EP0235528A1 - Process for preparing stable ozonized oils from unsaturated vegetable oils - Google Patents
Process for preparing stable ozonized oils from unsaturated vegetable oils Download PDFInfo
- Publication number
- EP0235528A1 EP0235528A1 EP87100725A EP87100725A EP0235528A1 EP 0235528 A1 EP0235528 A1 EP 0235528A1 EP 87100725 A EP87100725 A EP 87100725A EP 87100725 A EP87100725 A EP 87100725A EP 0235528 A1 EP0235528 A1 EP 0235528A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- oils
- unsaturated vegetable
- ascorbic acid
- vegetable oils
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
Definitions
- the invention relates to a process for the production of stable ozonized oils from unsaturated vegetable oils with removal of physiologically questionable low molecular weight aldehydes and ketones.
- the process according to the invention provides valuable products which are suitable for therapeutic and cosmetic use in humans and animals.
- reaction of ozone with unsaturated fatty acids produces peroxidic products as therapeutically valuable active substances and low-molecular aldehydes and ketones, especially malondialdehyde, as undesirable by-products.
- the peroxidic products are used, for example, in dermatology for fungal diseases, leg ulcers, poorly healing wounds, infected wounds and the like.
- the ketones and aldehydes formed as by-products are therapeutically ineffective and largely physiologically questionable. The latter is particularly true for malondialdehyde, which occurs in considerable quantities when ozonization of unsaturated vegetable oils is complete (see Registry of Toxic Effects of Chemical Substances, U.S. Department of Health and Human Services, 1984).
- the object of the invention is to provide ozonized products from unsaturated vegetable oils which are therapeutically valuable products, are stable for a long time and have the lowest possible content of low molecular weight aldehydes and ketones, in particular malondialdehyde.
- the invention relates to a process for producing stable ozonized oils from unsaturated vegetable oils by introducing an ozone-oxygen mixture into the oil until saturation, which is characterized in that after the ozonization, an extraction treatment in an acidic environment in the presence of a redox system, preferably a biological redox system which is capable of a moderate radical reaction and which carries out in the presence of an artificial or natural antioxidant or reducing agent.
- a redox system preferably a biological redox system which is capable of a moderate radical reaction and which carries out in the presence of an artificial or natural antioxidant or reducing agent.
- unsaturated vegetable oils are olive oil, safflower oil, wheat germ oil, linseed oil, almond oil, nut oil, sunflower oil, poppy seed oil, sesame oil, castor oil, croton oil, soybean oil and palm oil. Olive and safflower oils are preferred. Olive oil is especially preferred.
- the redox system used which is capable of radical reactions, acts in the organism both as an electron acceptor and as an electron donor.
- Preferred examples of redox systems are ascorbic acid, the essentially membrane-associated redox system vitamin E, vitamin A and the biological quinoid / benzoid systems. Ascorbic acid is particularly preferred.
- a pH of 3.5 to 6.5 has proven to be particularly suitable for carrying out the extraction treatment.
- ascorbic acid or citric acid can be used.
- antioxidants or reducing agents are butylated hydroxyanisole, gallate and hydrogen sulfite.
- the ozone-oxygen mixture is produced in compliance with the regulations for the production or filling of medical oxygen.
- the ozone is generated by a silent electrical discharge (absolutely nitrogen-free to avoid the formation of aggressive and reactive nitrogen oxides, especially radicals).
- the ozonization of the oil is carried out with a continuous pass with a gas flow in the range of 1 to 2 liters per minute.
- the ozone concentration used is preferably in the range from 50 to 70 ⁇ g per ml.
- the oil is bubbled through using a cylindrical vessel with the highest possible “water column” with thermostatting at about 20 ° C.
- a continuous flow is important, especially just before the saturation limit, which becomes apparent when the product solidifies at 20 ° C.
- For 12 liters with a total height of the cylindrical vessel of 60 cm and a diameter of approx. 20 cm, a uniform bubbling time of 180 to 300 hours is required, depending on the ozone concentration of the initial ozone-oxygen mixture.
- aqueous extraction solution For the extraction treatment, about 2 to 20, in particular 3 to 10 and preferably about 5 ml of aqueous extraction solution are used per 1 g of ozonized oil.
- the extraction is preferably carried out by shaking for 10 to 60 minutes. The shaking process can be carried out several times to increase the effectiveness. Any excess sulfite still present in the extract can be removed by shaking out the oily phase with 2% aqueous ascorbic acid solution.
- Particularly preferred combinations for the extraction treatment according to the invention are ascorbic acid + butylated hydroxyanisole, citric acid and butylated hydroxyanisole as well as ascorbic acid and hydrogen sulfite.
- the determination is based on the reaction of malondialdehyde with 2-methylindole in alcoholic-hydrochloric acid solution to form a stable, intensely colored complex.
- Determination of malondialdehyde in ozonized oil About 1 g of the solid oil is weighed exactly and warmed to liquefy under an N2 atmosphere (approx. 30 ° C). Since the oil is immiscible with the reagents, 1 ml of distilled H2O are added in addition to 2 ml of methyl indole and stirred with a magnetic stirrer under the N2 atmosphere during the 20 min reaction time to allow a complete reaction of the malondialdehyde. The alcoholic phase is then measured (after the fat has been removed) in comparison with the calibration series that is applied in parallel each time.
- the product obtained has a peroxide number (POZ) of 929 and a malondialdehyde content of 445 ⁇ g / g of oil.
- the extraction treatment removed 85 percent of the malondialdehyde, while the peroxide number only decreased by 5.7 percent.
- the aqueous extract contains no peroxides, while the malondialdehyde has almost completely passed into the aqueous phase.
- Samples of the ozonated olive oil produced according to Example 1 are subjected to different extraction treatments. For this purpose, 1 g ozonized oil is shaken out with various aqueous solutions for 15 minutes. The POZ and malondialdehyde content are then determined. The results are summarized in the table below.
- x) 1 means that the parameter in question has not been determined
- x) 2 excess sulfite was completely removed by shaking the oil with 10 ml H2O (2 g ascorbic acid / 100 ml), whereby the POZ and malondialdehyde content of the ozonated oil did not change significantly: the peroxide number decreased from 876 to 860, the malondialdehyde content from 68 ⁇ g / g to 52 ⁇ g / g.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfharen zur Herstellung von stabilen ozonisierten Ölen aus ungesättigten Pflanzenölen unter Entfernung von physiologisch bedenklichen niedermolekularen Aldehyden und Ketonen. Das erfindungsgemäße Verfahren liefert wertvolle Produkte, die sich zur therapeutischen und kosmetischen Anwendung bei Mensch und Tier eignen.The invention relates to a process for the production of stable ozonized oils from unsaturated vegetable oils with removal of physiologically questionable low molecular weight aldehydes and ketones. The process according to the invention provides valuable products which are suitable for therapeutic and cosmetic use in humans and animals.
Die keimtötende Wirkung von ozonisiertem Olivenöl ist seit längerer Zeit bekannt (vgl. beispielsweise G. Cronheim, Journal of the American Pharmaceutical Association, Bd. 36 (1947), S. 274). Entsprechende Handelsprodukte wurden jedoch wegen ihrer leichten Zersetzbarkeit bald wieder aus dem Handel gezogen (vgl. M. Schönbauer, OzoNachrichten, Bd. 3 (1984), S. 28).The germicidal effect of ozonized olive oil has been known for a long time (see, for example, G. Cronheim, Journal of the American Pharmaceutical Association, Vol. 36 (1947), p. 274). Corresponding commercial products, however, were soon withdrawn from the market because of their easy decomposability (cf. M. Schönbauer, OzoNachrichten, Vol. 3 (1984), p. 28).
Bei der Umsetzung von Ozon mit ungesättigten Fettsäuren entstehen als therapeutisch wertvolle Wirkstoffe peroxidische Produkte und als unerwünschte Nebenprodukte niedermolekulare Aldehyde und Ketone, insbesondere Malondialdehyd.The reaction of ozone with unsaturated fatty acids produces peroxidic products as therapeutically valuable active substances and low-molecular aldehydes and ketones, especially malondialdehyde, as undesirable by-products.
Die peroxidischen Produkte werden aufgrund ihrer keimtötenden Wirkung gegenüber Bakterien, Pilzen und Hefen beispielsweise in der Dermatologie bei Pilzerkrankungen, Ulcus cruris, schlecht heilenden Wunden, infizierten Wunden und dergleichen eingesetzt. Demgegenüber sind die als Nebenprodukte gebildeten Ketone und Aldehyde therapeutisch ohne Wirkung und großenteils physiologisch bedenklich. Letzteres trifft insbesondere für Malondialdehyd zu, der bei vollständiger Ozonisierung von ungesättigten Pflanzenölen in nicht unbeträchtlichen Mengen auftritt (vgl. Registry of Toxic Effects of Chemical Substances, U.S. Department of Health and Human Services, 1984).Because of their germicidal action against bacteria, fungi and yeasts, the peroxidic products are used, for example, in dermatology for fungal diseases, leg ulcers, poorly healing wounds, infected wounds and the like. In contrast, the ketones and aldehydes formed as by-products are therapeutically ineffective and largely physiologically questionable. The latter is particularly true for malondialdehyde, which occurs in considerable quantities when ozonization of unsaturated vegetable oils is complete (see Registry of Toxic Effects of Chemical Substances, U.S. Department of Health and Human Services, 1984).
Aufgabe der Erfindung ist es, ozonisierte Produkte aus ungesättigten Pflanzenölen bereitzustellen, die therapeutisch wertvolle Produkte darstellen, über lange Zeit hinweg stabil sind und einen möglichst geringen Gehalt an niedermolekularen Aldehyden und Ketonen, insbesondere Malondialdehyd, aufweisen.The object of the invention is to provide ozonized products from unsaturated vegetable oils which are therapeutically valuable products, are stable for a long time and have the lowest possible content of low molecular weight aldehydes and ketones, in particular malondialdehyde.
Im Verlauf von Untersuchungen, die zur Lösung dieser Aufgabe angestellt wurden, wurde festgestellt, daß sich Malondialdehyd aus Produkten, die durch Einleiten eines Ozon-Sauerstoff-Gemisches bis zur Sättigung des Produkts erhalten worden sind, leicht zu weit über 50 Prozent mit Wasser extrahieren läßt. Dieses Verfahren ist jedoch nicht praktikabel, da dabei die therapeutisch nutzbaren Peroxide zu etwa 90 Prozent zerfallen. Erfindungsgemäß wurde ein spezielles Extraktionsverfahren aufgefunden, das eine weitgehende Entfernung von Malondialdehyd ermöglicht, ohne daß es zu einer erheblichen Verminderung der Peroxidzahl, die ein Maß für den Gehalt an peroxidischen Produkten und somit für die Güte des Produkts darstellt, kommt.In the course of investigations which were carried out to achieve this object, it was found that malondialdehyde can easily be extracted from water which has been obtained by introducing an ozone-oxygen mixture to saturation of the product to far more than 50 percent with water . However, this method is not practical since the peroxides which can be used therapeutically disintegrate to about 90 percent. According to the invention, a special extraction process has been found which enables extensive removal of malondialdehyde without significantly reducing the Peroxide number, which is a measure of the content of peroxidic products and thus of the quality of the product.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von stabilen ozonisierten Ölen aus ungesättigten Pflanzenölen durch Einleiten eines Ozon-Sauerstoff-Gemisches in das Öl bis zur Sättigung, das dadurch gekennzeichnet ist, daß man nach der Ozonisierung eine Extraktionsbehandlung in saurem Milieu in Gegenwart eines Redoxsystems, vorzugsweise eines biologischen Redoxsystems, das zu einer gemäßigten radikalischen Reaktion fähig ist und in Gegenwart eines künstlichen oder natürlichen Antioxidationsmittels oder Reduktionsmittels durchführt. Als ungesättigte Pflanzenöle kommen beispielsweise Olivenöl, Distelöl, Weizenkeimöl, Leinöl, Mandelöl, Nußöl, Sonnenblumenöl, Mohnöl, Sesamöl, Rizinusöl, Krotonöl, Sojaöl und Palmöl in Frage. Oliven- und Distelöl werden bevorzugt. Ganz besonders bevorzugt wird Olivenöl.The invention relates to a process for producing stable ozonized oils from unsaturated vegetable oils by introducing an ozone-oxygen mixture into the oil until saturation, which is characterized in that after the ozonization, an extraction treatment in an acidic environment in the presence of a redox system, preferably a biological redox system which is capable of a moderate radical reaction and which carries out in the presence of an artificial or natural antioxidant or reducing agent. Examples of unsaturated vegetable oils are olive oil, safflower oil, wheat germ oil, linseed oil, almond oil, nut oil, sunflower oil, poppy seed oil, sesame oil, castor oil, croton oil, soybean oil and palm oil. Olive and safflower oils are preferred. Olive oil is especially preferred.
Das verwendete Redoxsystem, das zu radikalischen Reaktionen fähig ist, wirkt im Organismus sowohl als Elektronenakzeptor als auch als Elektronendonator. Bevorzugte Beispiele für Redoxsysteme sind Ascorbinsäure, das im wesentlichen membranassoziierte Redoxsystem Vitamin E, Vitamin A und die biologischen chinoiden/benzoiden-Systeme. Besonders bevorzugt wird Ascorbinsäure.The redox system used, which is capable of radical reactions, acts in the organism both as an electron acceptor and as an electron donor. Preferred examples of redox systems are ascorbic acid, the essentially membrane-associated redox system vitamin E, vitamin A and the biological quinoid / benzoid systems. Ascorbic acid is particularly preferred.
Zur Durchführung der Extraktionsbehandlung hat sich ein pH-Wert von 3,5 bis 6,5 als besonders geeignet erwiesen. Zur Gewährleistung dieses pH-Bereichs können beispielsweise Ascorbinsäure oder Citronensäure eingesetzt werden.A pH of 3.5 to 6.5 has proven to be particularly suitable for carrying out the extraction treatment. To ensure this pH range, for example, ascorbic acid or citric acid can be used.
Bevorzugte Beispiele für Antioxidationsmittel bzw. Reduktionsmittel sind Butylhydroxyanisol, Gallat und Hydrogensulfit.Preferred examples of antioxidants or reducing agents are butylated hydroxyanisole, gallate and hydrogen sulfite.
Nachstehend wird die Erfindung unter Bezugnahme auf Olivenöl näher erläutert. Entsprechende Ausführungen gelten auch für die Verwendung von Distelöl und anderen ungesättigten Pflanzenölen.The invention is explained in more detail below with reference to olive oil. Corresponding statements also apply to the use of safflower oil and other unsaturated vegetable oils.
Es wird reines Olivenöl entsprechend DAB 8 verwendet. Die Herstellung des Ozon-Sauerstoff-Gemisches erfolgt dabei unter Beachtung der Vorschriften zur Herstellung oder Abfüllung von medizinischem Sauerstoff. Das Ozon wird durch stille elektrische Entladung (absolut stickstofffrei, um die Bildung von aggressiven und reaktionsfähigen Stickoxiden, insbesondere Radikalen, zu vermeiden) gebildet. Bei der Ozonisierung des Öls wird mit einem kontinuierlichen Durchlauf mit einem Gasfluß im Bereich von 1 bis 2 Liter pro Minute gearbeitet. Die verwendete Ozon-Konzentration liegt vorzugsweise im Bereich von 50 bis 70 µg pro ml. Die Durchperlung des Öls erfolgt unter Verwendung eines zylindrischen Gefäßes mit möglichst hoher "Wassersäule" unter Thermostatisierung bei ca. 20°C. Dabei ist ein kontinuierlicher Durchfluß, insbesondere kurz vor der Sättigungsgrenze, die sich durch Festwerden des Produkts bei 20°C bemerkbar macht, wichtig. Für 12 Liter bei einer Gesamthöhe des zylindrischen Gefäßes von 60 cm und einem Durchmesser von ca. 20 cm ist eine gleichmäßige Durchperlungszeit von 180 bis 300 Stunden je nach Ozonkonzentration des Ozon-Sauerstoff-Ausgangsgemisches erforderlich.Pure olive oil according to DAB 8 is used. The ozone-oxygen mixture is produced in compliance with the regulations for the production or filling of medical oxygen. The ozone is generated by a silent electrical discharge (absolutely nitrogen-free to avoid the formation of aggressive and reactive nitrogen oxides, especially radicals). The ozonization of the oil is carried out with a continuous pass with a gas flow in the range of 1 to 2 liters per minute. The ozone concentration used is preferably in the range from 50 to 70 μg per ml. The oil is bubbled through using a cylindrical vessel with the highest possible “water column” with thermostatting at about 20 ° C. A continuous flow is important, especially just before the saturation limit, which becomes apparent when the product solidifies at 20 ° C. For 12 liters with a total height of the cylindrical vessel of 60 cm and a diameter of approx. 20 cm, a uniform bubbling time of 180 to 300 hours is required, depending on the ozone concentration of the initial ozone-oxygen mixture.
Zur Extraktionsbehandlung werden pro 1 g ozonisiertes Öl etwa 2 bis 20, insbesondere 3 bis 10 und vorzugsweise etwa 5 ml wässrige Extraktionslösung verwendet. Die Extraktion erfolgt vorzugsweise durch eine 10- bis 60-minütige Ausschüttelung. Zur Steigerung der Effektivität kann der Ausschüttelvorgang mehrfach durchgeführt werden. Im Extrakt eventuell noch vorhandenes überschüssiges Sulfit kann durch Ausschütteln der öligen Phase mit 2-prozentiger wässriger Ascorbinsäurelösung entfernt werden.For the extraction treatment, about 2 to 20, in particular 3 to 10 and preferably about 5 ml of aqueous extraction solution are used per 1 g of ozonized oil. The extraction is preferably carried out by shaking for 10 to 60 minutes. The shaking process can be carried out several times to increase the effectiveness. Any excess sulfite still present in the extract can be removed by shaking out the oily phase with 2% aqueous ascorbic acid solution.
Maßgebend für die Qualität des Produkts sind insbesondere die Peroxidzahl, bestimmt gemäß Sully (DGF-Einheitsmethoden zur Untersuchung von Fetten, Fettprodukten und verwandten Stoffen, Deutsche Gesellschaft für Fettwissenschaft, Münster/Westfalen, 1950, S. 76) und der Gehalt an Malondialdehyd (bestimmt gemäß H. Scherz et al., Mikrochem. Acta, Heft 5, 1967).Decisive for the quality of the product are in particular the peroxide number, determined according to Sully (DGF standard methods for the investigation of fats, fat products and related substances, German Society for Fat Science, Münster / Westphalia, 1950, p. 76) and the content of malondialdehyde (determined according to H. Scherz et al., Mikrochem. Acta, Issue 5, 1967).
Besonders bevorzugte Kombinationen für die erfindungsgemäße Extraktionsbehandlung sind Ascorbinsäure + Butylhydroxyanisol, Citronensäure und Butylhydroxyanisol sowie Ascorbinsäure und Hydrogensulfit.Particularly preferred combinations for the extraction treatment according to the invention are ascorbic acid + butylated hydroxyanisole, citric acid and butylated hydroxyanisole as well as ascorbic acid and hydrogen sulfite.
Nachstehend wird die Erfindung anhand von Beispielen näher erläutert.The invention is explained in more detail below with the aid of examples.
Die Bestimmung beruht auf der Reaktion von Malondialdehyd mit 2-Methylindol in alkoholisch-salzsaurer Lösung zu einem beständigen, intensiv gefärbten Komplex.The determination is based on the reaction of malondialdehyde with 2-methylindole in alcoholic-hydrochloric acid solution to form a stable, intensely colored complex.
0,1 g 2-Methylenindol in 100 ml reinem EtOH gelöst; kurz vor der Verwendung 25 ml konz. HC1 zugesetzt.
Eichreihe: 45,86 mg Malondialdehydtetraäthylacetal werden mit 3 ml konz. HC1 versetzt und 3 min auf 50°C erwärmt. Danach wird mit destilliertem H₂O auf 500 ml ergänzt. 100, 200, 300, 400 und 500 µl dieser Lösung werden auf 1 ml aufgefüllt und mit 2 ml 2-Methylindollösung versetzt. Gleichzeitig wird ein Blindwert bestimmt, wobei 1 ml destilliertes H₂O mit 2 ml Reagenslösung versetzt wird. Nach 20 min wird die Extinktion bei 555 nm gemessen.0.1 g of 2-methylene indole dissolved in 100 ml of pure EtOH; shortly before use 25 ml conc. HC1 added.
Calibration series: 45.86 mg malondialdehyde tetraethyl acetal are mixed with 3 ml conc. HC1 added and heated to 50 ° C for 3 min. Then it is supplemented with distilled H₂O to 500 ml. 100, 200, 300, 400 and 500 µl of this solution are made up to 1 ml and 2 ml of 2-methanol solution are added. At the same time, a blank value is determined, 1 ml of distilled H₂O being mixed with 2 ml of reagent solution. After 20 min, the absorbance is measured at 555 nm.
Bestimmungen von Malondialdehyd im ozonisierten Öl: Etwa 1 g des festen Öls wird genau eingewogen und unter N₂-Atmosphäre zur Verflüssigung etwas erwärmt (ca. 30°C). Da das Öl mit den Reagentien nicht mischbar ist, werden außer 2 ml Methylindol noch 1 ml destilliertes H₂O zugesetzt und während der 20 min Reaktionszeit unter N₂-Atmosphäre mit einem Magnetrührer gerührt, um eine vollständige Reaktion des Malondialdehyds zu ermöglichen. Gemessen wird dann die alkoholische Phase (nach dem Absetzen des Fettes) im Vergleich mit der jedes Mal parallel angesetzten Eichreihe.Determination of malondialdehyde in ozonized oil: About 1 g of the solid oil is weighed exactly and warmed to liquefy under an N₂ atmosphere (approx. 30 ° C). Since the oil is immiscible with the reagents, 1 ml of distilled H₂O are added in addition to 2 ml of methyl indole and stirred with a magnetic stirrer under the N₂ atmosphere during the 20 min reaction time to allow a complete reaction of the malondialdehyde. The alcoholic phase is then measured (after the fat has been removed) in comparison with the calibration series that is applied in parallel each time.
In einem trockenen, entfetteten Kolben mit aufgesetztem Kühler werden 10 ml Eisessig und 10 ml Chloroform zur Entlüftung der Mischung 2 min unter Rückfluß erhitzt, danach 1 kg KJ in 1,3 ml H₂O (frisch zubereitet) zugegeben, ohne das Sieden zu unterbrechen, und nach weiteren 2 min etwa 1 g Öl (genau eingewogen) zugesetzt. Nach 4 min werden 50 ml destilliertes H₂O zugegeben und auf Zimmertemperatur abgekühlt.In a dry, degreased flask with an attached cooler, 10 ml of glacial acetic acid and 10 ml of chloroform are vented for 2 minutes under reflux to vent the mixture, then 1 kg of KJ in 1.3 ml of H₂O (freshly prepared) are added without boiling interrupt, and after a further 2 minutes add about 1 g of oil (weighed exactly). After 4 min, 50 ml of distilled H₂O are added and the mixture is cooled to room temperature.
Nach Zugabe von 1 ml 1-prozentiger Stärkelösung werden unter Umschwenken mit 0,1 n Natriumsulfatlösung bis zur Farblosigkeit der wässrigen Schicht titriert.After adding 1 ml of a 1% starch solution, titrate with 0.1 N sodium sulfate solution until the aqueous layer is colorless.
a ... verbrauchte ml Thiosulfatlösung
E ... Einwaage in ga ... used ml of thiosulfate solution
E ... weight in g
12 Liter Olivenöl (gemäß DAB 8) werden in ein zylindrisches Gefäß von ca. 20 cm Durchmesser gegeben. Die Füllhöhe beträgt ca. 60 cm. Das Gefäß wird auf 20°C thermostatisiert. Durch das GEfäß wird 240 Stunden lang gleichmäßig ein Ozon-Sauerstoff-Gemisch mit einer Durchlaufgeschwirdigkeit von 1 bis 2 Liter/min durchgeperlt. Dieses Ozon-Sauerstoff-Gemisch ist durch stille elektrische Entladung von reinem, stickstofffreiem Sauerstoff hergestellt worden. Seine Ozon-Konzentration beträgt ca. 60 µg/ml.12 liters of olive oil (according to DAB 8) are placed in a cylindrical vessel with a diameter of approx. 20 cm. The filling height is approx. 60 cm. The vessel is thermostatted to 20 ° C. An ozone-oxygen mixture with a flow rate of 1 to 2 liters / min is evenly bubbled through the vessel for 240 hours. This ozone-oxygen mixture was produced by the silent electrical discharge of pure, nitrogen-free oxygen. Its ozone concentration is approximately 60 µg / ml.
Das erhaltene Produkt weist eine Peroxidzahl (POZ) von 929 und einen Malondialdehyd-Gehalt von 445 µg/g Öl auf.The product obtained has a peroxide number (POZ) of 929 and a malondialdehyde content of 445 µg / g of oil.
100 g des ozonisierten Öls werden unter Stickstoffatmosphäre unter Rühren auf 30 °C bis zur Ver flüssigung langsam entfernt und mit 500 ml einer 2-prozentigen Ascorbinsäurelösung in Gegenwart von 5 ml 38-prozentiger NaHSO₃-Lösung versetzt. Nach 15-minütigem Ausschütteln werden die Phasen getrennt und die ölige Phase erneut mit 300 ml einer 2-prozentigen Ascorbinsäurelösung ausgeschüttelt, um das überschüssige Sulfit vollständig zu entfernen. Bei erneuter Peroxidzahlbestimmung des Produkts ergibt sich ein Wertvron 876. Im Wässrigen Extrakt ergibt sich eine POZ von 0. Das ölige Produkt ehthält Malondialdehyd in einer Menge von 68 µg/g Öl und der wässrige Extract 424 µg/g Extraktionsmittel.100 g of the ozonated oil are stirred under a nitrogen atmosphere at 30 ° C. until Ver liquid slowly removed and mixed with 500 ml of a 2 percent ascorbic acid solution in the presence of 5 ml of 38 percent NaHSO₃ solution. After shaking for 15 minutes, the phases are separated and the oily phase is shaken again with 300 ml of a 2% ascorbic acid solution in order to completely remove the excess sulfite. When the peroxide number of the product is determined again, a value of 876 results. The POZ in the aqueous extract is 0. The oily product contains malondialdehyde in an amount of 68 µg / g oil and the aqueous extract contains 424 µg / g extractant.
Dies bedeutet, daß durch die Extraktionsbehandlung der Malondialdehyd zu 85 Prozent entfernt worden ist, während sich die Peroxidzahl nur um 5,7 Prozent verrigerte. Der wässrige Extrakt enthält, wie gewünscht, keine Peroxide, während der Malondialdehyd fast vollständig in die wässrige Phase übergegangen ist.This means that the extraction treatment removed 85 percent of the malondialdehyde, while the peroxide number only decreased by 5.7 percent. As desired, the aqueous extract contains no peroxides, while the malondialdehyde has almost completely passed into the aqueous phase.
Proben des gemäß Beispiel 1 hergestellten ozonisierten Olivenöls werden unterschiedlichen Extraktionsbehandlungen unterworfen. Hierzu wird jeweils 1 g ozonisiertes Öl mit verschiedenen wässrigen Lösungen 15 Minuten lang ausgeschüttelt. Anschließend werden POZ und Malondialdehydgehalt ermittelt. Die Ergebnisse sind in nachstehender Tabelle zusammengestellt.
Sämtliche hier angeführten Werte sind Mittelwerte aus 2 Bestimmungen.
x)1 bedeutet, daß der betreffende Parameter nicht bestimmt wurde,
x)2 überschüssiges Sulfit wurde durch einmaliges Ausschütteln des Öls mit 10 ml H₂O (2 g Ascorbinsäure/100 ml) vollständig entfernt, wobei sich POZ und Malondialdehydgehalt des ozonisierten Öls nicht wesentlich veränderten: die Peroxidzahl sank von 876 auf 860, der Malondialdehydgehalt von 68 µg/g auf 52 µg/g.
X ButylhydroxyanisolAll values listed here are mean values from two determinations.
x) 1 means that the parameter in question has not been determined,
x) 2 excess sulfite was completely removed by shaking the oil with 10 ml H₂O (2 g ascorbic acid / 100 ml), whereby the POZ and malondialdehyde content of the ozonated oil did not change significantly: the peroxide number decreased from 876 to 860, the malondialdehyde content from 68 µg / g to 52 µg / g.
X butylated hydroxyanisole
Besonders günstige Ergebnisse werden demnach durch Kombination von Ascorbinsäure und Butylhydroxyanisol, Citronensäure und Butylhydroxyanisol sowie Ascorbinsäure und Hydrogensulfit erhalten.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87100725T ATE42965T1 (en) | 1986-03-01 | 1987-01-20 | PROCESS FOR THE PRODUCTION OF STABLE OZONIZED OILS FROM UNSATURATED VEGETABLE OILS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3606735A DE3606735C2 (en) | 1986-03-01 | 1986-03-01 | Process for the production of stable ozonized oils from unsaturated vegetable oils |
DE3606735 | 1986-03-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0235528A1 true EP0235528A1 (en) | 1987-09-09 |
EP0235528B1 EP0235528B1 (en) | 1989-05-10 |
Family
ID=6295281
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87100725A Expired EP0235528B1 (en) | 1986-03-01 | 1987-01-20 | Process for preparing stable ozonized oils from unsaturated vegetable oils |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0235528B1 (en) |
AT (1) | ATE42965T1 (en) |
DE (1) | DE3606735C2 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996025409A1 (en) * | 1995-02-16 | 1996-08-22 | Cosmart Ag | Cosmetic or pharmaceutical compositions containing an ozonide-enriched natural vegetable oil, and uses thereof |
FR2784388A1 (en) * | 1998-10-07 | 2000-04-14 | Bernard Sonnois | Ozonized oil obtained using pure oxygen, useful as cellular regeneration promoter in cosmetic or pharmaceutical applications, e.g. for treating skin, joint or circulatory disorders |
WO2000078699A1 (en) * | 1999-06-18 | 2000-12-28 | E.I. Du Pont De Nemours | Oxidative cleavage of unsaturated oils and products obtained therefrom |
WO2001037829A1 (en) * | 1999-11-25 | 2001-05-31 | Gomez Moraleda Manuel Antonio | Composition comprising ozonized oils and/or other ozonized natural and/or synthetic products and their use in pharmaceutical, cosmetic, dietetic or food supplement compositions in human and veterinary medicine |
WO2006021924A1 (en) * | 2004-08-26 | 2006-03-02 | Pieter Josua Le Roux | Therapeutic oil from plant origine |
EP1681338A1 (en) * | 2003-10-02 | 2006-07-19 | Sun Care Fuels Corporation | Modifier for biodiesel fuel, fuel, methods relating to those |
WO2007046122A2 (en) * | 2005-10-17 | 2007-04-26 | Bioo3Pharma S.R.L. | Ozonised oil, process for the preparation and use thereof in medical field |
WO2010039064A1 (en) * | 2008-10-03 | 2010-04-08 | Sca Hygiene Products Ab | Wipe with odour control substance |
RU2462271C1 (en) * | 2008-10-03 | 2012-09-27 | Ска Хайджин Продактс Аб | Deodorising wet wipes |
ITUB20155250A1 (en) * | 2015-11-24 | 2017-05-24 | Apuzzo Dario | New nutraceutical composition, orally administered, useful for exercising a powerful stimulation of the metabolism, in particular of the muscular energy metabolism. |
IT202000024967A1 (en) * | 2020-10-23 | 2022-04-23 | Giovanni Sandomenico | OZONIZED FLUID FOR PROTECTION - DEFENSE OF THE FIRST RESPIRATORY TRACT |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10157260B4 (en) * | 2001-11-22 | 2005-12-15 | Pharmoxid Arznei Gmbh + Co. Kg | Spreadable ointment with ozonides and peroxides of fatty acids or their esters |
DE102012007239A1 (en) | 2012-04-10 | 2013-10-10 | Wolfgang Winkelmann | A pharmaceutical composition containing an oxygenated unsaturated fatty acid and an organic solvent |
DE102015001289A1 (en) | 2015-01-29 | 2016-08-04 | Wolfgang Winkelmann | Pharmaceutical compositions and pesticides containing oxygenated vegetable oils or fatty acids |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2083572A (en) * | 1928-04-25 | 1937-06-15 | Susan M Mckee | Process of treating oil |
DE1068251B (en) * | 1959-11-05 | Chemische Fabrik Stockhausen S. Oie, Krefeld | Process for the production of water-soluble or emulsifiable, electrolyte-resistant lubricants |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5869207A (en) * | 1981-10-21 | 1983-04-25 | Nippon Petrochem Co Ltd | Purification of epoxidized product |
DE3373675D1 (en) * | 1983-01-06 | 1987-10-22 | Lepeltier Marie Francoise | Process for the preparation of peroxydated fats by biological low energy transformation, products obtained by this process, mixtures of these products with additives and new medicines made up of these products |
-
1986
- 1986-03-01 DE DE3606735A patent/DE3606735C2/en not_active Expired - Fee Related
-
1987
- 1987-01-20 AT AT87100725T patent/ATE42965T1/en not_active IP Right Cessation
- 1987-01-20 EP EP87100725A patent/EP0235528B1/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1068251B (en) * | 1959-11-05 | Chemische Fabrik Stockhausen S. Oie, Krefeld | Process for the production of water-soluble or emulsifiable, electrolyte-resistant lubricants | |
US2083572A (en) * | 1928-04-25 | 1937-06-15 | Susan M Mckee | Process of treating oil |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996025409A1 (en) * | 1995-02-16 | 1996-08-22 | Cosmart Ag | Cosmetic or pharmaceutical compositions containing an ozonide-enriched natural vegetable oil, and uses thereof |
FR2730636A1 (en) * | 1995-02-16 | 1996-08-23 | Cosmart Ag | NATURAL VEGETABLE OIL ENRICHED IN OZONIDES, COSMETIC OR PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME AND USES THEREOF |
FR2784388A1 (en) * | 1998-10-07 | 2000-04-14 | Bernard Sonnois | Ozonized oil obtained using pure oxygen, useful as cellular regeneration promoter in cosmetic or pharmaceutical applications, e.g. for treating skin, joint or circulatory disorders |
WO2000078699A1 (en) * | 1999-06-18 | 2000-12-28 | E.I. Du Pont De Nemours | Oxidative cleavage of unsaturated oils and products obtained therefrom |
US6768029B1 (en) | 1999-06-18 | 2004-07-27 | Cambridge Biopolymers Limited | Oxidative cleavage of unsaturated oils and products obtained therefrom |
WO2001037829A1 (en) * | 1999-11-25 | 2001-05-31 | Gomez Moraleda Manuel Antonio | Composition comprising ozonized oils and/or other ozonized natural and/or synthetic products and their use in pharmaceutical, cosmetic, dietetic or food supplement compositions in human and veterinary medicine |
ES2162586A1 (en) * | 1999-11-25 | 2001-12-16 | Moraleda Manuel Gomez | Composition comprising ozonized oils and/or other natural and/or synthetic ozonized products and use thereof in pharmaceutical, cosmetic, dietetic or food supplement compositions, in the human and veterinary fields |
EP1681338A1 (en) * | 2003-10-02 | 2006-07-19 | Sun Care Fuels Corporation | Modifier for biodiesel fuel, fuel, methods relating to those |
EP1681338A4 (en) * | 2003-10-02 | 2008-11-19 | Sun Care Fuels Corp | Modifier for biodiesel fuel, fuel, methods relating to those |
WO2006021924A1 (en) * | 2004-08-26 | 2006-03-02 | Pieter Josua Le Roux | Therapeutic oil from plant origine |
WO2007046122A2 (en) * | 2005-10-17 | 2007-04-26 | Bioo3Pharma S.R.L. | Ozonised oil, process for the preparation and use thereof in medical field |
WO2007046122A3 (en) * | 2005-10-17 | 2007-06-14 | Biopharma 3M S R L | Ozonised oil, process for the preparation and use thereof in medical field |
WO2010039064A1 (en) * | 2008-10-03 | 2010-04-08 | Sca Hygiene Products Ab | Wipe with odour control substance |
RU2462271C1 (en) * | 2008-10-03 | 2012-09-27 | Ска Хайджин Продактс Аб | Deodorising wet wipes |
ITUB20155250A1 (en) * | 2015-11-24 | 2017-05-24 | Apuzzo Dario | New nutraceutical composition, orally administered, useful for exercising a powerful stimulation of the metabolism, in particular of the muscular energy metabolism. |
IT202000024967A1 (en) * | 2020-10-23 | 2022-04-23 | Giovanni Sandomenico | OZONIZED FLUID FOR PROTECTION - DEFENSE OF THE FIRST RESPIRATORY TRACT |
Also Published As
Publication number | Publication date |
---|---|
ATE42965T1 (en) | 1989-05-15 |
DE3606735C2 (en) | 1994-11-10 |
EP0235528B1 (en) | 1989-05-10 |
DE3606735A1 (en) | 1987-09-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0235528B1 (en) | Process for preparing stable ozonized oils from unsaturated vegetable oils | |
DE3874428T2 (en) | MULBERRY TREE EXTRACTS CONTAINING LIPOSOME COMPOSITION. | |
EP0060553B1 (en) | Preparation for treating outer skin wounds and process for manufacturing said preparation | |
DE69807070T2 (en) | TOCOFEROL ESTERN AND THEIR USE IN COSMETICS AND PHARMACEUTICAL | |
DE4210112A1 (en) | POLYETHOXYLATED VITAMIN E AND METHOD FOR THE PRODUCTION THEREOF | |
DE1917393A1 (en) | Perfumed and flavored products | |
DE2102172C3 (en) | New means of treating and caring for the skin | |
DE3633453A1 (en) | COMPOSITIONS BASED ON LYSINE AND ARGININE SALTS | |
DE2700448C2 (en) | Ointment for the treatment of ulcus cruris | |
DE2129654B2 (en) | Medicament for reducing capillary permeability and increasing capillary stability from the extraction of the flavanol-containing fruits of Vitis vinifera | |
AT414082B (en) | PROCESS FOR THE PREPARATION OF TOCOTRIENOL-ENRICHED PREPARATIONS | |
EP0339382B1 (en) | Process for deodorizing mixtures of fatty acid esters | |
DE69711633T2 (en) | STABLE DERIVATIVES OF UBIQUINOL, METHOD FOR THE PRODUCTION THEREOF AND THEIR PHARMACEUTICAL USE | |
DE19728609C2 (en) | Triglyceride-sorbic acid-pantothenyl-acetal peroxides from natural vegetable oils | |
DE3643323C2 (en) | ||
EP0005121B1 (en) | Process for stabilisation of 4-methyl-5-(2'-chlorethyl)-thiazol | |
DE1568320B2 (en) | Cosmetic active ingredient and cosmetic agent with water-retaining properties | |
DE580515C (en) | Process for the production of triaryl stib iodides and their solutions | |
EP0951904B1 (en) | Agent for enhancing dermal microcirculation | |
DE2855860C2 (en) | Process for the purification of organic peroxides containing water | |
DE2531260A1 (en) | D-panthenol anhydrous spray solutions - contg an oil as solvent and an alcohol and a chlorinated hydrocarbon as solubilisers | |
DE60122696T2 (en) | METHODS AND COMPOSITION FOR IMPROVED OXYGEN FEED FOR CELLS | |
DE2714342C2 (en) | Bis (acetylsalicylic acid) thiaalkanediol ester and therapeutic composition | |
DE850054C (en) | Toilet or shaving soap | |
DE624231C (en) | Process for the production of hydrogenated tachysterin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH FR IT LI NL |
|
17P | Request for examination filed |
Effective date: 19871015 |
|
17Q | First examination report despatched |
Effective date: 19880713 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH FR IT LI NL |
|
REF | Corresponds to: |
Ref document number: 42965 Country of ref document: AT Kind code of ref document: T |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: DR. ING. A. RACHELI & C. |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20031217 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20040116 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20040129 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20040130 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20040413 Year of fee payment: 18 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050120 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050131 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050131 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050131 |
|
BERE | Be: lapsed |
Owner name: *J. HANSLER G.M.B.H. Effective date: 20050131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050801 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050930 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20050801 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
BERE | Be: lapsed |
Owner name: *J. HANSLER G.M.B.H. Effective date: 20050131 |