and 20 mmol/L.
• the pre-determined second lower level is between 0 and 6 mmol/L.
• the method further comprises removing the excess a-oxocarboxylic acid from the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material having the pre-determined second lower POV level.
• the excess ⁇ -oxocarboxylic acid is removed from the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material via a liquid-liquid extraction.
• the method further comprises treating the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material after removing the ⁇ -oxocarboxylic acid to reduce the acidity of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is treated with a carbonate salt to reduce the acidity of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• compositions comprising: (a) a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, and (b) an ⁇ -oxocarboxylic acid, wherein the a- oxocarboxylic acid is present in the composition in an amount sufficient to decrease the POV from a first level to a pre-determined second lower level.
• compositions comprising: (a) a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, and (b) an ⁇ -oxocarboxylic acid, wherein the a- oxocarboxylic acid is present in the composition in an amount sufficient to reduce, prevent, or ameliorate an increase in the POV of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the a-oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material at a concentration ranging from 0.001 to 10 weight percent.
• the perfumery raw material is citrus oil.
• the a-oxocarboxylic acid is present in the composition in an amount sufficient to prevent the pre- determined second lower level from changing with time.
• the concentration of the ⁇ -oxocarboxylic acid in the composition ranges from 0.001 to 10 weight percent.
• the ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material as an inorganic salt.
• the ⁇ -oxocarboxylic acid is present in the composition as an inorganic salt.
• the salt is an ammonium salt formed by reacting the a-oxocarboxylic acid with a compound selected from the group consisting of: 2-(dimethylamino)ethanol, N, N-dimethyldodecylamine, Tris[2 (2 (methoxyethoxy)ethyl] amine, and N-methyl diethanolamine.
• the ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material as a salt of a mono or divalent cation.
• the ⁇ -oxocarboxylic acid is present in the composition as a salt of a mono or divalent cation.
• the ⁇ -oxocarboxylic acid is selected from the group consisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, a-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.
• BRIEF DESCRIPTION OF THE FIGURES BRIEF DESCRIPTION OF THE FIGURES
• Figure 1 shows an exemplar proposed reaction between an a-oxocarboxylic acid and an organic hydroperoxide according to certain aspects presented herein.
• Figure 2 shows a representation of the rate of reduction of POV in a perfumery raw material according to certain aspects presented herein.
• Figure 3 shows POV of a skin cream by a method according to certain aspects presented herein.
• Figure 4 shows POV of a skin cream by a method according to certain aspects presented herein.
• Figure 5 shows the change in POV of a model perfume treated by a method according to certain aspects presented herein.
• Figure 6 shows the change in POV of a model perfume treated by a method according to certain aspects presented herein.
• Figure 7 shows the POV of a liquid soap formulation treated by a method according to certain aspects presented herein.
• Figure 8 shows the percent reduction in POV of a liquid soap formulation treated by a method according to certain aspects presented herein.
• Figure 9 shows the POV of a shampoo formulation treated by a method according to certain aspects presented herein.
• Figure 10 shows the percent reduction in POV of a shampoo formulation treated by a method according to certain aspects presented herein.
• Figure 11 shows the POV of an all-purpose cleaner spray formulation treated by a method according to certain aspects presented herein.
• Figure 12 shows the percent reduction in POV of an all-purpose cleaner spray formulation treated by a method according to certain aspects presented herein.
• Figure 13 shows the POV of a skin cream formulation treated by a method according to certain aspects presented herein.
• Figure 14 shows the percent reduction in POV of a skin cream formulation treated by a method according to certain aspects presented herein.
• Figure 15 shows the POV of an anti-perspirant stick formulation treated by a method according to certain aspects presented herein.
• Figure 16 shows the percent reduction in POV of an anti-perspirant stick formulation treated by a method according to certain aspects presented herein.
• perfumery raw materials such as, for example, essential oils, natural extracts, and synthetic ingredients
• oxidation resulting in the formation of chemical species including peroxides, organic hydroperoxides, peroxyhemiacetals.
• food raw materials such as, for example, fats oils, or derivatives thereof
• autoxidation process results in the formation of the intermediate chemical species glyceride hydroperoxides.
• the glyceride hydroperoxides may further degrade into aldehydes and ketones. Without intending to be limited to any particular theory the autoxidation process may result in an unpleasant and unpalatable rancidity of the food raw material.
• the peroxide value defined as the amount of equivalents of oxidizing potential per 1 kilogram of material is an indication of the extent of the oxidation.
• the POV of formulated perfumes, body care products, homecare products, cosmetic products, and perfumery raw materials is subject to regulatory limits due to skin sensitization issues, such as, for example, contact dermatitis.
• an unacceptably high POV can result in a perfumery raw material failing quality control testing, and therefore being deemed unusable.
• an unacceptably high POV can result in a food raw material, or a formulated food product (also referred to herein as a flavored article) having a rancid taste.
• Skin exposure may be the result of an incidental exposure (such as, for example, of a hard surface cleaner or a hand dishwashing soap when the user does not wear a pair of gloves when using the product).
• skin exposure may be the result of a long-term, or intentional exposure (such as, for example, of a shampoo, or skin moisturizer).
• the term "peroxide value” or "POV” refers to the amount of equivalents of oxidizing potential per 1 kilogram of material. Without intending to be limited to any particular theory, the POV of a material is determined analytically.
• POV does not refer to a chemical compound or group of compounds, but is often used loosely and interchangeably with the products of autoxidation within a sample that cause a response during a POV test. These autoxidation products differ depending upon the particular material being tested.
• one POV test is an iodometric oxidation-reduction titration.
• All POV-responsive compounds share the property that they are capable of oxidizing the iodide ion to molecular iodine within the time period specified for the test; in fact, the iodide oxidation reaction is the basis for the test.
• "POV" is a numerical value that represents the molar sum total of the all the iodide-oxidizing species in a particular sample.
• limonene and linalool are unsaturated terpenes commonly found as major components in many essential oils. Both limonene and linalool are easily oxidized by atmospheric oxygen to form hydroperoxides.
• the hydroperoxides of limonene and linalool are known to be sensitizers capable of causing contact dermatitis. Consequently, limonene, and natural products containing limonene may only be used as perfumery raw materials when the recommended organic hydroperoxide level is below 20 mmol/L (or 10 mEq/L).
• essential oils and isolates derived from the Pinacea family may only be used as perfumery raw materials when the recommended organic hydroperoxide level is below 10 mmol/L (or 5 mEQ/L).
• fats oils, or derivatives thereof are known to undergo an autoxidation process that leads to unpleasant and unpalatable rancidity.
• glyceride hydroperoxides are an intermediate chemical species in the autoxidation process, which further degrade into aldehydes and ketones that produce the rancid aroma.
• the POV of a perfumery raw material may be determined by any method readily selectable by one of ordinary skill in the art. Non limiting examples include, iodometric titration, high-performance liquid chromatography, and the like.
• Perfumery raw materials include, but are not limited to essential oils, natural extracts, and synthetic ingredients.
• the POV of a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material may be determined by any method readily selectable by one of ordinary skill in the art. No limiting examples include, iodometric titration, high-performance liquid chromatography, and the like.
• the POV of a formulated body care product may be determined by any method readily selectable by one of ordinary skill in the art. Non-limiting examples include iodometric titration, high-performance liquid chromatography, and the like.
• the a-oxocarboxylic acid reacts with the organic hydroperoxide via oxidative decarboxylation, thereby consuming the organic hydroperoxide, reducing the organic hydroperoxide's oxidative potential.
• the resulting reaction results in the oxidation of the ⁇ -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.
• An exemplar proposed reaction, using pyruvic acid as the ⁇ -oxocarboxylic acid and limonene-hydroperoxide as the organic hydroperoxide is depicted in Figure 1.
• one aspect presented herein provides a method for reducing the POV of a perfumery raw material, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the perfumery raw material having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the perfumery raw material for a time sufficient to reduce the first POV level to a predetermined second lower level.
• An alternate aspect presented herein provides a method for reducing, preventing, or ameliorating perfumery raw material-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an ⁇ -oxocarboxylic acid to the perfumery raw material having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the perfumery raw material for a time sufficient to reduce the first POV level to a pre-determined second lower level, wherein the pre-determined second lower level is sufficient to reduce, prevent, or ameliorate the perfumery raw material-induced skin irritation of the subject.
• An alternate aspect presented herein provides a method for reducing the POV of a formulated perfume, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the formulated perfume having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the formulated perfume for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• An alternate aspect presented herein provides a method for reducing, preventing, or ameliorating formulated perfume-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an a-oxocarboxylic acid to the formulated perfume having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the formulated perfume for a time sufficient to reduce the first POV level to a pre- determined second lower level, wherein the pre-determined second lower level is sufficient to reduce, prevent, or ameliorate the formulated perfume-induced skin irritation of the subject.
• An alternate aspect presented herein provides a method for reducing the POV of a formulated personal care product, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the formulated personal care product having a first POV level; and mixing the a- oxocarboxylic acid into the formulated personal care product for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• An alternate aspect presented herein provides a method for reducing, preventing, or ameliorating formulated personal care product-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an ⁇ -oxocarboxylic acid to the formulated personal care product having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the formulated personal care product for a time sufficient to reduce the first POV level to a pre-determined second lower level, wherein the pre-determined second lower level is sufficient to reduce, prevent, or ameliorate the formulated personal care product-induced skin irritation of the subject.
• An alternate aspect presented herein provides a method for reducing the POV of a formulated cosmetic product, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the formulated cosmetic product having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the formulated cosmetic product for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• An alternate aspect presented herein provides a method for reducing, preventing, or ameliorating formulated cosmetic product-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an ⁇ -oxocarboxylic acid to the formulated cosmetic product having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the formulated cosmetic product for a time sufficient to reduce the first POV level to a predetermined second lower level, wherein the pre-determined second lower level is sufficient to reduce, prevent, or ameliorate the formulated cosmetic product-induced skin irritation of the subject.
• An alternate aspect presented herein provides a method for reducing the POV of a formulated homecare product, comprising the steps of: adding an a-oxocarboxylic acid to the formulated homecare product having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the formulated homecare product for a time sufficient to reduce the first POV level to a pre- determined second lower level.
• An alternate aspect presented herein provides a method for reducing, preventing, or ameliorating formulated homecare product-induced skin irritation of a subject in need thereof, comprising the steps of: (a) adding an ⁇ -oxocarboxylic acid to the formulated homecare product having a first POV level; and (b) mixing the ⁇ -oxocarboxylic acid into the formulated homecare product for a time sufficient to reduce the first POV level to a predetermined second lower level, wherein the pre- determined second lower level is sufficient to reduce, prevent, or ameliorate the formulated homecare product-induced skin irritation of the subject.
• the method is performed at room temperature. In one aspect, the method is performed at a temperature ranging from -20 degrees Celsius to 78 degrees Celsius.
• the perfumery raw material is selected from the group consisting of a synthetic ingredient, a natural product, an essential oil, and a natural extract.
• the perfumery raw material is citrus oil.
• the perfumery raw material is treated prior to the incorporation into a perfume.
• the perfumery raw material is treated after the incorporation into a perfume.
• the pre- determined second lower level is between 5 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 19 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 18 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 17 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 16 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 15 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 14 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 13 mmol/L.
• the pre-determined second lower level is between 5 and 12 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 11 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 10 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 9 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 8 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 7 mmol/L. In an alternate aspect, the pre-determined second lower level is between 5 and 6 mmol/L.
• the pre-determined second lower level is between 6 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 7 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 8 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 9 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 10 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 11 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 12 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 13 and 20 mmol/L.
• the pre-determined second lower level is between 14 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 15 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 16 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 17 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 18 and 20 mmol/L. In an alternate aspect, the pre-determined second lower level is between 19 and 20 mmol/L.
• the pre-determined second lower level is 20 mmol/L. In an alternate aspect, the pre-determined second lower level is 19 mmol/L. In an alternate aspect, the predetermined second lower level is 18 mmol/L. In an alternate aspect, the pre-determined second lower level is 17 mmol/L. In an alternate aspect, the pre-determined second lower level is 16 mmol/L. In an alternate aspect, the pre-determined second lower level is 15 mmol/L. In an alternate aspect, the pre- determined second lower level is 14 mmol/L. In an alternate aspect, the pre- determined second lower level is 13 mmol/L. In an alternate aspect, the pre-determined second lower level is 12 mmol/L.
• the predetermined second lower level is 11 mmol/L. In an alternate aspect, the pre-determined second lower level is 10 mmol/L. In an alternate aspect, the pre-determined second lower level is 9 mmol/L. In an alternate aspect, the pre-determined second lower level is 8 mmol/L. In an alternate aspect, the pre-determined second lower level is 7 mmol/L. In an alternate aspect, the pre-determined second lower level is 6 mmol/L. In an alternate aspect, the predetermined second lower level is 5 mmol/L. In an alternate aspect, the pre-determined second lower level is 4 mmol/L. In an alternate aspect, the pre-determined second lower level is 3 mmol/L. In an alternate aspect, the pre-determined second lower level is 2 mmol/L. In an alternate aspect, the pre-determined second lower level is 1 mmol/L. In an alternate aspect, the pre-determined second lower level is less than 1 mmol/L.
• the pre-determined second lower level is a 10% reduction in the POV. In an alternate aspect, the pre-determined second lower level is a 20, or 30, or 40, or 50, or 60, or 70, or 80, or 90, or 100% reduction in the POV.
• An alternate aspect presented herein provides a method for reducing the POV of a food raw material, comprising the steps of: adding an a-oxocarboxylic acid to the food raw material having a first POV level; and mixing the a-oxocarboxylic acid into the food raw material for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• An alternate aspect presented herein provides a method for reducing the POV of a flavored article, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the flavored article having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the flavored article for a time sufficient to reduce the first POV level to a pre-determined second lower level.
• reducing the POV of a flavored article or a food raw material prevents, reduces, or inhibits the formation of the intermediate glyceride hydroperoxides in the flavored article or the food raw material.
• Reducing, or inhibiting, or preventing the formation of the intermediate glyceride hydroperoxides in the flavored article or the food raw material may prevent, reduce, or delay the development of rancidity in the flavored article or the food raw material.
• a flavored article includes, for example, a food product (e.g., a beverage), a sweetener such as a natural sweetener or an artificial sweetener, a pharmaceutical composition, a dietary supplement, a nutraceutical, a dental hygienic composition and a cosmetic product.
• a food product e.g., a beverage
• a sweetener such as a natural sweetener or an artificial sweetener
• a pharmaceutical composition e.g., a dietary supplement, a nutraceutical, a dental hygienic composition
• the flavored article may further contain at least one flavoring.
• the at least one flavoring may further modify the taste profile or taste attributes of the flavored article.
• the flavored article is a food product including, for example, but not limited to, fruits, vegetables, juices, meat products such as ham, bacon and sausage, egg products, fruit concentrates, gelatins and gelatin-like products such as jams, jellies, preserves and the like, milk products such as ice cream, sour cream and sherbet, icings, syrups including molasses, corn, wheat, rye, soybean, oat, rice and barley products, nut meats and nut products, cakes, cookies, confectioneries such as candies, gums, fruit flavored drops, and chocolates, chewing gums, mints, creams, pies and breads.
• fruits, vegetables, juices, meat products such as ham, bacon and sausage, egg products, fruit concentrates, gelatins and gelatin-like products such as jams, jellies, preserves and the like
• milk products such as ice cream, sour cream and sherbet, icings
• syrups including molasses, corn
• the food product is a beverage including, for example, but not limited to, juices, juice containing beverages, coffee, tea, carbonated soft drinks, such as COKE and PEPSI, non-carbonated soft drinks and other fruit drinks, sports drinks such as GATORADE and alcoholic beverages such as beers, wines and liquors.
• a flavored article may also include prepared packaged products, such as granulated flavor mixes, which upon reconstitution with water provide non-carbonated drinks, instant pudding mixes, instant coffee and tea, coffee whiteners, malted milk mixes, pet foods, livestock feed, tobacco, and materials for baking applications, such as powdered baking mixes for the preparation of breads, cookies, cakes, pancakes, donuts and the like.
• a flavored article may also include diet or low-calorie food and beverages containing little or no sucrose. Flavored articles may also include condiments such as herbs, spices and seasonings, flavor enhancers (e.g., monosodium glutamate), dietetic sweeteners and liquid sweeteners.
• condiments such as herbs, spices and seasonings, flavor enhancers (e.g., monosodium glutamate), dietetic sweeteners and liquid sweeteners.
• the flavored article is a pharmaceutical composition, a dietary supplement, a nutraceutical, a dental hygienic composition or a cosmetic product.
• Dental hygiene compositions are known in the art and include, for example, but not limited to, a toothpaste, a mouthwash, a plaque rinse, a dental floss, a dental pain reliever (such as ANBESOL) and the like.
• the dental hygiene composition includes one natural sweetener.
• the dental hygiene composition includes more than one natural sweetener.
• the dental hygiene composition includes sucrose and corn syrup, or sucrose and aspartame.
• a cosmetic product includes, for example, but not limited to, a face cream, a lipstick, a lip gloss and the like.
• Other suitable cosmetic products of use in this disclosure include a lip balm, such as CHAPSTICK or BURT'S BEESWAX Lip Balm.
• An alternate aspect presented herein provides a method for increasing the shelf life of a food raw material, comprising the steps of: adding an a-oxocarboxylic acid to the food raw material having a first POV level; and mixing the a-oxocarboxylic acid into the food raw material for a time sufficient to reduce the first POV level to a pre- determined second lower level.
• the reduction of the first POV level to a pre- determined second lower level prevents, reduces, or inhibits the formation of the intermediate glyceride hydroperoxides in the food raw material, resulting in the prevention, reduction, inhibition of the development of rancidity in the food raw material.
• the food raw material may be employed as a solvent for a flavoring ingredient, or, alternatively, the food raw material itself may be a flavoring ingredient.
• An alternate aspect presented herein provides a method for increasing the shelf life of flavored article, comprising the steps of: adding an ⁇ -oxocarboxylic acid to the flavored article having a first POV level; and mixing the ⁇ -oxocarboxylic acid into the flavored article for a time sufficient to reduce the first POV level to a pre- determined second lower level.
• the reduction of the first POV level to a pre- determined second lower level prevents, reduces, or inhibits the formation of the intermediate glyceride hydroperoxides in the flavored article, resulting in the prevention, reduction, inhibition of the development of rancidity in the flavored article.
• the food raw material is selected from the group consisting of a fat, an oil, or a derivative thereof.
• the derivative thereof is selected from the group consisting of a monoglyceride, a diglyceride, and a phospholipid.
• the phospholipid is selected from the group consisting of a lecithin, a phosphatidyl ethanolamine, and a modified triglyceride.
• the food raw material is treated prior to the incorporation into a flavored article. In an alternate aspect the food raw material is incorporated after the incorporation into a flavored article.
• the food raw material is a cooking oil.
• cooking oils suitable for treatment according to the aspects described herein include, but are not limited to: olive oil, palm oil, soybean oil, canola oil (rapeseed oil), corn oil, peanut oil, other vegetable oils, and animal-based oils, such as, for example, butter or lard.
• the method is performed at room temperature. In one aspect, the method is performed at a temperature ranging from -20 degrees Celsius to 78 degrees Celsius.
• the pre-determined second lower level is between 0 and 6 mmol/L. In an alternate aspect, the pre-determined second lower level is between 0 and 5 mmol/L. In an alternate aspect, the pre-determined second lower level is between 0 and 4 mmol/L. In an alternate aspect, the pre-determined second lower level is between 0 and 3 mmol/L. In an alternate aspect, the pre-determined second lower level is between 0 and 2 mmol/L. In an alternate aspect, the pre-determined second lower level is between 0 and 1 mmol/L. [0111] In one aspect, the pre-determined second lower level is between 1 and 6 mmol/L.
• the pre-determined second lower level is between 2 and 5 mmol/L. In an alternate aspect, the pre-determined second lower level is between 3 and 5 mmol/L. In an alternate aspect, the pre-determined second lower level is between 4 and 5 mmol/L.
• the pre-determined second lower level is 5 mmol/L. In an alternate aspect, the pre-determined second lower level is 4 mmol/L. In an alternate aspect, the predetermined second lower level is 3 mmol/L. In an alternate aspect, the pre-determined second lower level is 2 mmol/L. In an alternate aspect, the pre-determined second lower level is 1 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.9 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.8 mmol/L. In an alternate aspect, the pre- determined second lower level is 0.7 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.6 mmol/L.
• the predetermined second lower level is 0.5 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.4 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.3 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.2 mmol/L. In an alternate aspect, the pre-determined second lower level is 0.1 mmol/L. In an alternate aspect, the pre-determined second lower level is 0 mmol/L.
• the pre-determined second lower level is a 10% reduction in the POV. In an alternate aspect, the pre-determined second lower level is a 20, or 30, or 40, or 50, or 60, or 70, or 80, or 90, or 100% reduction in the POV.
• the a-oxocarboxylic acid has FEMA-GRAS status.
• the a-oxocarboxylic acid is selected from the group consisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, a- ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.
• the at least one ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material as a salt.
• the salt may be formed by reacting the at least one ⁇ -oxocarboxylic acid with an organic base.
• the resultant salt may be a mono-salt.
• the resultant salt may be a mono-salt, or a di-salt.
• Examples of suitable organic bases include, but are not limited to the organic bases described in Examples 7-11 below, polymeric amines, polyetylamines, and the like.
• the salt may be formed by reacting the at least one a-oxocarboxylic acid with a cation selected from the group consisting of: Na + , K + , Mg 2+ , and Ca 2+ .
• An example of an ammonium salt includes the ammonium salt formed by reacting the at least one ⁇ -oxocarboxylic acid with N-methyl diethanolamine.
• the molar ratio of the at least one a-oxocarboxylic acid to N-methyl diethanolamine may be 1 :2, or 1: 1, or 2: 1.
• the ammonium salt of the at least one a-oxocarboxylic acid possesses surfactant properties.
• surfactant properties typically arise in molecules that contain an ionic and/or highly polar functional groups in the molecule, along with one or more spatially separated, long hydrophobic section(s). If a hydrophobic moiety, such as an alkyl group with a sufficient number of carbons (for example, C-8 to C-24) is bound to the ammonium salt of the at least one ⁇ -oxocarboxylic acid, the resulting molecule may demonstrate surfactant properties.
• an ammonium salt of the at least one ⁇ -oxocarboxylic acid possessing surfactant properties, or that is ionic and highly polar may be useful in a variety of home care and body care consumer products that come in contact with the user's skin during use.
• ammonium salts of the at least one ⁇ -oxocarboxylic acid having surfactant properties include, but are not limited to: the diammonium salt made from alpha- ketoglutaric acid and N, N-dimethyldodecylamine in a 1:2 molar ratio, and the monoammonium salt made from alpha-ketoglutaric acid and N, N-dimethyldodecylamine in a 1: 1 molar ratio.
• the ammonium salt of the at least one ⁇ -oxocarboxylic acid possesses emollient properties.
• emollient properties typically arise in molecules that are predominately hydrophobic and inert with low melting points (relative to body temperature) can act as emollients.
• Useful emollients have oily or grease-like physical properties, and act as softening agents and/or moisture barriers when applied to the skin.
• ammonium salt of the at least one a- oxocarboxylic acid listed above are ionic and highly polar in character, if a sufficient quantity of hydrophobic moieties can be incorporated into an ammonium salt of the at least one a- oxocarboxylic acid, the resulting molecule may display emollient characteristics.
• One approach is to use an amine that has three long, hydrophobic or oily substituents as the base component of the ammonium salt of the at least one ⁇ -oxocarboxylic acid.
• Such a molecule may have hydroperoxide consuming/POV lowering qualities along with emollient properties, and therefore provide additional benefits to the user. These would be useful in a variety of body care consumer products that are placed onto the skin during use and left on for extended periods for purposes of moisturizing, protecting, or softening the user's skin.
• ammonium salts of the at least one a-oxocarboxylic acid having emollient properties include, but are not limited to: the diammonium salt made from alpha- ketoglutaric acid and Tris[2 (2 (methoxyethoxy)ethyl] amine in a 1:2 molar ratio.
• the at least one a-oxocarboxylic acid may be reacted with N-methyl diethanolamine by dissolving the at least one ⁇ -oxocarboxylic acid in a solvent, such as, for example, acetone, and adding N-methyl diethanolamine to the solution.
• a solvent such as, for example, acetone
• the resultant opaque, white emulsion may then be vortexed, during which time a second phase may coalesce.
• the mixture may then be placed in a freezer for at least 30 minutes, causing the bottom phase to thicken to a waxy solid. While still cold, the top layer may then be easily removed via decantation and discarded. Residual acetone may be removed from the bottom product layer via a stream of nitrogen followed by treatment in a vacuum oven at room temperature, thereby resulting in a faint yellow, highly viscous oil at room temperature comprising the diammonium salt.
• Other compounds suitable to form an ammonium salt via reaction with the at least one ⁇ -oxocarboxylic acid include, 2-(dimethylamino)ethanol, and N, N-dimethyldodecylamine.
• the salt is an ammonium salt formed by reacting the a-oxocarboxylic acid with a compound selected from the group consisting of: 2-(dimethylamino)ethanol, N, N-dimethyldodecylamine, Tris[2 (2 (methoxyethoxy)ethyl] amine, and N-methyl diethanolamine.
• the ammonium salt of the at least one ⁇ -oxocarboxylic acid may prevent acid-catalyzed chemical reactions from occurring that can harm and/or degrade the treated formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the ammonium salt of the at least one ⁇ -oxocarboxylic acid may improve the solubility of the at least one ⁇ -oxocarboxylic acid.
• the ammonium salt of the at least one ⁇ -oxocarboxylic acid may provide an emulsifying effect.
• a salt of the at least one a- oxocarboxylic acid when added to an aqueous system comprising the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material may be an emulsifier.
• a composition may be useful for salad dressings, marinades, sauces, and the like.
• the ammonium salt of the at least one a-oxocarboxylic acid may be furher combined with at least one other agent.
• the at least one other agent is chitosan.
• alpha-ketoglutaric acid is added to a mixture of palmitic acid and chitosan.
• a composition may be an emulsifier for the food oil in an aqueous system, and may be useful for salad dressings, marinades, sauces, and the like.
• the time sufficient to reduce the POV to a pre- determined second lower level is 30, or 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(s).
• the time sufficient to reduce the POV to a pre- determined second lower level is greater than 24 hours. In one aspect, the time sufficient to reduce the POV to a pre- determined second lower level is 48, or 47, or 46, or 45, or 44, 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(s).
• the time sufficient to reduce the POV to a pre- determined second lower level is 60 minutes or less. In one aspect, the time sufficient to reduce the POV to a 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 minute.
• the amount of the a- oxocarboxylic acid and/or the rate at which the a-oxocarboxylic is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is controlled to ensure that an excess of the a- oxocarboxylic does not accumulate.
• An excess accumulation of the ⁇ -oxocarboxylic may result, for example, in acid-catalyzed damage to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the amount of the ⁇ -oxocarboxylic acid that is added to the formulated perfume, body care product, perfumery raw material, flavored article, or food raw material is dependent on several factors, including, but not limited to, the stability of the a- oxocarboxylic acid in solution, the solubility of the ⁇ -oxocarboxylic acid in the formulated perfume, body care product, perfumery raw material, flavored article, or food raw material, the pKa of the ⁇ -oxocarboxylic acid, the rate of reduction of the POV, the effect the a- oxocarboxylic acid has on the olfactive properties and/or taste of the formulated perfume, body care product, perfumery raw material, flavored article, or food raw material.
• pyruvic acid, phenylpyruvic acid, and 2-oxovaleric acid possess strong aromas are used as FEMA-GRAS flavoring components.
• the intrinsic odors of the ⁇ -oxocarboxylic acid may alter, or be incompatible with the organoleptic quality of a formulated perfume, for example.
• an alternative to using an odorless ⁇ -oxocarboxylic acid in the aspects described herein is the use of an ⁇ -oxocarboxylic acid that is compatible with the fragrance of the perfume, and when consumed by reaction with hydroperoxides, that also liberates a carboxylic acid that is compatible with the fragrance.
• indole-3- pyruvic acid nay be used to reduce the POV of a fragrance that has an indolic character (i.e. contains perceivable amounts of indole and/or skatole).
• an ⁇ -oxocarboxylic acid that is odorless examples include a-ketoglutaric acid.
• an odorless ⁇ -oxocarboxylic acid may reduce the POV of a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material with a lower impact on the organoleptic properties of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, compared to an ⁇ -oxocarboxylic acid that has an odor.
• the solubility of the ⁇ -oxocarboxylic acid may change if the composition comprising the ⁇ -oxocarboxylic acid is formulated differently.
• the solubility of the ⁇ -oxocarboxylic acid may be low in a perfume raw material such citrus oil.
• the solubility of the ⁇ -oxocarboxylic acid may increase, if the perfume raw material is added to a hydroalcoholic perfume base (a solution comprising from 80% to 90% ethanol in water).
• the amount of the ⁇ -oxocarboxylic acid in solution in the hydroalcoholic perfume base may have to be limited, to prevent alterations of the organoleptic properties on the perfume raw materials or the formulated perfume due to the acid-catalyzed degradation of the perfume raw material.
• Examples of aspects where the a-oxocarboxylic acid may be unstable in solution include oxaloacetic acid, which is unstable in aqueous solution.
• the oxaloacetic acid breaks down to pyruvic acid, and carbon dioxide.
• reduction of the POV of the formulated perfume, body care product, perfumery raw material, flavored article, or food raw material may be via the oxaloacetic acid, the pyruvic acid, or any combination thereof.
• the solubility of the a-oxocarboxylic acid in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is low.
• the ⁇ -oxocarboxylic acid may be practically insoluble in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the ⁇ -oxocarboxylic acid may be fully miscible in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• Examples of aspects where the solubility of the ⁇ -oxocarboxylic acid in formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is low include, but are not limited to pyruvic acid in citrus oil.
• the ⁇ -oxocarboxylic acid may be added at a concentration in excess of the solubility, thus forming a two-phase system, wherein one phase consists of the ⁇ -oxocarboxylic acid.
• components of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material may partition into the phase consisting of the ⁇ -oxocarboxylic acid. Exposure of the components of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material to the phase consisting of the ⁇ -oxocarboxylic acid may result in chemical changes/damage to acid-sensitive compounds in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material . [0146] By way of illustration, essential oils are composed largely of terpene compounds.
• terpenes are generally subject to acid-catalyzed rearrangements. Consequently, exposure of the components of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material to the phase consisting of the a-oxocarboxylic acid may result in chemical changes/damage to acid- sensitive compounds in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material , and consequently alter the organoleptic properties of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the ⁇ -oxocarboxylic acid is added at a rate that minimizes, or prevents the formation of the second phase consisting of the a- oxocarboxylic acid.
• rate of addition may be equal to the rate of the chemical reaction that reduces the POV of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• addition of the ⁇ -oxocarboxylic acid at the same rate as the chemical reaction may prevent the ⁇ -oxocarboxylic acid from accumulating and thereby keep the second phase volume minimized, which will reduce partitioning of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material into the highly acidic phase consisting of the ⁇ -oxocarboxylic acid.
• effective dispersion of the ⁇ -oxocarboxylic acid in to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material may increase the rate of the chemical reaction that reduces the POV of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material , by increasing the surface area of contact between the two phases of the two phase system.
• Examples of aspects where the solubility of the ⁇ -oxocarboxylic acid in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is not low include, but are not limited to 2- oxo-valeric acid. Without intending to be limited to any particular theory, in aspects where the solubility of the ⁇ -oxocarboxylic acid in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is not low may result in the formation of a single phase.
• the added a- oxocarboxylic acid is soluble in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material being treated, and therefore will be diluted immediately upon addition.
• the ⁇ -oxocarboxylic acid will also be consumed as it is being added.
• the concentration of the ⁇ -oxocarboxylic acid will remain low, and acid-induced changes will be minimized.
• the concentration of un-reacted ⁇ -oxocarboxylic acid is minimized by using a buffer, wherein the ⁇ -oxocarboxylic acid is present as a deprotonated anion.
• the anionic form of an ⁇ -oxocarboxylic acid will likely be unreactive toward a hydroperoxide relative to the protonated, acidic form. However, as the acidic form is consumed by reaction with hydroperoxides, the equilibrium of the ⁇ -oxocarboxylic acid-base pair will quickly reestablish itself in accordance with the pKa of ⁇ -oxocarboxylic acid; the anionic form will instantly capture a proton from the media to produce more of the hydroperoxide-reactive acidic form of the ⁇ -oxocarboxylic acid.
• the bulk acidity of the media can be maintained at a mild pH level, one that will not cause acid damage to the components of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material . But simultaneously, there will be a relatively low but fixed level of the ⁇ -oxocarboxylic acid in the reactive protonated form, replenished as soon as it is consumed from a sink of the relatively inert anionic form.
• pyruvic acid has a pKa of 2.50, buffering the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material to pH 5.5 (a difference of 3 log units), would result in 10 (or 1000) times the concentration of pyruvate anion, compared to pyruvic acid (as per the Henderson-Hasselbalch equation).
• the concentration of the ⁇ -oxocarboxylic acid ranges from 0.001 to 10 weight percent, after addition to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the concentration of the a-oxocarboxylic acid is 10 weight percent, after addition to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the concentration of the ⁇ -oxocarboxylic acid 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, after addition to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the ⁇ -oxocarboxylic acid can be added directly to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material , or, alternatively, the ⁇ -oxocarboxylic acid can be diluted prior to addition to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• Any diluent that may be used in perfumery may be used. Suitable diluents include, but are not limited to isopropanol, ethanol, diglyme, triethyleneglycol, and the like.
• the ⁇ -oxocarboxylic acid may be diluted 1: 1, or 1:2, or 1:3, or 1:4, or more with the diluent.
• the choice of diluent may also influence the amount of the ⁇ -oxocarboxylic acid that may be added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the choice of diluent may also influence the rate at which the ⁇ -oxocarboxylic acid that is be added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the pyruvic acid As the a- oxocarboxylic acid, and ethanol as the solvent, the pyruvic acid must be added in an amount, and/or a at a rate that minimizes the formation of an ester with the ethanol.
• the ⁇ -oxocarboxylic acid can be added to any volume of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the ⁇ -oxocarboxylic acid can be added can be added to 1000 ml of formulated perfume, body care product, or perfumery raw material, or 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 formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the a-oxocarboxylic acid may be added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material over 80 minutes.
• the a-oxocarboxylic acid may be added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material over 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(s).
• the ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material at a rate of 0.25 ml per minute. In some aspects, the rate of addition is greater than 0.25 ml per minute. In some aspects, the rate of addition is less than 0.25 ml per minute.
• the rate at which the ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is constant. In some aspects, the rate at which the a- oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material varies. In one aspect, the ⁇ -oxocarboxylic acid is added to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material at a rate equal to the rate at which the ⁇ -oxocarboxylic acid is oxidized.
• the rate at which the ⁇ -oxocarboxylic acid is oxidized may be determined by measuring the POV in the treated formulated perfume, body care product, or perfumery raw material. Referring to Figures 2 to 4, by way of illustration, the rate of reduction of POV may have a first rate, which is greater than a second rate. In the aspect illustrated, the duration of the first rate is less than the duration of the second rate.
• the ⁇ -oxocarboxylic acid may be added, and subsequently quenched after a period of time.
• the ⁇ -oxocarboxylic acid may be quenched 80 minutes after addition to the substance.
• the a-oxocarboxylic acid may 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(s) after addition to the substance.
• the method further comprises removing the excess a-oxocarboxylic acid from the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material having a POV of a predetermined second lower level.
• the excess ⁇ -oxocarboxylic acid is removed from the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material via a liquid- liquid extraction.
• the excess ⁇ -oxocarboxylic acid is removed from the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material via a liquid-liquid extraction using water.
• the method further comprises treating the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material after removing the excess ⁇ -oxocarboxylic acid to reduce the acidity of the substance.
• the treatment comprises the addition of a buffer, such as, for example, trethanolamine, or N-methyldiethanolamine, and the like.
• the substance is treated with a carbonate salt to reduce the acidity of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material .
• the method for reducing the POV of formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material comprises the steps of: a) introducing the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material into a reaction vessel, wherein the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is under an inert gas, such as, for example, argon; b) introducing the a-oxocarboxylic acid to the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material at a rate of 0.25 ml per minute, where
• the second phase of the ⁇ -oxocarboxylic acid in the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material is a "leave-in" composition of the ⁇ -oxocarboxylic acid.
• the amount ⁇ -oxocarboxylic acid present in the two phases is in equilibrium, and the reduction of POV may result in the a- oxocarboxylic acid moving from the phase consisting of ⁇ -oxocarboxylic acid, into the phase containing the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• Example 5 One example of this aspect is described in Example 5 below.
• the "leave-in" composition of the a-oxocarboxylic acid comprises a single phase composition with the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the composition further comprises a buffer, wherein the pH is configured to maintain the majority of the ⁇ -oxocarboxylic acid present in a non-pro tonated form, wherein the non- protonated form is incapable of reacting with the chemical species that contribute to the POV of the composition (including peroxides, organic hydroperoxides, peroxyhemiacetals).
• the amount of the a-oxocarboxylic acid present in non-protonated form is in equilibrium with an amount of amount of the a- oxocarboxylic acid present in protonated form, and the reduction of POV may result in the a- oxocarboxylic acid moving from the non-protonated from to the protonated form.
• the "leave-in" compositions of the ⁇ -oxocarboxylic acid is capable of reducing POV for a prolonged period of time.
• composition comprising: (a) a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, and (b) an ⁇ -oxocarboxylic acid, wherein the ⁇ -oxocarboxylic acid is present in the composition in an amount sufficient to decrease the POV from a first level to a pre-determined second lower level.
• the ⁇ -oxocarboxylic acid is present in the composition in an amount sufficient to prevent the pre-determined second lower level from changing with time. The time may be hours, days, weeks, or longer.
• One aspect presented herein provides a composition comprising: (a) a formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material, and (b) an ⁇ -oxocarboxylic acid, wherein the a- oxocarboxylic acid is present in the composition in an amount sufficient to reduce, prevent, or ameliorate an increase in the POV of the formulated perfume, body care product, cosmetic product, homecare product, perfumery raw material, flavored article, or food raw material.
• the concentration of the a-oxocarboxylic acid in the composition ranges from 0.001 to 10 weight percent.
• the a-oxocarboxylic acid is selected from the group consisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, a-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.
• the perfumery raw material is citrus oil.
• the at least one ⁇ -oxocarboxylic acid, or a salt thereof may be applied to, or incorporated into, or covalently bound to a solid substrate, wherein the solid substrate comprising the at least one ⁇ -oxocarboxylic acid, or a salt thereof is used to treat a formulated perfume, body care product, cosmetic product, perfumery raw material, flavored article, or food raw material.
• any inert, finely divided or high surface area material may be used as the solid support.
• examples include, but are not limited to: metals, glass, expanded ceramics, plastics, or inorganic solids.
• the solid support may comprise the bottom and/or the walls of a vessel containing the formulated perfume, body care product, cosmetic product, perfumery raw material, flavored article, or food raw material.
• the solid support has a high surface are: volume ratio.
• Such solid supports include, but are not limited to steel wool.
• An example of a composition treated according to the aspect employing a solid support as described above can be found in Example 24 below.
• the present invention is best illustrated but is not limited to the following examples.
• Example 1 Reduction of POV in Citrus Oil According to One Aspect Presented Herein Using Pyruvic Acid
• a 4: 1 v/v isopropanol/pyruvic acid solution was made. 20 mL of this pyruvic acid solution was dripped into the stirred citrus oils at a rate of 0.25 mL/minute via the use of a syringe pump. [0185] When the addition was complete, 10 mL of water and 100 mg of anhydrous sodium carbonate was added to the flask, and the stirring was maintained. When the visible evolution of C0 2 had stopped (about 2 - 4 minutes), the aqueous layer was removed with a pipette and discarded. POV measurements were made on the mixed citrus oil before and after the pyruvic acid treatment. [0186] POV before treatment was 27.261 mEq/L, and the POV after treatment was 4.786 mEq./L. This was about an 82% reduction in POV.
• Example 6 Reduction of POV in a Skin Cream Formulation According to One Aspect Presented Herein Using 2-Oxovaleric Acid or Phenylglyoxylic Acid.
• a skin cream formulation comprising of 0.5 parts cetylstearyl alcohol, 6.0 parts wool wax alcohol, and 93.5 parts white petroleum jelly was created as per the German Pharmacopoeia DAB 2008.
• the skin cream was divided into two separate preparations.
• a highly oxidized limonene sample was added to both preparations, with the first preparation receiving a concentration of oxidized limonene approximately one third of the concentration of the oxidized limonene in the second preparation.
• Analysis of the oxidized limonene sample showed the sample to contain a mixture of limonene hydroperoxide isomers.
• the initial POV of both the first and second skin cream preparations was taken, prior to treatment with 2-oxovaleric acid or phenylglyoxylic acid as follows: 2-oxovaleric acid (second preparation), or phenylglyoxylic acid (first preparation) was thoroughly blended into the skin cream preparations. The POV of the preparations were measured, during addition of the 2-oxovaleric acid. After addition of the 2-oxovaleric acid or phenylglyoxylic acid, the treated preparations were allowed to stand at room temperature. The POV data obtained was corrected for the exact weight of the aliquot of cream titrated at each individual time point, and normalized as a percentage to the starting POV.
• the second preparation containing the highest amount of the oxidized limonene sample was treated with approximately 2.3 % w/w 2-oxovaleric acid. The results are shown below in Figure 3.
• the first preparation containing the lowest amount of the oxidized limonene sample was treated with approximately 3.9 % w/w 2-phenylglyoxylic acid. The results are shown below in Figure 4.
• Example 7 Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS #328-50-7) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:2 Molar Ratio.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• Approximately 400 mg (2.0% w/v) of the AKG-DiNMDEA salt was dissolved in 20 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition.
• An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below.
• Example 8 Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS #328-50-7) and ⁇ , ⁇ -dimethyldodeclyamine (DiMeC12A, CAS #112-18-5) in a 1:2 Molar Ratio.
• This solid was warmed up to 30 - 35° C to re-liquify the product so that entrapped acetone could be removed via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This gave a white, waxy solid containing the diammonium salt (AKG- DiMeC12A salt).
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• Approximately 400 mg (2.0% w/v) of the AKG-DiMeC 12A salt was dissolved in 20 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition.
• An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below. Time in Minutes POV of Treated Perfume POV of Untreated Perfume
• a 0.14 weight % solution of AKG- DiMeC 12A in water was used for the measurement. This concentration was chosen so the results could be compared to the literature value for known surfactant sodium dodecyl sulfate (SDS) at 5 mM, which is appproximately 0.15 weight %.
• SDS sodium dodecyl sulfate
• SDS at 5 mM concentration (approximately 0.15 weight %, which is very close to the 0.14 weight % used here) at 273K, has an air- water surface tension in the range of 33.5 to 35.5 mN/m depending on the pH (see Hernainz, F. et al, Colloids Surf. A, 2002, 196, 19-24).
• Example 9 Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid and (CAS #328-50-7) and 2-(dimethylamino(ethanol (Deanol, CAS #108-01-0) in a 1:2 Molar Ratio.
• Residual acetone was removed from the bottom product layer via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This produced clear, colorless, viscous oil at room temperature containing the diammonium salt (AKG DiDeanol salt).
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of orange, grapefruit, and bergamot oils as the perfume oil. The mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent). Approximately 200 mg (1.0% w/v) of the AKG DiDeanol salt was dissolved in 20 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition. An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below.
• Example 10 Formation of an Ammonium Salt via the Reaction of Pyruvic Acid (CAS #328-50-7) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of lime, orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).
• Approximately 150 mg (1.0% w/v) of the PA-NMDEA salt was dissolved in 15 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition.
• An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below.
• Example 11 Formation of an Ammonium Salt via the Reaction of Phenylglyoxylic Acid (PhGA, CAS #611-73-4) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio.
• PhGA Phenylglyoxylic Acid
• NMDEA N-methyl diethanolamine
• Example 11 Formation of an Ammonium Salt via the Reaction of Phenylglyoxylic Acid (PhGA, CAS #611-73-4) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio.
• PhGA Phenylglyoxylic Acid
• NMDEA N-methyl diethanolamine
• the crystalline product containing the diammonium salt (PhGA-NMDEA salt ) was extremely hygroscopic, and would liquefy very rapidly if exposed to ambient atmosphere; the white mass of needles had to be kept under vacuum or a rigorous nitrogen blanket to remain crystalline. A weight/yield was not obtained due to the hygroscopicity.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of lime, orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).
• Approximately 150 mg (1.0% w/v) of the PhGA-NMDEA salt was dissolved in 15 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition.
• An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below.
• Example 14 Formation of an Ammonium Salt via the Reaction of ⁇ - ⁇ -2-Furanacetic Acid (CAS #1467-70-5) and N, N-dimethyldecylamine (DiMeClOA, CAS #1120-24-7) in a 1:1 Molar Ratio.
• the amine solution was added dropwise with stirring over the course of 5 minutes to the crude alpha-oxo-2-furanacetic acid solution; no visible indication of reaction was seen, and no warming was noticeable.
• the mixture was shaken briefly but vigorously, and cooled in a freezer for 30 minutes. Even when cold, still no precipitation of product occurred, so the acetone was removed via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This gave brown, viscous oil in quantitative yield that crystallized to a tan solid after standing at freezer temperature for several days.
• AKG-diTMEEA Diammonium Salt formed via the Reaction of alpha-ketoglutaric acid and tris[2-(2-(methoxyethoxy)ethyl]amine
• Example 16 Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS #328-50-7) and N, N-dimethyldodecylamine (CAS #112-18-5) in a 1:2 Molar Ratio.
• AKG-DiMeC12A N-dimethyldodecylamine
• Example 17 Formation of an Ammonium Salt via the Reaction of Pyruvic Acid (CAS #127-17-3) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio.
• a-ketoglutaric acid is a strong acid, wherein a solution of 0.114 g of a-ketoglutaric acid in 10 mL of water had a measured pH of 1.75. Consequently, the amount of the a- ketoglutaric acid in solution in a hydro alcoholic perfume base may have to be limited, to prevent alterations of the organoleptic properties on the perfume raw materials.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, to which, a mixture of orange, grapefruit, and bergamot oils was added.
• the mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• Approximately 240 mg (1.2% w/v) of ⁇ -ketoglutaric acid was dissolved in 20 mL of the mixed citrus perfume, and a POV measurement was taken the following day. The results are shown in the table below.
• Example 19 Reduction of POV in a Model Perfume According to One Aspect Presented Herein Using Oxaloacetic Acid
• Oxaloacetic acid is known to be unstable in aqueous solutions (see H. A. Krebs, Biochemistry (1942) 36, 303-305), leading to evolution of carbon dioxide and pyruvic acid. Nonetheless, oxaloacetic acid is effective in reducing the POV in solutions that will solubilize it (for example, hydroalcoholic perfumes). However, it is unclear whether the POV reduction occurs via oxaloacetic acid directly, or via liberated pyruvic acid, or both. An analysis of the reaction products (acetic acid versus malonic acid) could distinguish the two pathways, but this was not pursued here.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, to which, a mixture of orange, grapefruit, and bergamot oils was added.
• the mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• Approximately 166 mg (0.83% w/v) of oxaloacetic acid was dissolved in 20 mL of the mixed citrus perfume, and POV measurements were taken at the times indicated in the table below.
• the l-(2-hydroxyethyl)-2-imidazolidinone amine solution was added dropwise with stirring over the course of 3 minutes to the phenylglyoxylic acid solution; no visible indication of reaction was seen, and no warming was noticable.
• the mixture was shaken briefly but vigorously, and cooled in a freezer for 30 minutes. Even when cold, still no precipitation of product occurred, so the acetone solvent was removed via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This gave clear, pale yellow, highly viscous oil in quantitative yield.
• PhGA-HEI Diammonium Salt formed via the Reaction of phenylglyoxylic acid and 1 (2 hydroxy ethyl) -2 -imidazolidinone
• Example 21 Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS #328-50-7) and l-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS #3699-54-5) in a 1:2 Molar Ratio.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of lime, orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).
• Example 22 Formation of an Ammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS #328-50-7) and ⁇ , ⁇ -dimethyldodeclyamine (DiMeC12A, CAS #112-18-5) in a 1:1 Molar Ratio (referred to herein as AKG-mono(DiMeC12A)).
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of orange, grapefruit, and bergamot oils as the perfume oil. The mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• the solution was placed in a freezer for 30 minutes, during which time light pink needle-like crystals had fallen out.
• the mother liquor was removed with a pipet; it was shown to contain a substantial amount of lower purity material that could be further recovered by blowing down the solvent under a stream of nitrogen to give a deep orange solid.
• the two portions of product were recombined pending the development of a more efficient crystallization procedure.
• the yield was quantitative.
• a model perfume was made using 90/10 v/v ethanol/water as a solvent, and a mixture of orange, grapefruit, and bergamot oils as the perfume oil.
• the mixed citrus oil was loaded into the solvent at approximately 19.4% v/v (6 mL oil into 25 mL solvent).
• Approximately 244 mg (1.2% w/v) of the I-3-PA-NMDEA salt was dissolved in 20 mL of the mixed citrus perfume, and POV measurements were taken as a function of time after the addition.
• An untreated perfume sample was handled similarly to the treated perfume and also tested, because the POV can rise rapidly with handling of the sample (opening the bottle, agitation, etc.). The results are shown in the table below.
• Example 24 Reduction of POV in a Model Perfume According to One Aspect Presented Herein Using a Diammonium salt made from a-Ketoglutaric Acid (CAS #328-50-7) and N-methyl diethanolamine (NMDEA, CAS #105-59-9) in a 1:2 molar ratio Incorporated on a Solid Support. [0259] It had been observed that a reduction of POV in citrus oils could be produced even with a-oxocarboxylic acid salts that were practically insoluble in the citrus oil being treated.
• a single pad was cleaned as follows: The pad was placed in a 250 mL glass beaker and covered completely with pentane. The beaker was sonicated for three minutes, the pentane drained, and the procedure repeated with acetone. The acetone was also drained, and the pad dried in a vacuum oven at room temperature for one hour. The pad weighed 19.229 g both before and after the cleaning procedure, so no discernable weight loss was observed as a result of the cleaning.
• a solution was made from 3.0 g of AKG-DiNMDEA and 10 mL of fragrance grade ethanol.
• the pad was loaded by spreading the solution over the stainless steel pad via pipet, and drying the ethanol off under vacuum at room temperature. This was best accomplished with the solution split into about three portions, with a drying step in between each; there was some run-off when attempted in one portion, because the pad could not completely hold that much solution.
• the viscous AKG-DiNMDEA appeared to cling to the pad tightly enough so that the pad could be transferred between containers without loss of the liquid coating.
• Treatment of mixed citrus oil A sample of mixed citrus oil was made by combining lime, orange, grapefruit, and bergamot oils, so that a variety of terpene hydroperoxides would be present in the treated mixture being tested. Into two separate 250 mL glass bottles, 150 mL each of the mixed citrus oil was placed. This allowed for a significant atmospheric headspace to be present in the closed bottles, which would be replenished by fresh atmosphere/oxygen upon every opening of the bottle to withdraw an aliquot for testing. This arrangement was designed to mimic the oxygen exposure resulting from typical handling in production of a drum of citrus oil raw material, and should lead to realistic levels of autoxidation in the contained oils.
• the AKG-DiNMDEA coated pad was placed in one of the bottles (the Treated Sample) and totally submerged under the mixed citrus oil therein. In the second bottle, nothing besides the mixed citrus oil was placed (the Untreated Sample). These bottles were allowed to stand on the laboratory bench under ambient temperature and lighting conditions throughout the testing period. Periodically, an aliquot was withdrawn from each bottle for POV testing. Downward flow of the coating off of the pad, as evidenced by the appearance of a puddle of AKG-DiNMDEA collecting at the bottom of the vessel, took several weeks to occur to a noticeable extent. The interphase contact area presumably became lower as this flow progressed, likely reducing the efficiency of the reduction reaction. Nonetheless, significant protection of the treated citrus oil from autoxidation-induced POV increase occurred, as reported below.
• Example 25 Reduction of POV in a Selection of Consumer Products According to One Aspect Presented Herein.
• This Example reports the treatment of exemplary consumer product formulations.
• the consumer product formulations had a measurable level of oxidation as received, as shown in the table below, but the POV levels were low except the all-purpose cleaner. All of the samples had not been fragranced, so the POV was be associated with autooxidized base components.
• the five consumer product formulations were spiked with an extremely oxidized limonene that was produced in a photoreactor as a source of mixed limonene hydroperoxide isomers (the POV was 1434 mmol/L).
• the oxidized limonene was spiked into each at a level of 10 ⁇ ⁇ per gram, so approximately 14.3 mmol/L of POV would be added to the existing, as-received POV.
• Sample Preparation 40 mL (Sample #3) or 40 g (Samples #1, 2, 4 & 5) were each spiked with 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 as described in the table below with 0.5-1% (w/w) of a 2-oxocarboxylic acid ammonium salt, then mixed to homogeneity. Each of the five pairs of two samples, treated & un-treated, were allowed to stand on the benchtop in ambient laboratory light at room temperature, and POV measurements were taken periodically. The results are described below.
• Example 26 Reduction of POV in a Selection of Essential Oils Obtained from Non- Citrus Sources According to One Aspect Presented Herein.
• each oil sample was split in half, so two 10 mL aliquots were placed in separate vials to create a "Treated” and an "Untreated” sample.
• AKG-DiTMEEA was added as per the Dosing chart below.
• the pine oil had an extremely high POV, so the dosing 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 measurements were taken. It can be seen that 8 days of such handling of the untreated oils caused significant increases in POV measurement.

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