EP1246884A1 - Verfahren zum schutz einer substanz, die zur oxidativen zersetzung neigt - Google Patents

Verfahren zum schutz einer substanz, die zur oxidativen zersetzung neigt

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Publication number
EP1246884A1
EP1246884A1 EP99959658A EP99959658A EP1246884A1 EP 1246884 A1 EP1246884 A1 EP 1246884A1 EP 99959658 A EP99959658 A EP 99959658A EP 99959658 A EP99959658 A EP 99959658A EP 1246884 A1 EP1246884 A1 EP 1246884A1
Authority
EP
European Patent Office
Prior art keywords
substance
antioxidant
compositions
food
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99959658A
Other languages
English (en)
French (fr)
Inventor
Rena Reznik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RAD International Ltd
Original Assignee
RAD International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RAD International Ltd filed Critical RAD International Ltd
Priority claimed from PCT/IL1999/000693 external-priority patent/WO2000039248A1/en
Publication of EP1246884A1 publication Critical patent/EP1246884A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation

Definitions

  • the present invention relates to protecting a substance liable to oxidative deterioration and to materials which are so protected
  • antioxidant material is isolated from rosemary by extraction with a non-polar solvent, removal of the solvent and steam distillation, giving an aqueous dispersion, which was filtered, antioxidant being obtained from the solid material by further processing including extraction with aqueous alkali at pH at least 10 5
  • An isolated antioxidant is 7 ⁇ , 11 , 12-t ⁇ hydroxy-6, 10-(epoxymethano)ab ⁇ eta- 8,11 ,13-t ⁇ en-20-one
  • US 4,877,635 (Todd) describes a process for producing an oil-soluble extract of a Labiatae herb claimed to contain essentially all of the antioxidant substances in the herb, in the course of which acetone- or methyl ethyl ketone-insolubles, defined as pro-oxidant substances, are, so far as practicable, removed by precipitation US 5,023,017 (Todd) relates to a stable Labiatae antioxidant solution, having a pH 84-11 8, prepared from an initial solvent extract of the herb, and claimed to contain (besides ⁇ 75% water, and an edible alcohol and/or polyol) essentially all of the antioxidant substances in the herb, which is preferably rosemary, sage or thyme
  • rosmarinic acid is valuable in view of its antnnflammatory properties, see e g US 4,329,361 (Zenk et al )
  • rosmarinic acid is also known for its use in skin-treatment or cosmetic compositions, see e g JP 63162611 , JP 9067251 and US 5,393,526 (Castro)
  • rosmarinic acid is claimed to be useful in a composition for protection against erythema and inflammatory reactions caused by exposure to UV rays, and to have antioxidant, antibacterial and antifungal activity, see FR 2652001 (cf JP 06145034)
  • the action of rosmarinic acid as a 5-l ⁇ poxygenase inhibitor is also featured in JP 1121217, where, extracted from pe ⁇ lla species, it is used as a constituent of an antiallergic food
  • a still further object of the invention is to provide a process protection for a substance liable to oxidative deterioration by inclusion of water-soluble antioxidant material prepared by permitting maximum recovery of the industrially useful components from plants of the Labiatae family, such components including essential oils, completely water-soluble antioxidant material and known components which are both water-insoluble and organic solvent soluble, such as vitamin E and carnosic acid
  • the present invention accordingly provides in one aspect a substance liable to oxidative deterioration, which is characterized by the fact that it incorporates as antioxidant for that substance, at least one compound selected from sub-groups ( ⁇ ), ( ⁇ ) and ( ⁇ ), namely ( ⁇ ) rosmarinic acid,
  • the invention provides use of at least one compound selected from sub-groups ( ⁇ ), ( ⁇ ) and ( ⁇ ), namely ( ⁇ ) rosmarinic acid, ( ⁇ ) salts of the carboxylic acid function in rosmarinic acid, ( ⁇ ) esters and amides of the carboxylic acid function in rosmarinic acid, in admixture with a substance liable to oxidative deterioration, in at least a minimum amount necessary to confer antioxidative protection on said substance, provided that when said substance is a dermato-cosmetic composition, said at least one compound is used in an amount less than 0 1 % of the admixture, and that said at least one compound excludes mixtures in a form as extracted from natural sources and comprising any compound in sub-groups ( ⁇ ), ( ⁇ and ( ⁇ ), together with any other ant ⁇ ox ⁇ dant(s)
  • the invention provides a method for treating a substance liable to oxidative deterioration, in order to confer antioxidative protection on said substance, which comprises admixing said substance with at least one compound selected from sub-groups ( ⁇ ), ( ⁇ ) and ( ⁇ ), namely ( ⁇ ) rosmarinic acid, ( ⁇ ) salts of the carboxylic acid function in rosmarinic acid, ( ⁇ ) esters and amides of the carboxylic acid function in rosmarinic acid, in at least a minimum amount necessary to confer said protection on said substance, provided that when said substance is a dermato-cosmetic composition, said at least one compound is used in an amount less than 0 1 % of the admixture, and that said at least one compound excludes mixtures in a form as extracted from natural sources and comprising any compound in sub-groups ( ⁇ ), ( ⁇ and ( ⁇ ), together with any other ant ⁇ ox ⁇ dant(s)
  • the proviso as to the dermato-cosmetic composition excludes the disclosure of FR 2,652,
  • FIG. 1 illustrates chromatographic fractionation of antioxidant material from rosemary, having utility in accordance with an embodiment of the invention
  • FIG. 2 illustrates chromatographic fractionation of antioxidant material from oregano, having utility in accordance with an embodiment of the invention
  • antioxidant in a form selected from completely water-soluble materials containing a major proportion of non-antioxidant diluent, and which are solid at ambient temperatures, and aqueous solutions thereof,
  • said antioxidant comprises at least one of
  • a sodium rosma ⁇ nate preferably isolated from tissue of plants of the Labiatae family, most preferably by use of an aqueous extractant
  • the substance incorporating antioxidant according to the invention is selected from sub-groups (I), (II) and (III), namely
  • compositions (I) pharmaceutical compositions, cosmetic compositions, animal feedstuff compositions and food compositions adapted for human consumption,
  • compositions selected from pharmaceutical compositions, cosmetic compositions, animal feedstuff compositions and food compositions adapted for human consumption,
  • compositions selected from pharmaceutical compositions, cosmetic compositions, animal feedstuff compositions and food compositions adapted for human consumption, which composition comprises an ingredient liable to oxidative deterioration
  • Such food composition may be e g , selected from sugar-based confectionery, manufactured cereals, fruit or vegetable products, beverages or beverage concentrates, ground meat products and vegetable analogues thereof
  • Such food composition may comprise at least one additional ingredient selected from the water-soluble vitamins thiamine, ⁇ boflavin, niacin, py ⁇ doxine, pantothenic acid, biotin, fo c acid, cobalamin and ascorbic acid, the oil-soluble vitamins retinol, calciferol, tocopherol and menadione, in combined form the elements sodium, potassium, calcium, phosphorus, magnesium, chlorine, sulfur, iron, copper, iodine, manganese, cobalt, zinc molybdenum, fluorine, selenium and chromium, unsaturated fatty acids which are known to metabolized in the body to prostaglandins, and physiologically compatible derivatives of said fatty acids, food colorants and pigments, acceptable dispersing and suspending agents, and
  • an amount of ant ⁇ ox ⁇ dant(s) effective to prevent oxidation of the ingredient liable to oxidative deterioration should be used Generally, from about 0 0001 to about 1 %, preferably from about 0 0005 to about 0 1% by weight of the food composition may be used, depending on the nature of the composition and the type of oxidative activity which is to be inhibited
  • Colorants or pigments, used in food compositions, which are liable to oxidative deterioration are for example, polyene pigments and colorants such as ⁇ -carotene
  • compositions which contain fats or oils comprising fatty acids or their esters, either saturated or unsaturated may be preserved using ant ⁇ ox ⁇ dant(s) according to the invention
  • fatty acids are well known and are listed in Noller, Textbook of Organic Chemistry, 2nd Ed pp 108-113 and 138-146 (1958), which is incorporated by reference herein
  • Typical but non-limiting examples of food compositions, including fats and oils adapted for use therein, are soybean oil, corn oil, cottonseed oil, olive oil, butter, margarine, salad creams and mayonnaises, dairy products, ice cream, frozen vegetables, soups, fried foods and
  • a particular aspect of the present invention resides in the use of rosmarinic acid and its derivatives as described herein, for the purpose of antioxidative protection of vitamins and their analogs and functional derivatives of the vitamins and the analogs
  • the water-soluble vitamins thiamine, ⁇ boflavin, niacin, py ⁇ doxine, pantothenic acid, biotin, fo c acid, cobalamin and ascorbic acid the oil-soluble vitamins retinol, calciferol, tocopherol and menadione, and their analogs and functional derivatives thereof, especially such analogs and derivatives having analogous biological activity
  • vitamins which are themselves known to be antioxidants in particular ascorbic acid (including its salts and esters) and ⁇ -tocopherol (including its esters) can themselves be protected from deterioration by use of rosmarinic acid and its derivatives
  • the substance liable to oxidative deterioration, the oxidation which is inhibited in accordance with the present invention includes the essential oils, such as those derived, for example, from citrus fruit and flowers
  • the antioxidants utilized in accordance with the invention are selected from rosmarinic acid, salts of the carboxylic acid function in rosmarinic acid, and esters and amides of the carboxylic acid function in rosmarinic acid Rosmarinic acid may be isolated from natural sources e g as described in certain of the above-mentioned published documents, or it (and indeed its salts, esters and amides) may be chemically synthesized It may also be made by enzymatic or cell culture procedures, see e g US 5,011 ,775 (Rao) and published documents mentioned therein, the contents of this patent and of such documents, being incorporated herein by reference
  • Example 1 shows inter alia that the prior art practice of obtaining antioxidant material from Labiatae family plants, from organic solvent soluble extracts, while rejecting aq fractions, and/or rejecting acetone-insolubles, results in substantial loss of potentially valuable antioxidant Moreover, Example 1 (c) shows surprisingly, that contrary to Viani and Todd, useful completely water-soluble antioxidant material can be obtained by alkaline extraction
  • the method is based on the rate of oxidation of linoleic acid (LA) to its conjugated diene hydroperoxide (Pryor et al , in J Org Chem , 1993, 58 (13) 3521 -3532), and 2,2'-azob ⁇ s (2-am ⁇ d ⁇ nopropane) 2HCI (ABAP) is used to provide a constant rate of radical production
  • LA linoleic acid
  • ABAP 2,2'-azob ⁇ s (2-am ⁇ d ⁇ nopropane) 2HCI
  • a 1 % LA aq emulsion was prepared with 1 % Tween 20 and 0 05M sodium phosphate buffer (pH 7 4)
  • a control sample contained 0 025 ml of the LA emulsion + 2 87 ml of the buffer + 0 1 ml 0 05M ABAP
  • a test sample contained 0 05 ml of the LA emulsion + 2 7-2 8
  • a column of 8cm x 1cm is packed with MacroPrep-methyl (hydrophobic interaction 40 ⁇ m, Bio-Rad) was washed exhaustively with water and ethanol, and then used for purification of the water extract lyophilizate (see Example 1(f), above) 200 mg of the lyophilizate was dissolved in 1 ml water, and the solution was loaded on the MacroPrep column that had been pre-equilibrated with water Elution was carried out using a 0 1 % acetic acid/ 70 30 ethanol in water gradient starting with a 100 0 ratio at 0 minutes and ending with a 0 100 ratio at 220 minutes, and at a flow rate of 2 0 ml/minute Peaks are monitored by UV absorption at 280nm The column effluent was collected after 85 minutes (193 ml) and the active material was found to be eluted between 85 to 100 minutes (36 ml, 30-40%o ethanol (balance water))
  • a concentrate was first prepared containing 40% lecithin, 40% oil (e g soybean oil), 20% propylene glycol and 4% based on the foregoing mixture of 65% ( ⁇ 2 6% pure) sodium rosmannate Rosmarinic acid can alternatively be substituted for the sodium salt
  • the thus-prepared concentrate can then be used in a bulk oil which it is desired to protect against oxidative deterioration
  • oil is soybean oil
  • test results at 60°C were as follows Antioxidant Concentration Days until oxidation
  • Vitamin E 0 06% 4

Landscapes

  • Cosmetics (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP99959658A 1998-12-24 1999-12-22 Verfahren zum schutz einer substanz, die zur oxidativen zersetzung neigt Withdrawn EP1246884A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL12772498A IL127724A0 (en) 1998-12-24 1998-12-24 Method for protecting a substance liable to oxidative deterioration
PCT/IL1999/000693 WO2000039248A1 (en) 1998-12-24 1999-12-22 Method for protecting a substance liable to oxidative deterioration

Publications (1)

Publication Number Publication Date
EP1246884A1 true EP1246884A1 (de) 2002-10-09

Family

ID=11072296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99959658A Withdrawn EP1246884A1 (de) 1998-12-24 1999-12-22 Verfahren zum schutz einer substanz, die zur oxidativen zersetzung neigt

Country Status (2)

Country Link
EP (1) EP1246884A1 (de)
IL (1) IL127724A0 (de)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0039248A1 *

Also Published As

Publication number Publication date
IL127724A0 (en) 1999-10-28

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