![]() PROTEIN HYDROLYSAT OF FABACEES AS A HYPOALLERGENIC PROTEIN SOURCE IN FOOD COMPOSITIONS
专利摘要:
The subject of the present invention is a protein hydrolyzate of Fabaceae, in particular of bean and / or faba bean, its process of preparation and its use as a protein source, in partial or total replacement of cow's milk proteins, in food compositions. Protein hydrolyzate Fabaceae, especially bean or faba bean, according to the invention has improved nutritional properties, especially in terms of amino acid composition and digestibility, and provides a hypoallergenic protein source in food compositions . Such food compositions are thus particularly suitable for feeding infants, adolescents, pregnant or lactating women and the elderly. 公开号:FR3076982A1 申请号:FR1850508 申请日:2018-01-23 公开日:2019-07-26 发明作者:Astrid Leichtnam Marie-Laure;Monique Broca Stephanie 申请人:LABORATOIRES GILBERT; IPC主号:
专利说明:
FABACEOUS PROTEIN HYDROLYSAT AS A HYPOALLERGENIC PROTEIN SOURCE IN FOOD COMPOSITIONS Technical area The present invention relates to protein-based food compositions. State of the art Proteins are one of the three main families of macronutrients found in food. Proteins are all made up of the same amino acids, only the proportion and sequence of which vary. Man uses only 20 amino acids to meet his structural, functional and energy needs. Among these 20 amino acids, 8 are said to be "essential", that is to say that the body cannot synthesize them; they must therefore be brought exclusively by food. These are isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan and valine. In addition, there are 2 semiessential amino acids: arginine and histidine which must, in some cases, be assimilated through food. So there are ten non-essential amino acids that are synthesized by the body itself. These are alanine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, proline, serine and tyrosine. Proteins mainly have two food origins: animal and vegetable. Animal protein comes from milk, meat, fish, crustaceans and eggs. Vegetable proteins are found mainly in cereals and legumes. Certain plants such as algae, reported by their dry weight, are also rich in protein. The quality of food protein intake is mainly related to the composition of essential amino acids and digestibility. The overall quantification of amino acids in a protein fraction (essential and semi-essential amino acids) is compared to a reference protein to calculate its chemical index (CI). This reference protein was established virtually on the basis of the technical, analytical and epidemiological data available to date; its composition makes it possible to cover all the essential amino acid requirements. Proteins of animal origin naturally have a high CI (CI> 100), which is generally higher than proteins of plant origin. The Dietary Reference Intakes are estimated at 50 g of protein / day for an adult. If these intakes are covered by animal proteins, then the essential amino acid requirements are also covered. On the other hand, certain vegetable proteins may have a limited content of one or more essential amino acids (IC <100), for example lysine for cereals and sulfur amino acids (methionine, cysteine) for legumes. So, with an equal protein supply, vegetable proteins will not meet the essential amino acid requirements, while animal proteins will meet them. Digestibility, on the other hand, is generally slightly higher for animal proteins than for vegetable proteins. In human food, animal proteins therefore meet needs better than vegetable proteins. However, the availability of animal proteins is starting to be limited due to saturated production and the harmful effects of their production on the environment. Infant formulas are partial or total substitutes for breast milk. Infant formulas have historically been developed from cow's milk. Their composition has evolved over time to improve their nutritional and digestive properties. However, in recent decades, the growing number of allergic reactions and sensitizations to cow's milk proteins, even after protein hydrolysis, have led to the development of alternatives to animal protein hydrolysates, which are classified as hypoallergenic. These alternative preparations completely devoid of animal proteins (cow or goat), contain vegetable proteins hydrolyzed or not, such as soy or rice proteins. Soy is a protein crop that has been used for many years. However, soy contains isoflavones, i.e. plant hormones that have pseudo-estrogenic properties that can interfere with the hormonal system of humans and therefore with the development of children. Some methods reduce the level of isoflavone in soybeans, but cannot completely eliminate it. On the other hand, the increased use of soy in diets has led to an increase in allergies to soy. As for rice, this cereal has the disadvantage of having a low level of lysine, an essential amino acid. On the other hand, rice contains high levels of arsenic, which requires specific purification treatments and / or batch selections, but without real control of this contaminant. There is always a need for alternative solutions making it possible to provide protein food compositions, in particular infant formulas, having both a hypoallergenic character and good nutritional qualities, in particular in terms of amino acid composition and protein digestibility. detailed description The inventors have highlighted a new protein source having nutritional qualities close to those of cow's milk proteins, while being hypoallergenic. This new protein source is of plant origin. It is a protein hydrolyzate of Fabaceae, preferably broad bean and / or faba bean. The vegetable protein hydrolyzate of Fabaceae, in particular of broad bean and / or faba bean, according to the invention has many advantages: it is rich in proteins (at least 85%, preferably at least 90%, more preferably at least 95 % protein by mass of dry matter), has a sodium concentration of less than 4.5%, preferably less than 4%, for example less than 0.2%, does not include gluten, has a controllable content of contaminants and presents an aminogram as close as possible to the reference protein, ie the theoretical ideal protein meeting human needs. It preferably does not include trace elements capable of interacting with the hormone-pituitary system. Furthermore, the process for producing the vegetable protein hydrolyzate according to the invention is simple to implement and makes it possible to produce the hydrolyzate on an industrial scale with a good yield, for example greater than 23%, while preserving the initial qualities of the vegetable protein source, in particular of the broad bean and / or field bean. The process for producing the vegetable protein hydrolyzate advantageously makes it possible to obtain a hydrolyzate with a low sodium content and a high purity. The plant protein hydrolyzate of Fabaceae, in particular of broad bean and / or field bean, according to the invention is therefore particularly suitable for the preparation of food compositions intended for the feeding of infants, adolescents, pregnant or lactating women and the elderly. A first object of the invention is a vegetable protein hydrolyzate of Fabaceae, characterized in that it comprises at least 85% protein, the percentage being expressed in g per 100 g of dry matter of the protein hydrolyzate, and in that that it comprises sodium at a concentration of less than 4.5%, the percentage being expressed in g per 100 g of the protein hydrolyzate. The vegetable protein hydrolyzate as defined above is preferably a bean and / or faba bean vegetable protein hydrolyzate. The vegetable protein hydrolyzate as defined above is preferably obtained by enzymatic hydrolysis. Another object of the invention is a food composition comprising a vegetable protein hydrolyzate as defined above. The food composition is preferably selected from the group consisting of an infant preparation, bar, snack, powder preparation, dessert cream, cottage cheese, milk-based shake, fruit shake, drinking yogurt, cookie, bread, rusk, pasta and soup. Another subject of the invention is a process for the preparation of a plant protein hydrolyzate of Fabaceae, in particular as defined above, comprising the following steps: a) solubilization of the proteins of a Fabaceae flour in an aqueous medium at a pH less than or equal to 8.5, in order to obtain solubilized proteins, b) optionally, purification of said solubilized proteins, to obtain purified solubilized proteins, said purification step preferably comprising a precipitation step at a pH of 4 to 5, c) enzymatic hydrolysis of the solubilized proteins, to obtain a vegetable protein hydrolyzate, d) optionally drying said protein hydrolyzate and / or freezing. Another subject of the invention is a process for preparing a food composition, characterized in that said process comprises a step of mixing at least one vegetable protein hydrolyzate as defined above or obtained according to the process such as defined above with at least one other food ingredient. Another subject of the invention relates to the use of a vegetable protein hydrolyzate as defined above or obtained according to the method as defined above, as partial or total substitute for proteins from cow's milk, rice, soy and / or any other protein source, in a food composition, in particular for reducing the allergenic nature of said composition, reducing the content of contaminant (s) in said composition and / or obtaining a composition without isoflavone. Vegetable protein matter The protein material used to obtain the protein hydrolyzate according to the invention is therefore a vegetable protein material from a plant. The vegetable protein material is preferably obtained from a legume of the family Fabaceae, more preferably of the genus Vicia, even more preferably of the species Vicia faba. Vicia faba is a broad bean or field bean. The vegetable protein material can be obtained from a variety of broad bean or faba bean or from a mixture of at least two varieties of broad bean and / or broad bean. The vegetable protein material is preferably obtained from at least one bean of the variety selected from the group consisting of the variety Seville bean, Aguadulce, Marsh bean, Muchamiel and Piccola and / or from at least one faba bean the variety selected from the group consisting of the variety Olan, Diva, Iréna, Castel (formerly called Axel), Espresso, Divine, Gladice, Organdi, Nordica and Diver. The vegetable protein material is preferably obtained from a faba bean of the Olan variety and / or from a faba bean of the Iréna variety. The vegetable protein material can be obtained from the whole plant or from a part of the plant, for example root, stem, leaf and / or seed. The terms "seed" and "seed" are synonymous here. In a preferred embodiment, the part of the plant used to obtain the vegetable protein material is the seed. The seed is preferably shelled beforehand. The vegetable protein material can be a flour, a concentrate and / or an isolate. A flour generally comprises from 23% to 33% of vegetable proteins (the percentage being expressed in g per 100 g of flour). Flour can be obtained by husking and grinding seeds, in particular bean and / or faba bean seeds. A vegetable protein concentrate generally comprises from 60 to 75% vegetable proteins (the percentage being expressed in g per 100 g of concentrate). A concentrate of vegetable protein material can be obtained from a flour as defined above, for example by a turboseparation step. Turboseparation eliminates large particles of starch. A vegetable protein isolate generally comprises at least 85% vegetable protein, for example from 85% to 90% or at least 90% protein (the percentage being expressed in g per 100 g of isolate). A vegetable protein isolate can be obtained by a protein extraction step, either from a flour as defined above, or from a concentrate as defined above. The protein extraction step generally comprises a step of solubilization of proteins at basic pH greater than or equal to 9, for example in the presence of water and sodium hydroxide, and a step of precipitation of proteins at isoelectric pH, preferably at pH 4.5. The precipitation step can be followed by a centrifugation step. An isolate of vegetable protein matter is made up of native proteins, that is to say proteins little or not transformed compared to the proteins contained in the initial grain. Native proteins retain their initial chain lengths and therefore have a high molecular weight. Vegetable protein hydrolysate The vegetable protein hydrolyzate is obtained from a vegetable protein material as defined above. The vegetable protein hydrolyzate is therefore a protein hydrolyzate of legumes, preferably of the Fabaceae family, more preferably of the genus Vicia, more preferably still of the species Vicia faba. The vegetable protein hydrolyzate is preferably a bean and / or faba bean protein hydrolyzate. The vegetable protein hydrolyzate can be in liquid form, in particular in frozen liquid form, or in dry form. The frozen liquid form and the dry form allow indeed a good conservation of the vegetable protein hydrolyzate. In a preferred embodiment, the vegetable protein hydrolyzate is in dry form. The expression "in dry form" means that the vegetable protein hydrolyzate comprises at least 95%, preferably at least 96%, preferably at least 97%, more preferably at least 98%, more preferably still at least 99% dry matter, the percentage being expressed in g per 100 g of the hydrolyzate. The plant protein hydrolyzate in dry form is, for example, lyophilized or atomized. By “atomized vegetable protein hydrolyzate” is meant a spray-dried vegetable protein hydrolyzate. The vegetable protein hydrolyzate is preferably a hydrolyzate as defined above comprising at least 85% protein, the percentage being expressed in g per 100 g of dry matter of the protein hydrolyzate. The protein content can be measured by any method well known to those skilled in the art. The protein content is for example obtained by multiplying by 6.25 the mass of nitrogen in the composition, the latter being obtained by the Kjeldhal method. The vegetable protein hydrolyzate is preferably a hydrolyzate as defined above, characterized in that it is low in sodium. The vegetable protein hydrolyzate thus preferably comprises sodium at a concentration of less than 4.5% (the percentage being expressed in g per 100g of the protein hydrolyzate). The vegetable protein hydrolyzate as defined above is preferably characterized by an ash content greater than or equal to 3%, for example greater than or equal to 3.5% or 4%, the percentage being expressed in g per 100g of the protein hydrolyzate. In a particular embodiment, the protein hydrolyzate as defined above is for example characterized by an ash content greater than or equal to 6%, preferably greater than or equal to 7%, the percentage being expressed in g per 100 g of l protein hydrolyzate. By the term "ash" is meant the solid residues remaining after the combustion of the vegetable protein hydrolyzate. A preferred protein hydrolyzate is a protein hydrolyzate as defined above comprising peptides of average size less than 700 Da, preferably less than 650 Da, more preferably less than 620 Da, more preferably still less than 600 Da. In a particular embodiment, the protein hydrolyzate comprises peptides of average size less than 590 Da, for example less than 585 Da or less than 560 Da. The vegetable protein hydrolyzate is for example a hydrolyzate as defined above comprising: - sodium at a concentration of less than 4.5%, more preferably less than 4%, the percentage being expressed in g per 100g of the protein hydrolyzate, - at least 85% protein, the percentage being expressed in g per 100g of dry matter of the protein hydrolyzate, - an ash content greater than or equal to 3%, the percentage being expressed in g per 100g of the protein hydrolyzate and / or - peptides of average size less than 600 Da. In an advantageous embodiment, the vegetable protein hydrolyzate is a hydrolyzate as defined above comprising: - sodium at a concentration of less than 4.5%, more preferably less than 4%, the percentage being expressed in g per 100g of the protein hydrolyzate, - at least 85% protein, the percentage being expressed in g per 100g of dry matter of the protein hydrolyzate, - an ash content greater than or equal to 7%, the percentage being expressed in g per 100g of the protein hydrolyzate, and / or - peptides of average size less than 600 Da. Such a hydrolyzate is for example obtained using a preparation process as defined below, in which the pH is adjusted with a solution of sodium hydroxide during the step of solubilization of proteins. In another advantageous embodiment, the vegetable protein hydrolyzate is a hydrolyzate as defined above comprising: sodium at a concentration of less than 1%, more preferably less than 0.5%, more preferably still less than 0.2%, the percentage being expressed in g per 100g of the protein hydrolyzate, - calcium at a concentration greater than or equal to 0.5%, more preferably greater than or equal to 1%, more preferably still greater than or equal to 1.4%, the percentage being expressed in g per 100 g of the protein hydrolyzate, - at least 90% protein, preferably at least 94% protein, the percentage being expressed in g per 100g of dry matter of the protein hydrolyzate, - an ash rate greater than or equal to 3% and / or less than 6%, the percentage being expressed in g per 100g of the protein hydrolyzate, and / or - peptides of average size less than 570 Da, preferably less than 560 Da. Such a hydrolyzate is for example obtained using a preparation process as defined below, in which the pH is adjusted with lime during the step of solubilization of proteins. The vegetable protein hydrolyzate according to the invention is hypoallergenic. By the term "hypoallergenic" is meant here a product whose ingestion causes little or no allergic reaction. The hypoallergenic nature of a product can be evaluated as illustrated in example 2. The vegetable protein hydrolyzate according to the invention does not include gluten and, preferably, does not include isoflavone. The vegetable protein hydrolyzate according to the invention comprises less than 0.1 ppm, preferably less than 0.08 ppm, more preferably less than 0.05 ppm of arsenic. The plant protein hydrolyzate according to the invention mainly comprises proteins of lower molecular weight than native proteins (i.e. not hydrolyzed), thus allowing better intestinal absorption of these proteins. The vegetable protein hydrolyzate preferably comprises at least 85%, preferably at least 88%, more preferably at least 90% of proteins having a molecular weight of less than 3 kDa, the percentage being expressed in g per 100 g of protein. The vegetable protein hydrolyzate preferably comprises at least 55%, preferably at least 60%, more preferably at least 62%, more preferably at least 64% of proteins having a molecular weight of less than 1 kDa, the percentage being expressed in g per 100 g of protein. In an advantageous embodiment, the protein hydrolyzate comprises at least 64% or at least 68% of proteins having a molecular weight of less than 1 kDa, the percentage being expressed in g per 100 g of protein The vegetable protein hydrolyzate preferably comprises at least 40%, preferably at least 45%, more preferably at least 50%, of proteins having a molecular weight of less than 0.8 kDa, the percentage being expressed in g per 100 g of proteins. In an advantageous embodiment, the protein hydrolyzate comprises at least 50%, at least 52% or at least 55% of proteins having a molecular weight of less than 0.8 kDa, the percentage being expressed in g per 100 g of protein . The vegetable protein hydrolyzate preferably comprises at least 4%, preferably at least 4.5%, more preferably at least 4.8%, for example at least 5%, of proteins having a molecular weight of less than 0.204 kDa. The vegetable protein hydrolyzate preferably comprises: - at most 0.10%, preferably at most 0.06%, of ornithine, - from 2.8% to 4.1%, preferably from 3.1% to 3.5% of threonine, - from 8.8% to 12.3%, preferably from 9.4% to 11.8% of aspartic acid, - from 3.8% to 5.7%, preferably from 4.1% to 5.4% of serine, - from 5.4% to 8.5%, preferably from 5.8% to 7.9% of lysine, - from 3.8% to 5.2%, preferably from 4.1% to 4.7% of valine, - from 3.4% to 4.7%, preferably from 3.6% to 4.4% of proline, - from 3.3% to 4.5%, preferably from 3.5% to 4.1% of alanine, - from 3.6% to 4.9%, preferably from 3.7% to 4.5% of phenylalanine, - from 3.2% to 4.6%, preferably from 3.4% to 4.2% of isoleucine, - from 3.3% to 4.5%, preferably from 3.5% to 4.3% of glycine, - from 2.4% to 3.9%, preferably from 2.6% to 3.4% of tyrosine, - from 7.8% to 11.0%, preferably from 8.3% to 10.0% of arginine, - from 5.9% to 8.3%, preferably from 6.4% to 7.6% of leucine, - from 2.1% to 3.4%, preferably from 2.3% to 3.2% of histidine, - from 14.4% to 21.3%, preferably from 15.5% to 20.0% of glutamic acid, - from 0.6% to 1.1%, preferably from 0.69% to 0.82% of tryptophan, - from 0.4% to 0.9%, preferably from 0.63% to 0.73% of methionine, and / or - from 0.4% to 1.7%, preferably from 0.52% to 0.82% of cysteine and cystine, the percentages being expressed in g per 100 g of protein. The protein hydrolyzate according to the invention does not comprise carbohydrates (in particular starch or its derivatives), lipids or amino acids other than those present initially in Fabaceae, in particular in broad bean and / or faba bean, or possibly derived from the enzyme (s) used during the hydrolysis. The protein hydrolyzate is preferably obtained by a process comprising a step of solubilization of proteins at a pH less than or equal to 8.5, more preferably less than or equal to 8, for example 7.5. This originality of the process according to the invention leads to a protein hydrolyzate with a reduced sodium content. Sodium comes mainly from the sodium hydroxide used to obtain and / or maintain the desired pH. The sodium content can be further reduced by using lime in the form of milk of lime to maintain the desired pH. The protein hydrolyzate is obtained by hydrolysis, preferably by enzymatic hydrolysis, of a vegetable protein material as defined above. The protein hydrolyzate as defined above is preferably obtained by a process as defined below in the section "Process for the preparation of a vegetable protein hydrolyzate". Food composition The vegetable protein hydrolyzate is preferably used in a food composition, thus giving it a hypoallergenic character compared to a food composition which would be based on native cow's milk proteins. The present invention thus relates to a food composition comprising or consisting of at least one vegetable protein hydrolyzate as defined above in the section "vegetable protein hydrolyzate". The food composition as defined above can comprise at least 1% of vegetable protein hydrolyzate, preferably at least 5% of vegetable protein hydrolyzate, more preferably at least 10% of vegetable protein hydrolyzate, for example 10% 20%, 20% to 30%, 30% to 40%, 40% to 50%, 50% to 60%, 60% to 70%, 70% to 80%, 80% to 90% vegetable protein hydrolyzate, the percentage being expressed by mass over the total mass of the composition. The food composition as defined above preferably comprises from 10% to 20% of vegetable protein hydrolyzate, for example from 15% to 20% of vegetable protein hydrolyzate, the percentage being expressed by mass over the total mass decomposition. A preferred food composition is a composition as defined above, characterized in that at least 10%, preferably at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at at least 70%, at least 80%, at least 90%, at least 95% of the proteins of said composition are provided by the protein hydrolyzate, the percentage being expressed by mass over the total mass of proteins of the composition. The food composition can thus comprise at least one other protein source than the bean and / or faba bean vegetable protein hydrolyzate, such as an animal protein source and / or another vegetable protein source, preferably in the form of a hydrolyzate. protein. In another embodiment, the bean and / or faba bean protein hydrolyzate is the only protein source of the food composition, in particular when the food composition is an infant preparation. The food composition can be any type of composition making it possible to provide a protein source. The food composition can be an infant preparation, a yogurt, a soup, a drink, a food supplement, a powder preparation (such as a powder preparation to be rehydrated, for example with water and / or milk, or not ), bar (for example cereal bar), snack (also called "snacking"), dessert cream, cottage cheese, milk-based shake (also called "milkshake"), fruit shake (also called " smoothie >>), drinkable yogurt drink, cookie (for example dry or soft cookie), bread (for example fresh bread or toast), rusk, pasta, or combinations thereof. The food composition can be in powder form, in liquid or semi-liquid form. The composition may advantageously comprise at least one other food ingredient, i.e. other than the vegetable protein hydrolyzate. The present invention particularly relates to a food composition as defined above, characterized in that said food composition is an infant preparation and in that it comprises at least one other food ingredient, for example at least two, at least four, at least six, at least eight, at least ten or at least twelve food ingredients, said other food ingredient being preferably selected from the group consisting of an oil, a mineral, a nucleotide, a trace element, a sugar, a polysaccharide, an emulsifier, a vitamin, choline, inositol, an amino acid, an antioxidant, a lactic ferment, a probiotic other than a lactic ferment, a soluble fiber and combinations thereof. Sugar is for example selected from the group consisting of glucose, other monosaccharide, lactose, other disaccharide and their combinations. The polysaccharide is for example selected from the group consisting of a starch (for example a pregelatinized starch or a precooked starch), a starch hydrolyzate (such as a maltodextrin), another glucose polymer (for example a glucose syrup ) and their combinations. The soluble fiber is for example selected from the group consisting of galacto-oligosaccharides, fructo-oligosaccharides, inulin and combinations thereof. The oil is for example selected from the group consisting of palm oil, palm kernel oil, rapeseed oil, sunflower oil, oleic sunflower oil, soybean oil, coconut oil, micro-algae oil, fish oil rich in polyunsaturated fatty acids and combinations thereof. The mineral is for example selected from the group consisting of calcium carbonate, tricalcium phosphate, magnesium chloride, disodium phosphate, potassium chloride, dipotassium phosphate, ferric diphosphate, zinc gluconate, copper gluconate, sodium selenite, gluconate of manganese, potassium iodide and combinations thereof. The emulsifier is, for example, soy lecithin, sunflower lecithin, a citric ester of mono- and di-glycerides and fatty acid and combinations thereof. The vitamin is for example selected from the group consisting of retinol acetate, cholecalciferol, thiamine mononitrate, riboflavin, nicotinamide, pyridoxine hydrochloride, folic acid, calcium D-pantothenate, cyanocobalamin, phytomenadione, D-biotin, acetate of DL-alpha-tocopherol, sodium L-ascorbate and combinations thereof. The amino acid is for example selected from the group consisting of taurine, L-tryptophan, L-cystine, L-methionine, L-threonine and L-carnitine. The amino acid can be obtained by chemical synthesis or extracted from plants. The antioxidant is for example an extract rich in tocopherols and / or L-ascorbyle palmitate. In one embodiment, the food composition as defined above comprises at least one other food ingredient selected from the group consisting of a pregelatinized starch, a precooked starch, a starch hydrolyzate, such as a maltodextrin, a syrup glucose and combinations thereof. In another embodiment, the food composition as defined above does not include a pregelatinized starch, a precooked starch, a starch hydrolyzate, such as a maltodextrin and / or a glucose syrup. The food composition as defined above for example comprises at least one other food ingredient, for example at least two, at least four, at least six, at least eight, at least ten or at least twelve food ingredients, said other ingredient food being selected from the group consisting of starch, maltodextrin, lactose, other monosaccharide, other disaccharide, glucose polymer (for example glucose syrup), oligosaccharide (for example, galacto-oligosaccharide and / or fructo-oligosaccharide), lactic ferments, probiotic other than a lactic ferment, nucleotide, choline, inositol, taurine, amino acid, micro-algae oil, fish oil rich in polyunsaturated fatty acids, emulsifier (for example, soy lecithin and / or sunflower lecithin), antioxidant (for example, extract rich in tocopherols and / or L-ascorbyle palmitate), and combinations thereof. In a preferred embodiment, the food composition as defined above is in powder form. The food composition according to the invention comprising or consisting of a vegetable protein hydrolyzate of Fabaceae, in particular of broad bean and / or faba bean, is suitable for anyone, whether they are in good health, sick or having suitable nutritional needs. The food composition according to the invention comprising or consisting of a vegetable protein hydrolyzate of Fabaceae, in particular of broad bean and / or field bean, is very particularly suitable for food: - infants (ie children under one year of age) and young children (ie children from one to three years of age), in particular infants and young children with metabolic disorders, risk of allergies and / or proven allergies, or healthy infants and young children for whom the parents have chosen a vegetable diet, - elderly people (in particular over 60 years old) who have reduced digestive capacities for proteins and a decrease in protein synthesis, - Pregnant and / or lactating women whose protein requirements are significantly increased, the protein hydrolyzate according to the invention making it possible to facilitate the absorption and assimilation of the proteins necessary for intrauterine growth and to support well the protein intake necessary for lactation, and / or, - adolescents (in particular children from 12 to 18 years old) whose protein requirements are increased on the one hand by a significant weight gain, on the other hand by the evolution of the hormonal system and for which a source of easily assimilated proteins guarantees a supply of essential amino acids which is sometimes difficult to reach during this period when the diet is unbalanced. Process for the preparation of a vegetable protein hydrolyzate The present invention also relates to a process for the preparation of a vegetable protein hydrolyzate as defined above. To be absorbed and assimilated, a vegetable protein must be reduced to small peptides. In vivo, protein absorption requires two successive hydrolyses: - hydrolysis by endopeptidases (for example pepsin, trypsin and / or chymotrypsin) which reduce the chains into small polypeptides, and - hydrolysis by exopeptidases (in particular the intestinal enzymes of the brush border) which continue the hydrolysis by producing small peptides and amino acids which are absorbed by the enterocyte. Certain population categories, such as the elderly and infants, have a deficient or immature enzyme system that does not allow this bio-assimilation. It is therefore essential to provide them with proteins directly in the form of peptides. These peptides can be obtained by hydrolysis. The present invention particularly relates to a process for the preparation of a vegetable protein hydrolyzate of Fabaceae, in particular of broad bean and / or field bean, comprising the following stages: a) optionally, grinding of Fabaceae seeds, in particular of broad bean and / or faba bean, to obtain a flour of Fabaceae, b) solubilization of the proteins of a Fabaceae flour, for example as obtained at the end of step a), in order to obtain solubilized proteins, c) optionally, purification of the solubilized proteins, preferably by precipitation, to obtain purified solubilized proteins, d) enzymatic hydrolysis of the solubilized proteins, optionally purified, to obtain a vegetable protein hydrolyzate, and e) optionally, drying, for example by atomization or lyophilization, and / or freezing of said vegetable protein hydrolyzate. Grinding stage The method as defined above comprises an optional first step a) of grinding Fabaceae seeds, preferably broad beans and / or faba beans, to obtain a flour. The seeds used in step a) are preferably shelled seeds in order to eliminate the seed coat as much as possible. Dehulling makes it possible in particular to reduce the content of impurities, such as tannins and polyphenols, and cellulose, and thus to improve the yield of the protein solubilization step. Step a) is therefore preferably preceded by a seed husking step. Grinding the seeds is also called milling. The flour obtained at the end of the grinding stage preferably has less than 1% of particles of size greater than 250 μm, more preferably less than 1% of particles of size greater than 212 μm, more preferably less than 1% of particles larger than 180 μm, the percentage being expressed in grams per 100 g of flour. Solubilization step The method as defined above comprises a step of solubilizing the proteins of a Fabaceae flour, for example as obtained by the grinding step defined above, in order to obtain solubilized proteins. The solubilization is carried out in an aqueous medium, preferably at a pH less than or equal to 8.5, more preferably at a pH less than or equal to 8, more preferably at a pH less than or equal to 7.5. For example, the pH of the solubilization step is from 7 to 8.5, preferably from 7.3 to 8, for example 7.5. To obtain an aqueous medium, the flour is therefore mixed with water, preferably at a flour: water mass ratio less than or equal to 1: 4, preferably less than 1: 6, more preferably less than 1: 8. The mass ratio flour: water is for example comprised from 1: 8 to 1: 10, for example 1: 9. The mixture of flour and water obtained therefore preferably comprises at most 25% flour, preferably at most 15%, for example at most 12% flour, the percentage being expressed in g per 100 g of the mixture. The water is preferably osmosis water. The solubilization step is preferably carried out at a temperature ranging from 23 ° C to 27 ° C, for example at 25 ° C. The solubilization step is preferably carried out at least for 20 minutes and / or at most for 40 minutes, for example for 30 minutes. The pH adjustment can be obtained by adding an alkalizing agent, preferably sodium hydroxide and / or lime. The lime is preferably quicklime, for example in the form of milk of lime. Lime milk is obtained by dissolving quicklime in water. In a preferred embodiment, the pH is maintained at a pH less than or equal to 8.5, preferably less than or equal to 8, or preferably equal to 7.5 throughout the duration of the solubilization. In an advantageous embodiment, the solubilization step comprises or consists of the following steps: - mixing the flour with water, preferably in the proportions as defined above, to obtain a mixture, - adjustment of the pH of said mixture, to a pH as defined above, - incubation, preferably at a temperature as defined above and / or for a duration as defined above and / or at a pH as defined above, and - Separation of the solid and liquid phase, for example by decantation or centrifugal decantation, and recovery of the liquid phase, to obtain solubilized proteins. The solubilized proteins obtained at the end of the solubilization step are in the form of a protein cream. Purification stage The method as defined above optionally comprises a step of purifying the solubilized proteins. Purification is preferably precipitation to obtain purified solubilized proteins. Precipitation is preferably obtained by placing the solubilized proteins at a pH of 4 to 5, more preferably 4.5. The solid and liquid phases are then separated, preferably by centrifugation (for example by means of a plate centrifuge or a sedicant), and the liquid phase is eliminated. The precipitated proteins present in the solid phase are then preferably washed (for example by suspension in osmosis water maintained at pH 4.5, then centrifugal separation and elimination of the liquid phase), in order to improve the purity protein. Hydrolysis step The method as defined above comprises a step of enzymatic hydrolysis of the solubilized proteins, said solubilized proteins being able to be purified or not. In one embodiment of the invention, the hydrolysis step is carried out on a resolubilized isolate. In this case, the solubilized proteins obtained in step b) and optionally purified as obtained in step c) are dried beforehand, for example by atomization or lyophilization, to obtain an isolate. In a preferred embodiment, the hydrolysis step is not carried out from a resolubilized isolate, but directly from the solubilized proteins obtained in step b) or optionally purified as obtained step c). The hydrolysis step can be achieved with a single enzyme or a mixture of two or at least two enzymes. The enzyme (s) used in the hydrolysis step are proteases. The protease is preferably a neutrase or an alkalase. The hydrolysis step is for example carried out using at least one neutrase and / or at least one alkalase. The hydrolysis step is preferably carried out using at least one neutrase and / or at least one alkalase, to the exclusion of any other enzyme. The enzyme (s) used preferably do not include cellulase, hemicellulase, glucosidase, amylase and / or xylanase. More generally, the enzyme (s) used do not include a carbohydrate degrading enzyme. In a preferred embodiment, the hydrolysis step is carried out using a neutrase and an alkalase. When several enzymes are used during the hydrolysis step, they are preferably used at the same time, for example in the form of a mixture. The temperature, pH and / or duration of the hydrolysis step depends in particular on the enzyme (s) used. In an advantageous embodiment, the enzymatic hydrolysis step is carried out at a temperature between 45 ° C and 55 ° C, preferably at 50 ° C. The hydrolysis step is preferably carried out at a pH of 6.5 to 7.5, more preferably at pH 7. The duration of the enzymatic hydrolysis step is preferably between 1 hour and 3 hours, for example 2 hours. The enzymatic hydrolysis step as defined above can include or consist of: bringing the solubilized proteins, optionally purified, into contact with one or more enzymes, preferably as defined above, in particular at a temperature and / or pH and / or for a period of time as defined above, a step for deactivating the enzyme (s), for example by heat treatment, such as for 30 minutes at 90 ° C., and / or a step for separating the solid and liquid phase (preferably by centrifugation, for example in a sedicant) and recovery of the liquid phase, making it possible in particular to eliminate insoluble non-hydrolyzed proteins, to obtain a protein hydrolyzate. Concentration, drying and / or freezing stage The method as defined above can comprise a step of concentration, drying and / or freezing of said protein hydrolyzate. The concentration is for example carried out by evaporation under vacuum. The drying can be carried out by any method well known to a person skilled in the art, such as by atomization or lyophilization. Preferably, the process for the preparation of a plant protein hydrolyzate of Fabaceae as defined above does not include a step of adding one or more amino acids or one or more lipids. Process for the preparation of a food composition The present invention also relates to a method for preparing a food composition comprising a step of mixing a vegetable protein hydrolyzate as defined above with at least one other food ingredient. The food ingredient can in particular be as defined above. The food composition is in particular as defined above. Use of a vegetable protein hydrolyzate in food compositions A subject of the present invention is also the use of a protein hydrolyzate as defined above as a partial or total substitute for proteins from cow's milk, rice and / or soy and / or any other protein source, in a composition food, in particular to reduce the allergenic nature of said composition, reduce the contaminant (s) content (in particular arsenic) of said composition and / or obtain a food composition without isoflavone, while maintaining at least equivalent nutritional properties ( for example in terms of composition and / or digestibility). Other characteristics and advantages of the invention will emerge more clearly from the examples which follow, given by way of nonlimiting illustration. EXAMPLES EXAMPLE 1 Production of a vegetable protein hydrolyzate based on faba beans Example 1A: Materials and methods (i) Raw material A flour obtained from faba beans of the Olan variety carefully cleaned and shelled, said flour being characterized by a particle size at 99% less than 212 μm, is used directly. (ii) Solubilization of proteins Faba bean flour of the Olan variety is mixed with reverse osmosis water in a 1: 9 mass ratio. The pH is adjusted to 7.5 with a solution of NaOH. The pH is adjusted so as to be kept at a pH below 8 throughout the duration of the solubilization of the proteins. The solubilization is carried out at 25 ° C for 30 minutes. The solid and liquid phases are then separated by decantation and the liquid phase comprising the solubilized proteins is recovered. (iii) Purification The solubilized proteins are then purified by precipitation at pH 4.5. The solid and liquid phases are separated by centrifugation and the liquid phase is removed. (iv) Enzymatic hydrolysis The enzymatic hydrolysis is carried out at 50 ° C and at pH 7 for 3 hours using a mixture of neutrase and alkalase. The enzymes are then inactivated by heat treatment for 30 minutes at 90 ° C. (v) Concentration and drying The protein hydrolyzate obtained at the end of the hydrolysis step is centrifuged so as to recover the solid phase. The latter is concentrated by vacuum evaporation, then spray dried. Results The implementation of the process makes it possible to obtain 67 kg of vegetable protein hydrolyzate from 900 kg of flour containing at least 220 kg of vegetable proteins. The process yield is therefore 30%. The characteristics and properties of the vegetable protein hydrolyzate are detailed in Example 2 below. Example 1B: Materials and methods (i) Raw material A flour obtained from faba beans of the Olan variety carefully cleaned and shelled, said flour being characterized by a particle size at 99% less than 212 μm is directly used. (ii) Solubilization of proteins The flour is mixed with reverse osmosis water in a 1: 9 mass ratio. The pH is adjusted to 7.5 in the presence of lime in the form of milk of lime. The pH is adjusted so as to be kept at a pH below 8 throughout the duration of the solubilization of the proteins. The solubilization is carried out at 25 ° C for 30 minutes. The solid and liquid phases are then separated by decantation and the liquid phase comprising the solubilized proteins is recovered. (iii) Purification The solubilized proteins are then purified by precipitation at pH 4.5. The solid and liquid phases are separated by centrifugation and the liquid phase is removed. (iv) Enzymatic hydrolysis The enzymatic hydrolysis is carried out at 50 ° C and at pH 7 for 2 hours using a mixture of neutrase and alkalase. The enzymes are then inactivated by heat treatment at 90 ° C for 30 minutes. (v) Concentration and drying The protein hydrolyzate obtained at the end of the hydrolysis step is centrifuged so as to recover the solid phase. The latter is concentrated by vacuum evaporation, then spray dried. Results The implementation of this process makes it possible to obtain 55.4 kg of vegetable protein hydrolyzate from 875 kg of flour containing at least 213 kg of vegetable proteins. The process yield is therefore 26%. The characteristics and properties of the vegetable protein hydrolyzate are detailed in Example 2 below. EXAMPLE 2 Characteristics and properties of a faba bean vegetable hydrolyzate (i) Composition of a faba bean vegetable hydrolyzate Table 1 below indicates the characteristics of the vegetable protein hydrolyzate obtained according to Example 1A and 1 B. Table 1 Values for 100g unit Hydrolyzate according to EXAMPLE 1A Hydrolyzate according to EXAMPLE 1B Dry extract g 99,50099,500Humidity g <0.5<0.5Ashes g 10.5404,460Proteins N x 6.25 g 86,40095,000Sodium g 3,7460.083Calcium mg 36,2001,530,000Aminogram: per 100 g of proteinper 100 g of protein threonine g 2,920 3,380 3,060 3,221 Aspartic acid g 10,000 11.574 9,990 10.516 serine g 4,550 5,266 4,890 5,147 lysine g 5,930 6.863 7,440 7.832 valine g 3,960 4,583 4,000 4,211 proline g 3,710 4,294 3,590 3,779 alanine g 3,440 3,981 3,650 3,842 phenylalanine g 3,810 4,410 3,650 3,842 Total isoleucine g 3,550 4,109 3,380 3,558 wistaria g 3,480 4,028 3,940 4,147 tyrosine g 2,850 3,299 2,580 2,716 arginine g 8,040 9.306 9,380 9.874 leucine g 6,510 7,535 6,190 6,516 histidine g 2,320 2,685 2,930 3,084 Glutamic acid g 15,900 18.403 18,900 19,895 tryptophan g 0,640 0.741 0.717 0.755 methionine g 0.595 0.689 0.678 0.714 Cysteine + cystine g 0.549 0,635 0.509 0.536 unit Hydrolyzate according to EXAMPLE 1A Hydrolyzate according to EXAMPLE 1B PM distribution: PM> 35,000 % 0,0100,02018,000 <PM <35,000 % 0,1300,32010,000 <PM <18,000 % 0,8102,1006,000 <PM <10,000 % 2,0003,2503,000 <PM <6,000 % 5,0703,9101,000 <PM <3,000 % 27.78021.050800 <PM <1000 % 11.3709,460204 <PM <800 % 47.48054.820PM <204 % 5,3505,070Average PM da 581546 (ii) Hypoallergenic properties Material and methods In vivo tests are performed to assess the safety of vegetable protein hydrolyzate in animals allergic to cow's milk protein (PLV). Mice are first sensitized to cow's milk proteins so as to make them allergic to them. An allergic provocation test is then carried out. To this end, 3 groups are made up: the control group (administration of a composition comprising neither milk proteins nor vegetable proteins), a milk protein group and a vegetable hydrolyzate group. The immune and allergic response is then evaluated. Results The control group having received a composition without milk proteins or vegetable protein hydrolyzate does not exhibit allergic reactions (zero allergic manifestations and indicators of negative immune response). The milk protein group having received milk proteins, presents an allergic reaction (numerous allergic manifestations and indicators of the positive immune response). The hydrolyzate group that received the plant hydrolyzate does not exhibit allergic reactions (zero allergic manifestations and negative immune response indicators). The vegetable protein hydrolyzate according to the invention is therefore suitable for individuals who are allergic or liable to be allergic (allergic risk) to cow's milk proteins. EXAMPLE 3 Food compositions based on a bean or faba bean vegetable protein hydrolyzate EXAMPLE 3A: Infant preparation immediately for infants over 6 months An example of follow-on infant formula for infants over 6 months is shown in Table 2 below. The proteins of the infant preparation are provided exclusively by a bean and / or faba bean protein hydrolyzate at a concentration of 10% to 20% (in g per 100 g of preparation), for example as obtained in Example 1A or 1 B. Table 2 Average nutritional composition units Per 100 g of powder Per 100 ml of 13.5% reconstituted milk Energetic value K J 2,054 277 Energetic value kcal 491 66 Humidity g 2,500Ashes g 3,200Proteins = N x 6.25 g 12,000 1,620 lipids g 23,500 3,173 Medium Chain Triglycerides g 4,000 0,540 of which total AGS % of total fat 45of which AGMI % of total fat 39of which AGPI % of total fat 16linoleic ac mg 3,510,000 473.850 alpha-linolenic ac mg 380,000 51,300 DHA mg 126,000 17,010 EPA mg 22,000 2,970 carbohydrates g 56,700 7,655 lactose g - - maltodextrins g 36,200 4,887 glucose syrup g 8,000 1,080 precooked or pregelatinized starch g 12,500 1,688 Dietary fiber : GOS and FOS (90/10) g 2,100 0.284 minerals: sodium mg 170,000 22,950 potassium mg 550,000 74.250 chloride mg 380,000 51,300 calcium mg 580,000 78,300 phosphorus mg 350,000 47,250 magnesium mg 60,000 8,100 iron mg 6,000 0,810 zinc mg 7,000 0,945 copper gg 400,000 54,000 iodine gg 118,000 15.930 selenium gg 20,000 2,700 manganese gg 300,000 40,500 molybdenum gg 5,000 0.675 fluorides gg <491 <66 Vitamins: AT gg 525,000 70.875 D3 gg 12,500 1,688 B1 gg 530,000 71.550 B2 gg 1,050,000 141.750 PP - Niacin - B3 gg 5,200,000 702,000 Pantothenic Ac - B5 gg 3,950,000 533.250 B6 gg 420,000 56,700 Biotin - B8 - H gg 13,000 1,755 folate pg-DFE 125,000 16.875 Folic acid gg 75,000 10,125 B12 gg 1,900 0.257 VS mg 80,000 10,800 K1 gg 32,000 4,320 E mg 9,000 1,215 Other nutrients: L-Carnitine mg 10,000 1,350 Taurine mg 20,000 2,700 choline mg 190,000 25.650 inositol mg 25,000 3,375 nucleotides mg 15,000 2,025 EXAMPLE 3B: Adult food for oral clinical nutrition in the event of undernutrition or risk of undernutrition An example of an adult food suitable for oral clinical nutrition in the event of undernutrition or risk of undernutrition is shown in Table 3 below. The proteins of this food are provided exclusively by a bean and / or faba bean protein hydrolyzate at a concentration of 20% to 23% (in g per 100 g of the food), for example as obtained in Example 1A or 1 B. Table 3 Average nutritional composition nutrients units Per consumption unit, i.e. 200g Energetic value K J 1,316 Energetic value kcal 313 Proteins = N x 6.25 g 19,000 lipids g 11,500 of which total AGS g 1,500 of which AGMI g 7,100 of which AGPI g 2,900 carbohydrates g 33,000 lactose g - sugars g 10,000 maltodextrins g 15,000 glucose syrup g 5,000 precooked or pregelatinized starch g 3,000 Dietary fiber g 0,800 minerals: sodium mg 170,000 potassium mg 390,000 chloride mg 220,000 calcium mg 380,000 phosphorus mg 250,000 magnesium mg 65,000 iron mg 5,000 zinc mg 3,500 copper μο 450,000 iodine μθ 50,000 selenium μθ 20,000 manganese μθ 550,000 molybdenum μθ 30,000 fluorides μο 250,000 Vitamins: AT μο 280,000 D3 μο 3,200 B1 μο 550,000 B2 μο 500,000 PP - Niacin - B3 μο 5,000,000 Pantothenic acid - B5 μο 2,000,000 B6 μο 600,000 Biotin - B8 - H μο 11,000 Folic acid μο 90,000 B12 μο 0,900 VS mg 35,000 K1 μο 25,000 E mg 5,000 Other nutrients: choline mg 120,000
权利要求:
Claims (7) [1" id="c-fr-0001] 1. Plant protein hydrolyzate of Fabaceae, characterized in that it comprises at least 85% protein and in that it comprises sodium at a concentration of less than 4.5%. [2" id="c-fr-0002] 2. Vegetable protein hydrolyzate according to claim 1, characterized in that it is a bean and / or faba bean vegetable protein hydrolyzate. [3" id="c-fr-0003] 3. Vegetable protein hydrolyzate according to claim 1 or 2, characterized in that it is obtained by enzymatic hydrolysis. [4" id="c-fr-0004] 4. Food composition comprising a vegetable protein hydrolyzate according to one of claims 1 to 3. [5" id="c-fr-0005] 5. Food composition according to claim 4, characterized in that said food composition is selected from the group consisting of an infant preparation, bar, snack, powder preparation, dessert cream, cottage cheese, milk-based shake, shake with fruit, drinking yogurt, cookie, bread, rusk, pasta and soup. [6" id="c-fr-0006] 6. Method for preparing a plant protein hydrolyzate of Fabaceae, comprising the following steps: a) solubilization of the proteins of a Fabaceae flour in an aqueous medium at a pH less than or equal to 8.5, in order to obtain solubilized proteins, b) optionally, purification of said solubilized proteins, in order to obtain purified solubilized proteins, c) enzymatic hydrolysis of the solubilized proteins, to obtain a vegetable protein hydrolyzate, d) optionally drying said protein hydrolyzate and / or freezing. [7" id="c-fr-0007] 7. Method for preparing a vegetable protein hydrolyzate according to claim 6, characterized in that step b) of purification comprises a step of precipitation at a pH of 4 to 5. 5 8. Process for preparing a food composition, characterized in that said process comprises a step of mixing at least one vegetable protein hydrolyzate according to one of claims 1 to 3 or obtained according to the process of claim 6 or 7 with at least minus one other food ingredient. 10 9. Use of a vegetable protein hydrolyzate according to one of claims 1 to 3 or obtained according to the method of claim 6 or 7, as a partial or total substitute for proteins from cow's milk, rice, soya and / or any other source protein, in a food composition. 15 10. Use of a vegetable protein hydrolyzate according to claim 9 to reduce the allergenic nature of said composition, reduce the contaminant (s) content of said composition and / or obtain a composition without isoflavone. FRENCH REPUBLIC
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同族专利:
公开号 | 公开日 FR3076982B1|2021-09-10| TW201934016A|2019-09-01| WO2019145351A1|2019-08-01| EP3742906A1|2020-12-02|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3969540A|1975-09-11|1976-07-13|Albion Laboratories, Inc.|Enzymatically prepared metal proteinates| EP0210448A1|1985-07-29|1987-02-04|Societe Des Produits Nestle S.A.|Process for preparing a foodstuff based on vegetable proteins| EP0575452A1|1991-03-07|1993-12-29|Novo Nordisk A/S|Method for production of a vegetable protein hydrolyzate| WO2002069732A1|2001-03-05|2002-09-12|Council Of Scientific And Industrial Research|Process for preparation of protein hydrolysate from soy flour| US20150237885A1|2012-09-21|2015-08-27|Roquette Freres|Assembly of at least one vegetable protein and at least one dairy protein| US20160000133A1|2012-11-30|2016-01-07|Andana Gmbh|Food composition containing amino acids and cocoa| FR3013186A1|2013-11-19|2015-05-22|Roquette Freres|NOVEL NON-ALLERGENIC SNACKS CONTAINING PLANT PROTEINS|FR3104023A1|2019-12-10|2021-06-11|Urgo Recherche Innovation Et Innovation|Combination product contributing to the well-being of pregnant women| CN110558468A|2019-10-21|2019-12-13|邓凡|Modularized full-nutrition beverage formula without common allergens|
法律状态:
2018-12-12| PLFP| Fee payment|Year of fee payment: 2 | 2019-07-26| EXTE| Extension to a french territory|Extension state: PF | 2019-07-26| PLSC| Publication of the preliminary search report|Effective date: 20190726 | 2020-01-13| PLFP| Fee payment|Year of fee payment: 3 | 2020-12-15| PLFP| Fee payment|Year of fee payment: 4 | 2021-12-15| PLFP| Fee payment|Year of fee payment: 5 |
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申请号 | 申请日 | 专利标题 FR1850508|2018-01-23| FR1850508A|FR3076982B1|2018-01-23|2018-01-23|FABACEAN PROTEIN HYDROLYSATE AS A HYPOALLERGENIC PROTEIN SOURCE IN FOOD COMPOSITIONS|FR1850508A| FR3076982B1|2018-01-23|2018-01-23|FABACEAN PROTEIN HYDROLYSATE AS A HYPOALLERGENIC PROTEIN SOURCE IN FOOD COMPOSITIONS| TW108102616A| TW201934016A|2018-01-23|2019-01-23|Hydrolysat proteique de fabacees comme source proteique hypoallergenique dans des compositions alimentaires| PCT/EP2019/051609| WO2019145351A1|2018-01-23|2019-01-23|Protein hydrolysate of fabaceae as a source of hypoallergenic protein in food compositions| EP19700838.6A| EP3742906A1|2018-01-23|2019-01-23|Protein hydrolysate of fabaceae as a source of hypoallergenic protein in food compositions| 相关专利
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