Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
  • C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
  • C07H5/06—Aminosugars
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H1/00—Processes for the preparation of sugar derivatives
  • C07H1/06—Separation; Purification
  • C07H1/08—Separation; Purification from natural products
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
  • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
  • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K31/00—Medicinal preparations containing organic active ingredients
  • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
  • A61K31/7008—Compounds having an amino group directly attached to a carbon atom of the saccharide radical, e.g. D-galactosamine, ranimustine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/60—Sugars; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
  • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
  • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
  • A61K8/9783—Angiosperms [Magnoliophyta]
  • A61K8/9789—Magnoliopsida [dicotyledons]
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P17/00—Drugs for dermatological disorders
  • A61P17/16—Emollients or protectives, e.g. against radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/08—Anti-ageing preparations
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
  • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

• the invention provides a reproducible process for generating glucosannine from plants which allows high glucosamine content to be obtained while reducing the content of residual ammonium or sulfate ions.
• the invention also relates to food compositions or cosmetic compositions which comprise the obtained glucosamine-enriched plant compositions.
• glucosamine in the treatment of joint diseases is widely described in the patent literature as well as in the scientific literature, usually in combination with other compounds or extracts from various natural sources.
• Pure glucosamine is added as glucosamine hydrochloride or glucosamine sulfate, and comes from shellfish hydrolysis.
• WO2000/0074696 describes "Herbal compositions comprising glucosamine and Trypterygium wilfordii, Ligustrum lucidum and/or Erycibe schmidtii, for treating inflammation or degeneration of joint tissues, e.g. arthritis" where pure glucosamine is mixed with plant preparation.
• Other patents relate to compositions of plant carbohydrates as dietary supplements where glucosamine is originated from chitin, i.e. once again from shellfish hydrolysis (see for example EP 1172041 or EP 0923382).
• glucosamine as an anti-osteoarthritis agent has been intensively developed during the last decade. Glucosamine is suspected to be the sole active compound on joint disease such as osteoarthritis. Until recently, only symptomatic treatment such as non-steroidal anti-inflammatory drugs have been thought to be efficient.
• glucosamine is also related to the aging process of skin, which has been characterized mainly by the continuous loss of elasticity and the loss of moisture. Skin aging is reflected by major structural changes and variations in composition. Most notably aged skins have less collagen and glycosaminoglycans compared with young skins. Glycosanninoglycan nnolecules produced by the skin include hyaluronic acid (poly D-glucuronic acid-N-acetyl-D-glucosamine), chondroitin sulfate, and dermatan sulfate. Hyaluronic acid is produced in higher quantities by the skin cells in response to exfoliation. Hyaluronic acid has a large capacity for hydration.
• Glucosamine has been shown to significantly reduce dryness of the skin and exfoliation. Glucosamine increases the moisture content and improves the smoothness of the skin. These findings suggest that long-term intake of glucosamine is effective in improving moisture content and smoothness of the skin.
• oral supplement containing glucosamine lead to a reduction in the number of visible wrinkles and in the number of fine lines in a group of women who took the supplement.
• the use of an oral supplement containing glucosamine, minerals, and various antioxidant compounds can potentially improve the appearance of visible wrinkles and fine lines.
• US 6,413,525 describes methods of substantially exfoliating the skin.
• it relates to topically applied compositions containing an amino sugar in the form of N-acetyl-D-glucosamine.
• N-acetyl-D-glucosamine is known to be a rate-limiting factor in the hyaluronic acid production by living cells.
• the topical application of glucosamine assists in the continued production of hyaluronic acid.
• compositions for topical application containing N-acetyl-D-glucosamine have also been disclosed, for example, in JP 59 013 708 (soften and moisturize the skin) or US 5,866,142 (a composition for exfoliating the skin).
• Glucosamine 2-amino-2-deoxy-D-glucose
• fructose is an essential component of glycoproteins and proteoglycans, important constituents of many eukaryotic proteins. This is an essential component of mucopolysaccharides and chitin.
• Glycosaminoglycans are large complexes incorporated into connective tissue, skin, tendons, ligaments and cartilage.
• Industrial glucosamine is a pure compound obtained from the acidic hydrolysis of chitin from shellfish, a complex carbohydrate derived from N-acetyl-D-glucosamine.
• US 6,486,307 describes an improved method for chitin acidic hydrolysis: a method of producing glucosamine hydrochloride from chitin by grinding the chitin to a very fine size and digesting it with concentrated hydrochloric acid.
• Glucosamine can also be produced from enzymatic hydrolysis of shellfish.
• US 5,998,173 describes a process for directly producing N-acetyl-D- glucosamine from chitin utilizing an ensemble of the chitinase family of enzymes to hydrolyze chitin of crustacean shells.
• Patents have also been filed in relation with microbial fermentation processes where cultivated microorganisms biosynthesize glucosamine.
• US 6,372,457 describes a method and material for producing glucosamine by fermentation using a genetically modified microorganism.
• GB 649 791 concerns an improved process of drying chicory. This process comprises the steps of: cutting chicory roots, fermenting the chicory roots under anaerobic conditions at temperatures not substantially exceeding 70°C (best temperatures between 50 and 55°C) for 7 h to 8 h, and drying chicory at 150°C for about 30 minutes. However, these conditions do not allow generating glucosamine.
• WO2005/053710 shows that glucosamine can be formed from several raw plant materials by following a special drying process, therefore obtaining glucosamine contents of between 150 and 1000 mg per kg of dry matter.
• WO2006/120009 describes a process for generating glucosamine from plants wherein fresh plant materials, or re-hydrated dried plant materials or plant extracts, are heated at a temperature comprised between 70°C and 110°C for more than 10 h, wherein a glucosamine precursor, such as ammonium sulfate salt, is added to said plant materials, rehydrated plant materials or plant extracts.
• a glucosamine precursor such as ammonium sulfate salt
• WO2006/120007 relates to a process for generating glucosamine from plants similar to the one described in WO2006/120009, wherein a fertilizer acting as glucosamine precursor is added during the cultivation of the plants, before the harvest.
• a fertilizer acting as glucosamine precursor is added during the cultivation of the plants, before the harvest.
• these processes described in WO2006/120007 and WO2006/120009 lead to plant raw materials containing level of glucosamine higher than 0.5% based on dry matter (i.e. 5 g of glucosamine per kg of dry matter), these processes are difficult to control.
• the content of glucosamine in the product obtained depends, in particular, on the volume of processed raw material and the volume of the drying chamber.
• the heating process requires a limited thickness (few centimeters) of the plant material to be efficient, with high variations of the heating duration depending on the thickness. Consequently, processing large volumes of material at the industrial scale will require very large surface for the drying.
• the raw material or plant extract obtained through the processes described in WO2005/053710, WO2006/120007 and WO2006/120009 contains high amounts of glucosamine but also high amount of residual ammonium or sulfate ions (up to, respectively, 4% and 24% based on dry matter), which can be detrimental for certain uses in food or cosmetic applications.
• glucosamine-enriched plant composition obtainable by the process according to the invention.
• said glucosamine-enriched plant compositions contain a reduced amount of residual ammonium or sulfate ions.
• the invention relates to food compositions or cosmetic compositions which comprise said glucosamine-enriched plant composition obtainable by the process as described above.
• the invention provides a reproducible process for generating glucosamine from plant which allows high glucosamine content to be obtained while reducing the content of residual ammonium or sulfate ions.
• the process according to the invention is reproducible and, in particular, it does not require specific weight and/or volume for the starting plant materials.
• glucosamine, sulfate and ammonium contents are expressed either in percentages based on dry matter or in g per kg of dry matter unless indicated otherwise.
• heating refers to a heating process in the range of temperature between about 70°C and 110°C, for more than 10 h and, preferably, for less than one week. This heating process can be described as a drying process. The heating process can also consist in a liquid maceration, carried out at the same temperature and time conditions, and then followed by a drying phase.
• free glucosamine it has to be understood non- polymerized glucosamine.
• high amount of glucosamine or “high glucosamine content”, as used therein, means that the amount of glucosamine is higher than traces of glucosamine, higher than the amounts in the corresponding fresh (i.e. non-dried) material and higher than any content cited in literature or patents.
• glucosamine is present in announts higher than 0.5 % based on dry matter, preferably greater than 5% and, in particular, greater than 10% based on dry matter.
• glucosamine-enriched plant composition refers to the product obtained through the process according to the invention with or without extraction or purification steps.
• This glucosamine-enriched plant composition comprises a high amount of glucosamine as defined above.
• plant and "plant material”, as used herein, are considered as synonyms.
• plant or “plant material”
• plant material any plant material capable of generating glucosamine according to the process of the invention.
• the plant material used can be any part of the plant, e.g. leaves, tubers, fruits, seeds, roots, grains or cell cultures.
• Said plant material can also be any type of plant extract obtained by any extraction procedure known to the skilled person in the technical field of plant extraction, where said plant extract is capable of generating glucosamine according to the process of the invention.
• the obtained glucosamine-enriched plant compositions comprise a high glucosamine content and, for example, a glucosamine content higher than 0.5 % based on dry matter, preferably greater than 5% and, in particular, greater than 10% based on dry matter.
• the plant material is a fresh plant material, or re- hydrated dried plant material.
• the plant material is selected for its ability to generate free glucosamine through the process of the invention. It can comprise a mixture of plant materials which differ, for example, in the plant species used and/or in the part of plant used.
• the plant material is the roots of the plant.
• the plant material may, in particular, be selected from the group consisting of plant species containing sucrose, fructose or inulin such as Cichorium, Daucus, Helianthus, Beta.
• the plant material may be, for example, from root of chicory (Cichorium intybus), root of carrot (Daucus carota), tuber of Jerusalem artichoke (Helianthus tuberosum), root of beet (Beta vulgaris).
• the plant species is Cichorium intybus used for the production of roots containing inulin, or for the production of Belgian endive in fields or in hydroponic culture systems: i.e. chicon, witloof chicory, French endive, white endive, Dutch chicory, succory, common chicory, or Italian dandelion is Cichorium intybus.
• Witloof chicory is the common name used by most horticulturists for the cultivated plant, while Belgian endive is more used for the product ultimately sold in grocery stores to consumers.
• Endive is the second growth of the bud from the top of a chicory root. The first growth takes place in the field on a plant grown from seed. The second growth takes place out of the field, usually in a building, in the dark.
• Each root has one main bud leading to the development of the chicon (endive).
• fresh plant material treated according to the invention or plant material treated according to the invention can be used as starting material, and processed to obtain plant material with high glucosamine content according to the present invention.
• harvested, dried and then rehydrated plant material is used as starting material.
• Glucosamine may be formed in particular by the condensation of a nitrogen- containing moiety and a sugar moiety.
• the glucosamine precursors used according to the invention are compounds providing the nitrogen-containing moiety needed for the formation of glucosamine.. Preferably, they consist in ammonium salts. Examples of such ammonium salts are ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium dihydrogenophosphate or glutamine, among others.
• the preferred precursor of glucosamine is ammonium sulfate which has shown surprisingly good results in the process according to the invention and in WO2006/120009 and WO2006/120007.
• the receptacle once filled is closed.
• This step improves the reproducibility of the process of the invention.
• the content of glucosamine in the obtained glucosamine-enriched plant composition is not dependent on the volume of the processed plant material and on the volume of the drying or heating chamber.
• the efficiency of the heating step according to the invention is then not dependent on the thickness of the plant material.
• the receptacle as described above, is closed with a lid just placed above it.
• the lid is a screw cap or for example a flip-top lid.
• the receptacle as described above is a container, a jar, or a bottle.
• the heating step according to the process of the invention may last from 10 h to 120 h, for example from 12 h to 96 h, in particular, from 48 h to 96 h.
• the heating temperature of the process is preferably from 70°C to 110°C, and for example from 70°C to 91°C or from 75°C to 91°C, in particular, about 75°C.
• the drying step according to the invention can be performed through any suitable known methods to the person skilled in the art wherein the temperature remains under about 110°C in order to avoid degradation of glucosamine.
• usual dryers can be used. It is also possible to change the pressure conditions.
• a process for generating glucosamine from plants as described above which further comprises a step of extracting the obtained glucosamine-enriched plant compositions.
• This extraction step can consist, for example, in adding said obtained glucosamine-enriched plant compositions in water for about 30 min at room temperature.
• this extraction may consist in adding said obtained glucosamine-enriched plant compositions in watenethanol (50:50) for 60 min at room temperature.
• the resulting mixture is centrifuged and the supernatant is freeze-dried.
• said resulting mixture is filtered and the filtrate is further dried.
• said obtained glucosamine-enriched plant compositions can be extracted with a buffer solution of high pH, for example with a pH equal to or greater than 10.
• Carbonate buffer of pH 10.8 is preferably used for the extracting step according to the invention.
• the glucosamine-enriched plant compositions so obtained comprise a reduced amount of ammonium residue and, in particular, less than 0.5% of ammonium ions and preferably less than 0.1%.
• the invention further relates to a process for generating glucosamine from plants comprising a step of extracting the obtained glucosamine-enriched plant compositions with a buffer solution of pH equal to or greater than 10 as described above, which further comprises the following steps:
• concentrated hydrochloric acid can be used in order to adjust the pH of said obtained solution to 6.5 to 7.
• the glucosamine-enriched plant compositions obtained after extraction comprise reduced amounts of residual ammonium ions and sulfate ions.
• High amounts of ammonium ions and/or sulfate ions in the obtained glucosamine-enriched plant materials or plant extracts may be detrimental depending on the application's field. Indeed, high amounts of ammonium and sulfate ions are known as being aggressive for the skin, eyes and mucous membranes and should thus be avoided, in particular, in cosmetic field, for example, for the preparation of topical creams.
• glucosamine-enriched plant compositions which comprise reduced amounts of residual ammonium ions and sulfate ions as described above may thus be used in a wide range of applications and, for example, for the preparation of cosmetic compositions such as anti-aging topical creams.
• glucosamine-enriched plant composition obtainable by the process as described above.
• said glucosamine-enriched plant compositions comprise at least 0.5% of glucosamine based on dry matter and preferably greater than 5% of glucosamine and, in particular, greater than 10% of glucosamine based on dry matter.
• said glucosamine-enriched plant compositions comprise less than 0.5% of ammonium ions based on dry matter.
• it contains less than 0.5% of ammonium ions and less than 0.5% of sulfate ions based on dry matter, in particular, less than 0.1% of ammonium ions and less than 0.2% of sulfate ions based on dry matter.
• food compositions or cosmetic compositions which comprise the glucosamine-enriched plant compositions as described above.
• said cosmetic composition is a topical cream.
• EXAMPLE 1 Formation of glucosamine through the heating and drying process at the lab level.
• the container is open and the dices are spread out (10 cm dice layer) for drying in the same oven, keeping the temperature at 75°C.
• glucosamine is carried out on an ion exchange Dionex PA 20 capillary column (4x250mm) with DIONEX ICS5000 apparatus.
• Analysis of sulfate is carried out on an ion exchange Dionex lonPac AS11-HC12 Analytical column 4x250mm with DIONEX ICS2500 apparatus.
• Glucosamine 10.02% based on dry matter.
• EXAMPLE 2 Formation of glucosamine through the heating and drying process at the Pilot plant level.
• dices of chicory roots 10 kg are soaked in a solution of ammonium sulfate 0.5M (30L) overnight. After draining, dices represent above 35 kg wet weight and are placed in two stainless steel containers (available volume 75 L each) with a lid just placed above then in an oven (Binder) at a temperature of 75°C for 48 h.
• the extraction and analytical protocols are performed as in the example 1 (with adjustment of the volume of extraction).
• EXAMPLE 3 Extraction of glucosamine and removal of the ammonium residues.
• the analytical protocol is performed as in the example 1 (with adjustment of the volume of extraction).
• EXAMPLE 4 Extraction of glucosamine and removal of the ammonium and sulfate residues.
• the solution is centrifuged and EtOH is evaporated using a rotary evaporator. The remaining solution without the EtOH is then freeze-dried.
• the analytical protocol is performed as in the example 1 (with adjustment of the volume of extraction).
• EXAMPLE 5 Extraction of glucosamine and removal of the ammonium and sulfate residues with CaCI 2 at 12% without pH change.
• the solution is centrifuged and the EtOH is evaporated using a rotary evaporator. The remaining solution without the EtOH is then freeze-dried.
• the analytical protocol is performed as in the example 1 (with adjustment of the volume of extraction).

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