FR2896172A1 - NOVEL METHOD FOR STABILIZING POLYUNSATURATED FATTY ACIDS AND THE COMPOSITIONS THUS OBTAINED - Google Patents

Abstract

The present invention relates to the necessities of life, more particularly to food, nutrition and food supplements. The invention more precisely relates to a process for producing a powder coated with rich vegetable or animal oil fatty acid type omega-3 which consists of lamination of the omega-3 fatty acid-rich oil previously atomized and stabilized by addition of catechins, rendered fat-soluble by esterification with a fatty acid. Use in the agri-food, nutritional, dietary, neuraceutical, cosmetic and pharmaceutical fields.

Description

New process for stabilizing polyunsaturated fatty acids and

  compositions thus obtained. The present invention relates to the necessities of life, more particularly to food, nutrition and food supplements.

  The subject of the invention is a process for producing a film-coated powder for vegetable or animal oil, rich in omega-3 fatty acids, which consists in lamination of the high-yield oil. Omega-3 previously atomized. This oil is itself previously stabilized by adding catechins, in particular those extracted from green tea, and rendered fat-soluble by esterification with a fatty acid. Omega-3 fatty acids are important fatty acids; nutritional and therapeutic point. These are polyunsaturated acids of the n-3 series which come from various plant extracts such as rapeseed or soybean oil, kiwi seed oil, blackcurrant seed oil, oil 20 hazelnuts, or animal products such as fish, including tuna, halibut, sardines, cod liver, haddock, or even shark. Alpha-linolenic acid (ALA), which is itself an essential fatty acid, eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), is distinguished in this family. Scientists have been alerted to the many benefits of EPA and DHA in the 1970s, when Danish researchers observed that the Eskimos of Greenland had an unusually low incidence of heart disease and arthritis despite 30 they consumed a particularly rich diet er. fats for the needs of their survival. Research has shown that the fatty acids they absorb in greater quantities, EPA and DHA, are really beneficial to health. More recent research has shown that fish oils play an important role in the prevention of atherosclerosis, heart attacks, depression, and even cancer. Clinical trials have shown that fish oil replacement is effective in treating many health problems, including rheumatoid arthritis, diabetes, ulcerative colitis and Raynaud's disease. Omega-3 fatty acids have many virtues for the cardiovascular system and the central nervous system of young children, and are essential for metabolism to ensure development and growth. Thus, DHA and EPA have important biological properties in cellular functions, particularly in the central nervous system, and for the cardiovascular system. DHA and EPA are essential for a normal maturation of the nervous system of fetuses and young children, especially with regard to visual abilities and cognitive functions.

  Omega-3 fatty acids are widely used today as agri-food ingredients, particularly in certain foods; dairy products (butter, yogurts) enriched in omega-3 fatty acids, and in the nutraceutical field as dietary supplements, especially as cardioprotective agents, and more recently as factors regulating emotions.

  It is estimated that 85% of people in the western world have a deficient diet of Omega-series fatty acids. The recommended dose of EPA + DHA is 650 mg / day, increased to 1,000 mg during pregnancy and lactation. These values are very rarely al: hues.

  In clinical trials, daily doses of between 1 and 10 grams have been used, but few beneficial effects have been reported with doses greater than 5 grams / day of combined EPA + DHA. The clinical improvement following the beginning of the administration is manifest after a few weeks on the blood parameters (triglycerides and fibrinogen levels), but it can be manifested only after 3 months or more, of treatment in the diseases degenerative diseases such as atherosclerosis and rheumatoid arthritis.

  The formulation and packaging of the Omega-3 series rich fatty acid products are crucial for the quality and preservation of these products. The poor quality oils are not stable and may contain some undesirable and unreactive oxidation products. Good quality oils are often stabilized by the addition of vitamin E and are packaged in such a way as to protect them from light and oxygen. The problem has arisen of finding a way to greatly increase the stability of the Omega-3 family-containing compounds, and to enable them to act effectively and for a prolonged period of time. Various existing methods are intended to protect the fatty substances and in particular the fatty acids of the Omega family from oxidation. It is generally a question of incorporating stabilizing products such as antioxidants which help to limit their degradation and unsaturated oils. their conversion into epoxy or ketone derivatives.

  Indeed, the polyunsaturated fatty acids obtained are characterized by an insufficient degree of stability and not optimal, the degradation of the active ingredients occurring relatively quickly which leads to a decrease in activity of these compounds, themselves used for their antioxidant action .

  Another major problem concerns the galenic forms of currently available products on the market, particularly for Omega-3 fatty acid-based food supplements, which has been booming for some years now. The available forms are obviously not satisfactory because it is most often soft capsules. These capsules have a large volume which makes it difficult o-i for the least uncomfortable, their oral absorption. The usual dosage consists in taking one or more capsules daily for a long time (at least 2 months per treatment), and it is easy to understand that the availability of a suitable dosage form, that is to say easily unmanageable, is an essential problem. The object of the present invention is to develop a method which makes it possible to stabilize a fatty acid rich oil of the Omega-3 family, and to protect it from the subsequent oxidation in a substantially improved manner by means of a physical barrier.

  The subject of the invention is specifically a new process for stabilizing an oil rich in omega-3 fatty acids, by film coating which consists in applying a micro-coating to the oil previously made pulverulent.

  The invention also relates to the pulverulent products resulting from this method of manufacturing oil rich in omega-3 fatty acids.

  Micro-coating consists of trapping very fine solid or liquid particles of oil inside a membrane. This technology was born from research in the field of printing: one of the first applications was the creation of carbonless paper. Since then it has spread to various fields such as agrochemistry, food industry, pharmacy, and cosmetics. The interest of the microcapsules lies in the fact that the membrane which constitutes the outer coating, can be brought to play very different roles which can be divided into two categories: The first category concerns the membranes which behave like a waterproof wall vis- with respect to the content, which it releases when the time comes in destroying itself. The desired aim may be a protection of the contents against oxidation, light (the coating coat is then colored), hygroscopy, evaporation (for very volatile products such as essential oils), acidity, alkalinity, or protection of the user: protection of the gastric mucosa, masking of taste and smell for example The second category concerns membranes that behave like an active barrier: they are membranes semipermeable permitting exchanges between the inside and the outside of the capsule with modification of the chemical affinities.

  The encapsulation of enzymes or probiotics aims to delay or control their release. Indeed, the envelope is made of neutral matter completely assimilable by the body and the digestive enzymes digest it gradually. 45% of the shell is digested six hours after its ingestion. This kinetics being perfectly known, it is possible to release the active ingredient thus coated either at the level of the small intestine, for example, or continuously in the body, even if it is necessary to double coat the substance in a different manner, those times successively, by means of coating agents of different nature.

  The encapsulation techniques are very varied, and include for example: atomization, spray drying, emulsion, cold spraying, granulation and liposomes. Encapsulation techniques are numerous, but they are not always satisfactory in terms of protection of the compounds, or in terms of cost of production. Three microencapsulation techniques have been used for many years (over twenty years): membrane encapsulation in liposomes, matrix encapsulation with various polymers, molecular encapsulation in cyclodextrins. 5 First case: Liposomes

  The liposome is defined as a vesicle whose wall is formed of one or more layers, most often of a phospholipidic nature, enclosing an aqueous internal space. It is thus possible to encapsulate active principles of very different solubility (hydrophilic, amphiphilic and lipophilic). The liposomal vesicle is defined by two characteristics: its structure and its composition. This liposome term applies essentially to the entity comprising a ~ o vesicle and a composition containing phospholipids. Thus, there are related forms, non-vesicular lipid or phospholipid complexes. The related forms could be described as systems organized in aqueous phase comprising phospholipids and also vesicles formulated with nonionic surfactants called niosomes. The liposome formulation is complex; there are many requirements related to the approved raw materials, the technology of preparation, the characteristics of the active molecule to be encapsulated and finally the requirements related to the desired application (stability, release and targeting). Second Case: Polymers Polymers are formed by the binding of a large number of smaller molecules called monomers. Polymers in the natural state include proteins, DNA and latexes, such as rubber. Synthetic polymers include glass, concrete and plastics. The polymers used are usually lactic acid-based polymers such as polylactic acid and polylactic co-glycolic acid. Polymers have different shapes and sizes. They may be in the form of a tube or in a circular form enclosing the drug within the design of the polymer. They can also be biodegradable or non-biodegradable. Biodegradable polymers such as polylactic acid and polylactic / poly-glycolic acid are generally used since they must not be metabolized. Polymers can disseminate the substances they contain either by dissolution, diffusion, or osmosis. Once the capsule is dissolved, the protected product is disseminated during the dissolution period of the polymer. Mixing with various dissolution rates and layer structuring of the polymers: controls the amount released. • In diffusion, the dissemination of the protected product is controlled by the diffusion rate of the polymer. In osmosis, the protected product is contained in a polymer composed of two compartments: one compartment contains the active product and the other contains an inactive agent which can release the active product under certain conditions - an assistance layer.

  Third Case: Molecular Encapsulation Many mineral or organic molecules such as cyclodextrins, have a "cavity" allowing them to give rise to inclusion complexes. In this process, the "host" molecule admits into its cavity one or more other "guest" molecules without any covalent bond being established. The complexity of the complex is therefore only based on the quality of adaptation between the partners. These "molecular trap" properties are used in many fields to provide ion exchangers, catalysts, or to separate the components of complex mixtures. The present invention therefore consists of a novel method of protecting polyunsaturated fatty acids by microencapsulation coating of the grains after atomization to protect an oil rich in polyunsaturated fatty acids of the n-3 or n-6 series, from the oxidation by atmospheric oxygen.

  The manufacturing method that is the subject of the invention comprises the following two successive steps: Atomization: The first operation consists of emulsifying an oil rich in polyunsaturated fatty acids that can belong to the n-3 or n-6 series previously stabilized by addition of antioxidant. The antioxidant used is most often a polyphenol extract of green Io tea made liposoluble and added at a height of about 1500 ppm. A fish oil containing 35% of the omega-3 family thus protected is at least 5 times more stable than its non-antioxidated control when it is subjected to bubbling with air at a temperature of 80 ° C. atomization). It should be noted that the compounds resulting from the esterification of the oil, rich in fatty acids of the Omega-3 family by catechins extracted from green tea are the subject of a particular prior patent, in the name of the Applicant (patent application filed November 8, 2005 We have the 0511354 on behalf of the company POLARIS). The emulsion formulation contains mainly mannitol, glucose syrup, soy protein, caseinate, soy lecithin and water (about 60%) to which the oil (approx. %) is mixed and homogenized. The emulsion then contains approximately 40% to 50% solids. The quality of the emulsion is essential for the quality of the encapsulation by atomization: stability of the emulsion, size of the lipid globules that is to say fine (<1 m) and uniform distribution.

  During these various operations, an emphasis must be placed so as to limit the initiation of oxidation phenomena, that is to say to avoid mainly the incorporation of oxygen (air) and temperature rises. For this purpose, it is preferable to deaerate the water and to homogenize under vacuum or under pressure an inert gas (nitrogen). The powder is obtained by spray drying of this liquid and stable emulsion (at 40% solids content) (on a VIRO equipment, for example). The inlet temperatures are about 150 C. The exit temperatures are about 85 C.

  EXAMPLE 1 Composition of the powder obtained after drying: 50% polyunsaturated oil (in the form of an oil sold under the name EPAX 1050 TG originating from marine oils containing about 70% of EPA and DHA.) Glucose 27.7% D-Mannitol 10.0% Soybean Protein 5.0% Caseinate 5.0%, Antioxidants / Stabilizers 1.0% (Sodium Ascorbate, Tocopherols, Green Tea Extract.) Tetrasodium Diphosphate 0.5 % Calcium phosphate (fluidizer) 0.50 / 0 Soy lecithin 0.5% Micro-coating:

  The micro-coating technique used in the context of the present invention is a particular method of encapsulation, which includes the fact that a coating matrix is sprayed directly onto the omega-3-rich oil previously made pulverulent by atomization.

  The micro-coating technique consists in the fact that a matrix is sprayed on a powder in fluidization. This operation takes place after the atomization previously described. The coating matrix used is composed only of a vegetable fat (palm, coconut) with a high melting point. Example 2: Specifications of the coating matrix used: SOURCE: Fractions Palme / coco

  SPECIFICATIONS: Based on Natural Vegetable Fat: Melting Point 58-60 C Peroxide Index meq / Kg Max 2 Acid Index mgKOH / g Max 1 Iodine Value Index gI / 100g Max 5 Saponification Value mgKOH 185 - 215

  Fatty acid profile: (% of relative area GC) By GC Lauric acid C 12: 0 Max 0.2 Myristic acid C 14: 0 0.8-1.2 Palmitic acid C16: 0 30.0-34.0 Stearic acid C 18: 0 58.0-62.0 Acid elaidic C 18: 1 n-9 trans Max 3.5% oleic acid C 18: 1 n-9 cis 2.5-3.5 alpha linoleic acid C 18: 2 n6 0.1-0.3 arachidic acid C 20: 0 0.2-0.4

  To this matrix, 2 to 3% of soy lecithin is added. The latter has the particularity of forming a protective film vis-à-vis oxygen, air. In addition, lecithin increases the plasticity of the coating matrix.

  It is also useful to incorporate dyes or flavorings into the coating matrix. Film-coating is a short-duration operation, of the order of less than 5 minutes, and preferably less than 2 minutes.

  According to the process that is the subject of the present application, the powder is put into fluidization by mechanical means (blades). Other techniques use a heated atomized air bed (or N 2) (eg Glatt material, Hütling, etc.). In advance, the powder is preheated to about 30 ° C. so that the fat deposited can spread around the particle. The fat lo is sprayed at a temperature slightly above the melting point. The duration of mixing and spraying is short, and does not exceed three minutes. At the outlet, the coated powder is at about 40 ° C. If possible, it is preferable to cool the powder immediately. The amount of fat coating represents 10 to 13% of the total. The compounds obtained by means of the lecrit manufacturing process, are characterized by a quite remarkable stability, in comparison with products of the market themselves in the form of concentrated omega-3 oil powder. Typical composition of the powder obtained after coating: Polyunsaturated oil 44.5% Glucose syrup 24.5% Coating fat 10.7% D-Mannitol 10.0% Soy protein 4.5% Caseinate 14.5% Antioxidants / stabilizers 0.9% (sodium ascorbate, tocopherols, green tea extract.) Tetrasodium diphosphate 0.7% Calcium phosphate (fluidizer) 0.4% Soy lecithin 0.4% Example 3: Evaluation of stability of the compound according to the invention The stability of the product according to the invention was evaluated compared to oil powders concentrated in Omega-3 acids market. The stability test consists of measuring the evolution over time of the Peroxide Index (meqO / kg) in a sample of the test compound. This index increases with the degree of oxidation, that is to say the degradation of the test compound, the oxygen it contains being degraded to peroxide. The increase in the peroxide number is therefore inversely proportional to the degree of stability of the test compound. It is characteristic of the oxidation stability of the analyzed sample.

  The stability tests of the samples compared are carried out under identical conditions, placing the samples in the open air and at ambient temperature maintained at 25 ° C.

  The plot of the evolution of the peroxide index as a function of time (in 20 weeks) is established for the sample according to the invention, and for a sample of product of the market for comparison. The samples tested comprise an equivalent concentration of Omega-3 fatty acids, ie 180 mg DHA / g for the compound according to the invention, and 175 mg DHA / g for the commercial compound at the initial stage. The oxidation stability of two oil samples was compared. The results are collated in Figure 1.

  It appears that the peroxide index is maintained at a very low level for at least 30 weeks (less than 10) for the product prepared according to the invention, whereas the product of the market reaches 20 from the 10th week of conservation, to exceed 60 meqO / kg from the 20th week of conservation.

  The Omega-3 powder in question is produced by several known techniques (emulsification / atomization and micro-coating of an Omega-3 oil), the conjugation of which results in a powder of high stability (composition A) compared to the competing products d-. The compositions according to the invention thus have a much longer shelf life than the commercially available products, and can be advantageously used for all known applications of Omega-3 fatty acids in homeopathic products. : agri-food, nutritional, dietary, nutraceutical, cosmetic and pharmaceutical.

Claims (14)

  1. A method for stabilizing preparations rich in polyunsaturated fatty acids of the n-3 or n-6 series, characterized in that the oil of plant or animal origin, rich in polyunsaturated fatty acids previously made pulverulent by addition of filler and spray, spraying with a coating matrix directly onto the oil using a mixture of high melting point fats for micro-coating.   2. The method of claim 1, wherein the micro-coating operation is performed for a short time.   3. Method according to claim 1 or claim 2, characterized in that the micro-coating operation is carried out in less than 5 minutes.   4. Method according to one of the preceding claims, wherein the coating matrix used for the microencobage, is sprayed at a temperature slightly above the melting point.   5. Method according to one of the preceding claims, wherein the microencobage of the oil of vegetable or animal origin, previously made pulverulent, is performed by a mixture of palmitic acid and stearic acid.   6. Method according to one of the preceding claims, wherein the coating matrix is composed mainly of a vegetable fat based on palm oil and / or coconut oil high melting point.   7. Method according to one of the preceding claims, characterized in that the oil of plant or animal origin, rich in polyunsaturated fatty acids is previously stabilized by incorporation of antioxidants.   8. The method of claim 7 wherein is added to the microencobage matrix a protective film forming agent with respect to the oxygen of the air.   The process of claim 8 wherein the film forming agent is a lecithin.   The method of claim 7 wherein the amount of lecithin added ranges from 2 to 3%.   A method of stabilizing against oxidation of polyunsaturated fatty acid-rich preparations according to claim 7, characterized in that the amount of coating fat is 10 to 13% of the total.   12. Oils rich in polyunsaturated fatty acids obtained by a process according to one of the preceding claims, which contain 44.5% of polyunsaturated oil, 10.7% of coating fat and between 2 and 3% of lecithin of polyunsaturated fatty acid. soy.   13. Use of the oils rich in polyunsaturated fatty acids according to claim 12, in food, nutritional, dietary, nutraceutical, pharmaceutical and / or cosmetic preparations as a stabilizing or antioxidant agent.   14. Use of oils rich in polyunsaturated fatty acids according to claim 12, for all known applications of omega-3 acids in the food industry, so as to produce high stability products containing polyunsaturated fatty acids.