WO2016184450A1 - Couche de membrane matricielle à base d'alginate - Google Patents

Couche de membrane matricielle à base d'alginate Download PDF

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Publication number
WO2016184450A1
WO2016184450A1 PCT/DE2016/000214 DE2016000214W WO2016184450A1 WO 2016184450 A1 WO2016184450 A1 WO 2016184450A1 DE 2016000214 W DE2016000214 W DE 2016000214W WO 2016184450 A1 WO2016184450 A1 WO 2016184450A1
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WIPO (PCT)
Prior art keywords
matrix membrane
protein
medium
matrix
alginate
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PCT/DE2016/000214
Other languages
German (de)
English (en)
Inventor
Amir Ibrahim
Original Assignee
LÖSLER, Arnold
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Publication date
Application filed by LÖSLER, Arnold filed Critical LÖSLER, Arnold
Priority to DE112016001911.4T priority Critical patent/DE112016001911A5/de
Publication of WO2016184450A1 publication Critical patent/WO2016184450A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/60—Comminuted or emulsified meat products, e.g. sausages; Reformed meat from comminuted meat product
    • A23L13/62—Coating with a layer, stuffing or laminating
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/72—Encapsulation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • 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
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/733—Alginic acid; Salts thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/624—Coated by macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5052—Proteins, e.g. albumin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5073—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals having two or more different coatings optionally including drug-containing subcoatings

Definitions

  • the present invention relates to matrix membrane envelopes with alginate as the basic substance for the encapsulation and encapsulation of any liquid media as well as to a process for the preparation of the matrix membrane envelopes.
  • the present invention relates to matrix membrane bodies with a stable single or multi-layered matrix membrane shell with alginate as the basic substance, which is suitable for consumption, as well as a method for producing the matrix membrane body.
  • the present invention also relates to a device for producing the matrix membrane body according to the invention.
  • the invention also relates to stable matrix membranes and matrix membrane material with alginate as the basic substance in general and to a process for the preparation of stable matrix membranes and
  • the present invention further relates to a method for
  • Matrix membrane with alginate as the basic substance in particular by spraying, dipping and
  • the present invention also relates to other uses of
  • Microcapsules usually consist of a solid, liquid or gaseous
  • Nuclear material which is surrounded by a solid shell, the capsule wall.
  • the capsule size may be in the size range from 1 to 5000 ⁇ m (Hobein, B., Lutz, B., Kirschen Herbert Chemie, Mikroverkapselung, 2000, volume 49, Aulis Verlag Deubner & Co. KG, Cologne; Voigt, R ., Pharmaceutical Technology, For Study and Profession, 2000, Deutscher maschiner Verlag).
  • a process for the production of granules on a calcium alginate base is known, which can be filled with liquid food and beverages.
  • the membrane formation process is carried out by reaction between a salt of alginic acid in aqueous solution and a calcium salt in aqueous solution to form membranes.
  • the granules produced are then soaked in water to exchange the core liquid first against water and this finally by immersion in the desired, suitable for consumption liquid. For storage, the granules are kept immersed in the liquid suitable for consumption and also used together with it.
  • the method for portioning liquid alcohol according to DE 10 2009 038 170 A1 is based on a matrix encapsulation with alginate as the basic substance, wherein an alginate ball prepared from a calcium alginate compound is placed in a bath of liquid alcohol and the liquid contained in the Alginatkugel due to the production is displaced by the liquid alcohol. To improve the bite sensation, a thickener is added to the calcium-alginate compound.
  • a process for encapsulating long-chain alcohols wherein the long-chain alcohols are encapsulated by a polymer and optionally waxes and plasticizers.
  • the encapsulation here is to be understood as meaning that a protective layer is formed in order to limit or even prevent the dissolution or dispersion of the long-chain alcohols into the liquid phase.
  • the alginate solution is hereby dripped into a solution of divalent cations.
  • the substance to be encapsulated is in the alginate phase.
  • Matrix encapsulations with alginate as the basic substance, which are stabilized by additives, are described in WO2009024376 A1.
  • solids and liquids are enclosed in such a way that release of active substance takes place under physiological conditions only after passage through the stomach.
  • EP 1 025 869 A1 describes a process for the production of stable alginate material and alginate beads. According to the teaching there, excess, colloidosmotically disturbing divalent cations in the alginate matrix are bound by divalent or multivalent anions.
  • the core liquid contained in the capsule as a result of the preparation must first be removed and the desired liquid suitable for consumption must be introduced into the previously formed capsule.
  • a desired content can therefore be introduced exclusively by replacing the liquids in the interior of the capsule.
  • the content is not freely selectable in the known alginate-based capsules.
  • the known microcapsules are unfavorable in terms of their haptic properties such as bite and storage ability and durability and offer none sufficient fluid retention (barrier to aqueous media), why they usually need to store in a storage liquid.
  • the known microcapsules are limited in their size, shape and optical properties.
  • the object of the present invention is to provide an advantageous edible and stable matrix membrane material or matrix membrane material with alginate as the basic substance, which is suitable to directly encase or coat any type of liquid or solid media and surfaces and the storage and durability of the coated or coated liquid or solid media and improves the surfaces advantageous.
  • the object of the present invention is, in particular, to provide an improved process for encapsulating and enveloping liquid media with an edible and stable matrix membrane envelope with alginate as the basic substance, with which any type of liquid, in particular alcoholic liquids and drinks can be directly portioned and enveloped, and whereby the obtained stable matrix membrane bodies are superior in storability, stability and durability. Therefore, another object of the invention is to provide such improved matrix membrane bodies.
  • Another object is to provide a device for carrying out the method.
  • the object of the present invention is also to provide new uses of such an improved matrix membrane or matrix membrane material and novel methods characterized by the formation of such an improved matrix membrane.
  • Figure 1 Cross-section of a single-layer matrix membrane body according to the invention, comprising a core medium (1) and a single-layer matrix membrane shell (2) with alginate as the basic substance and additionally irreversibly denatured protein.
  • FIG. 2 cross-section of a multi-layer matrix membrane body according to the invention, comprising a core medium (1), a first matrix membrane layer (2) with alginate as the basic substance and optionally adjuvants such as maltodextrin and sugar esters (Sucro, E473), a second one
  • Carbohydrates, waxes and pulps are Carbohydrates, waxes and pulps.
  • FIG. 3 Concentration gradient (qualitative): Cross section of a two-layer matrix membrane (1.5 mm) of a matrix membrane body after sequential treatment in two
  • reaction medium 1 consisting of 750 ml of water, 1.86% by mass of sodium alginate, 0.27% by mass of sugar ester (Sucro, E473) and 0.53% by mass of maltodextrin for about 20 minutes with the calcium-containing core medium and then into the
  • Reaction medium 2 (2) consisting of 1.44% by mass of sodium alginate, 0.27
  • the new layer now contains additional protein (6), while the proportion of alginate (3) has decreased.
  • the proportion of maltodextrin (4) and sugar ester (5) is constant. Taking into account the stoichiometry, the matrix membrane composition behaves along the cross section (1.5 mm) as the ratios of the reactants in the reaction medium (qualitative representation).
  • FIG. 4 Concentration gradient (qualitative): Cross section of a two-layered matrix membrane (1, 5 mm) of a matrix membrane body after sequential treatment in two
  • Reaction media of different composition Single layer membrane body are in reaction medium 1 (2) consisting of 750 ml of water, 1, 60 mass percent sodium alginate, 1, 07 mass percent maltodextrin for about 20 min with the calcium-containing core medium (1) produced and stirred and then into the reaction medium 2 (2 ) consisting of 1, 17
  • Membrane composition are forced to form a layered membrane containing not only protein (6) in the new layer, but additionally chitosan (5), while the proportion of alginate (3) and maltodextrin (4) has decreased.
  • the matrix membrane composition behaves along the cross-section (1.5 mm) as the ratios of the reactants in the reaction medium (qualitative representation).
  • Figure 7 Sample run 1-4 according to Example 11 of the sample Blind (B): Caicium alginate without protein and without heat step
  • Figure 8 Sample Run 1-4 according to Example 11 of the sample Blind with heat treatment (BH), ie Caiciumalginatkugel without protein with heat step
  • FIG. 9 Sample run 1-4 according to Example 11 of the sample 16% den.P. (d.P.), i. Caicium alginate ball with already disperse denatured protein without heat step
  • Figure 10 Sample Run 1-4 according to Example 11 of the sample 16% denatured heat-step protein (d.P.H), i. Caicium alginate ball with already disperse denatured protein with heat step
  • d.P.H denatured heat-step protein
  • Figure 11 Sample Run 1-4 according to Example 11 of the sample 16% native protein (n.P.), i. Caicium alginate ball with originally native dissolved protein without heat step
  • Figure 12 Sample Run 1-4 according to Example 1 1 of the sample 16% native protein with heat step (n.P.H), i. Caicium alginate sphere with originally native dissolved protein with heat step
  • Figure 13 Total mass balance constant mass fraction
  • Figure 15 Samples taken at time point Oh, with three specimens each being added to a cylindrical vessel of distilled water at time point Oh (left to right: n.P.H, n.P., B.H., B., d.P.H., and d.P.).
  • FIG. 16 Recording of the samples at time 7h (from left to right: n.P.H, n.P., B.H., B., d.P.H. and d.P.). It was found that the exchange with distilled water in the samples B.H. d.P.H and P.H. It was faster that it could be easily recognized by pushing the ball towards the surface. The density difference between core medium (syrup) and distilled water is thereby also indicated.
  • FIG. 17 Recording of the samples at the time 200 h (from left to right: n.P.H, n.P., B.H., B., d.P.H. and d.P.). It was found that the exchange with distilled water for the samples n.P.H and P.H.
  • Figure 18 Graphical conductivity as a function of the residence time of the sample in distilled water between 0min - 350 min, n.P.H, n.P., B.H., B., d.P.H. and d.P.
  • the samples are compared with pre-denatured protein (d.P.) and the sample with native protein followed by heat treatment (n.P.H).
  • the graph for the samples with pre-denatured protein (dP) reaches a release level of 0.7 after only 220 min, ie 70% of the final value, compared to the graph for the sample with native protein and subsequent heat treatment (nPH) 270 min.
  • Figure 19 Graphical conductivity as a function of the residence time of the sample in distilled water between 0 min - 2000 min, n.P.H, n.P., B.H., B., d.P.H. and d.P.
  • the samples are compared with pre-denatured protein (d.P.) and the sample with native protein followed by heat treatment (n.P.H).
  • the graph for the sample with pre-denatured protein (dP) reaches a release level of 0.95 after only 467 minutes, ie 95% of the final value, compared to that for the graph for the sample with native protein and subsequent heat treatment ( nPH) with 1490 min.
  • FIG. 20 Time after which 95% of the final value of the conductivity has been reached.
  • FIG. 20 Time after which 95% of the final value of the conductivity has been reached.
  • FIG. 21 Production method according to Example 15 for producing an alginate-based solid matrix membrane on the surface of solid water-soluble media and crystalline solids such as salts and minerals, preferably dehydrated malic acid in crystalline form.
  • a matrix membrane envelope with alginate as the basic substance which contains 1 to 20% by mass of an irreversibly denatured protein, has advantageous haptic and optical properties over the known alginate capsules.
  • the advantageous matrix membrane sheath is also suitable, any
  • Liquid, especially alcoholic liquids and drinks to envelop directly, thereby allowing a direct portioning and wrapping a desired liquid, without first a Alginatumhüllung be generated in a reaction medium and the contents must be replaced by the desired liquid.
  • Matrix membrane bodies can be stably stored for a long time in closed containers without liquid storage medium.
  • alginate capsules or alginate casings by ionotropic hydrogel formation of aqueous solutions of soluble alginate salts, e.g. Potassium alginate and especially sodium alginate, or of aqueous solutions of their derivatives, e.g. their partial esters, with the help of certain polyvalent metal cations, especially calcium, is known.
  • the salts of alginic acid commonly referred to as alginates, are acidic carboxy group-containing polysaccharides consisting of D-mannuronic acid and L-guluronic acid linked by glycosidic linkages.
  • the polyvalent metal cations spontaneously form a water-insoluble gel, for example calcium alginate, by linking the polysaccharides.
  • the polyvalent cations of the metals barium, strontium, iron, silver, aluminum, manganese, selenium, copper or zinc are also suitable for this purpose.
  • Matrix membrane layer Matrix membrane layer, matrix membrane sheath, matrix membrane body, and / or
  • Matrix membrane or matrix membrane material described.
  • the term matrix here stands for a membrane with different components.
  • Matrix membrane bodies and matrix membrane envelopes with alginate as the basic substance can be prepared, for example, by introducing a solution of at least one salt of a polyvalent metal, in particular calcium lactate, into a solution of at least one soluble alginate, in particular sodium alginate.
  • the introduction can by dropping the Solution of the polyvalent metal salt in the alginate solution, for example by means of a nozzle, or by the solution of the polyvalent metal salt is placed dropwise by a lance to or under the surface of the alginate solution.
  • the introduction is preferably carried out by laying the solution of the polyvalent metal salt by means of a lance at or below the surface of the alginate solution.
  • Matrix membrane body then separated from the alginate solution.
  • the matrix membrane body obtained can be washed with water, dried and more
  • Monomer composition, block structure and the molecular weight of the alginate molecules have an influence on the maximum mass fraction of protein.
  • a further advantage of the invention is that the pore size of the matrix membrane layer, which is ultimately responsible for its permeability to liquid media and macromolecules, can be controlled by the mass fraction of protein used. By using a higher protein concentration within the scope of the invention, the barrier to macromolecules is increased.
  • the present invention relates to a matrix membrane body comprising a core medium and a shell surrounding the core medium, the shell having one or more
  • Matrix membrane layers comprising alginate as the basic substance with optionally adjuvants and wherein at least one matrix membrane layer contains 1 to 20 percent by mass of irreversibly denatured protein.
  • the at least one matrix membrane layer comprises 1 to 20 mass percent irreversibly denatured protein, preferably 2 to 20 mass percent irreversibly denatured protein, more preferably 4 to 20 mass percent irreversibly denatured protein, still more preferably 6 to 18 mass percent irreversibly denatured protein, and most preferably 14 to 17 mass percent irreversibly denatured protein.
  • the indication of the mass percent refers to 100 percent by mass of the total of the respective molar composition.
  • a mass fraction of 1% corresponds to 1 percent by mass.
  • 1 to 20 percent by mass of irreversibly denatured protein in the matrix membrane layer refers to the molar composition of
  • proteins are all animal or vegetable proteins. Preference is given to proteins which are suitable for consumption. Suitable animal proteins are e.g. Serum proteins, especially albumins and globulins, and gelatin. Proteins preferred according to the invention are ovalbumin, lactalbumin and bovine serum albumin, with ovalbumin being particularly preferred. For example, a suitable vegetable protein is soy protein. The proteins can be used independently or as a mixture. The use of protein or protein mixtures suitable for consumption produces matrix membrane coatings which are edible and excellently suited for consumption.
  • Suitable animal proteins are e.g. Serum proteins, especially albumins and globulins, and gelatin. Proteins preferred according to the invention are ovalbumin, lactalbumin and bovine serum albumin, with ovalbumin being particularly preferred.
  • a suitable vegetable protein is soy protein.
  • the proteins can be used independently or as a mixture. The use of protein or protein mixtures suitable for consumption produces matrix membrane coatings which are edible and excellently suited for consumption.
  • the present invention relates to a method for producing a matrix membrane body with alginate as the matrix matrix substance, comprising the steps:
  • Providing a core medium comprising a solution of a salt of a polyvalent metal
  • Matrix membrane body is formed, and wherein at least one reaction medium additionally containing 1 to 20% by mass of protein which is copolymerized into the forming matrix membrane layer;
  • matrix membrane bodies which comprise a core medium and a shell, wherein the shell comprises one or more matrix membrane layers with alginate as
  • Base substance comprises and wherein at least one matrix membrane layer 1 to 20
  • Metal cations is polymerized into the matrix membrane layer and then irreversibly denatured.
  • the order and sequence of the process steps is not specified. In particular, additional steps can take place before, between or following the mentioned method steps.
  • the introduction of the core medium into the reaction medium and the formation of the matrix membrane layer and generally the gelation of the dissolved alginate by means of the polyvalent metal cations is preferably carried out at room or ambient temperature.
  • matrix membrane bodies of, in particular, spherical, spherical, elliptical, egg-shaped, oval, or otherwise oblong rounded shape.
  • the protein is preferably added to the reaction medium.
  • An example of the preparation of a protein-containing reaction medium is described in Example 2.
  • the protein is intermolecularly incorporated into the alginate matrix with the aid of the polyvalent cations and formation of the alginate matrix (gel formation) and thus incorporated into the matrix membrane layer.
  • the reaction medium is 2 to 20
  • 4 to 20% by mass of protein are more preferably added to the reaction medium, more preferably 6 to 18% by mass of protein are added to the reaction medium and more preferably 14 to 17% by mass of protein are added to the reaction medium.
  • the indication of the mass percent refers to 100 percent by mass of the total of the respective molar composition.
  • a mass fraction of 1% corresponds to 1 percent by mass.
  • 1 to 20% by mass of protein corresponding to the Reaction medium is added to the molar composition of the reaction medium.
  • Matrix membrane layer takes place and therefore the protein content (mass percent protein) in the matrix membrane layer corresponds approximately to the protein content (mass percent protein) of the reaction medium. It is obvious to the person skilled in the art that the ratio of alginate to protein in the reaction medium and matrix membrane layer remains approximately unchanged.
  • the soluble salt of a polyvalent metal in a liquid composition may preferably be selected from solutions, in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, as well as
  • a composition comprising a solution of a polyvalent metal salt / a polyvalent metal salt / dissolved polyvalent metal salt is also referred to herein as the core medium.
  • the core medium may contain other ingredients in addition to the solution of a salt of a polyvalent metal.
  • Suitable salts of polyvalent metals are, for example, salts of the polyvalent metals iron, silver, strontium, aluminum, manganese, selenium, copper, zinc and in particular calcium.
  • Calcium is preferred according to the invention. Calcium cations are preferably used with lactate as the corresponding counterion.
  • the inventively preferred salt of a polyvalent metal is accordingly calcium lactate.
  • Other calcium salts are also provided. Calcium lactate is preferably used in a mass fraction of 2-3%, for example by adding it to the core medium. This corresponds to a stirred mixture of 500 ml core medium, about 12 g of pure calcium lactate (2.4 percent by mass).
  • the calcium lactate can be used according to the instructions for producing a core medium according to Example 1.
  • Other suitable polyvalent metal cations as well as mixtures of suitable metal cations can also be used.
  • the solution of at least one salt of a polyvalent metal according to the invention comprises at least one salt of a polyvalent metal.
  • the solution or the core medium consists of a solution of a salt of a polyvalent metal.
  • the polyvalent metal ion must be present at least in stoichiometric equilibrium with the dissolved alginate, preferably in excess of the alginate.
  • the soluble alginate in a liquid composition may preferably be selected from solutions, especially aqueous
  • composition comprising dissolved alginate / solution of a soluble alginate is also referred to herein as the reaction medium.
  • the reaction medium may contain other ingredients in addition to the dissolved alginate.
  • soluble alginate salts in particular water-soluble alginate salts of monovalent cations, such as potassium alginate or sodium alginate, or mixtures thereof, can be used according to the invention.
  • the alginate salt preferred according to the invention is sodium alginate.
  • the sodium alginate is added to the reaction medium.
  • Sodium alginate is preferably used in a mass fraction of 1 - 2%. This corresponds to 750 ml stirred reaction medium about 12 g of pure sodium alginate (1, 6 mass percent).
  • An inventive reaction medium comprising the solution of a soluble alginate can be prepared according to the instructions for the preparation of a reaction medium according to Example 1.
  • Core medium and reaction medium can be selected from solutions, in particular aqueous solutions, alcoholic solutions, oily solutions, colloidal solutions, as well as suspensions, dispersions or emulsions.
  • the introduction of the core medium into a reaction medium takes place by laying the core medium on the surface by means of a lance or by immersing the lance under the surface of a stirred reaction medium.
  • Spherical droplet formation and reaction to spherical matrix membrane bodies and other forms is thereby greatly improved and facilitated, since curing of the matrix membrane takes place directly at the interface between the dropping liquid (core medium) and alginate solution (reaction medium).
  • An exemplary embodiment of such a lance apparatus is described in Example 3. Furthermore, an undesirable leakage the liquid can be prevented by ensuring a hydrostatic compensation by an s-shaped arrangement of the hose pump, valve and outlet of the lance and that a conical outlet opening of the lance counteracts by capillary forces the hydrostatic pressure of the liquid column. Is the opening diameter or is the
  • Liquid column chosen too large over the outlet of the lance the core medium drips independently and uncontrollably from the lance due to its inertia and hydrostatic mass.
  • the reaction medium is stirred while the core medium is introduced.
  • the water-insoluble alginate gel is formed on the surface of the drop of the core medium.
  • the droplet is enveloped with a matrix membrane layer and a matrix membrane body is created in which the core medium is located.
  • the reaction medium is stirred for a further 35 minutes after introduction of the core medium.
  • the matrix membrane thickness increases.
  • the matrix membrane layer according to the invention is at least about 0.2 mm thick and can be at most infinitely thick.
  • the layer thickness of a matrix membrane layer according to the invention is preferably 0.2 mm to 4.0 mm, particularly preferred is a layer thickness of 1.0 mm to 2.0 mm. Most preferred is a layer thickness of 1.7 mm.
  • the layer thickness depends in particular on the residence time of the matrix membrane body in the reaction medium. To achieve a layer thickness of 1.7 mm, the
  • the layer thickness of the respective matrix membrane layer can be influenced.
  • single-layer matrix membrane bodies having an arbitrary layer thickness can be produced, ie matrix membrane bodies which have a single-layered matrix membrane shell, wherein the layer thickness of the matrix membrane layer can be arbitrarily controlled.
  • Joins the Introducing the core medium in a reaction medium to a further or multiple introduction of the formed matrix membrane body in a reaction medium creates a multi-layer matrix membrane body whose shell has two or more matrix membrane layers.
  • the layer thickness of the individual matrix membrane layers can be arbitrarily controlled by the residence time in the particular reaction medium and the layers can
  • reaction medium can be used, which may differ in their composition from each other. Even a simple matrix membrane layer acts as a barrier against yeasts, fungi and bacteria.
  • the matrix membrane bodies formed are removed from the reaction medium and subsequently introduced into another reaction medium.
  • the removal can be done by skimming or decanting, for example using a sieve, or centrifuging.
  • the matrix membrane bodies can optionally be rinsed briefly with water.
  • Matrix membrane layer formed a further matrix membrane layer. This process can be repeated as often as desired, with the reaction media being able to differ in their composition but not necessarily. However, it must always contain a sufficient amount of alginate in the respective reaction medium.
  • the mass fraction of sodium alginate is preferably 1 to 2% by mass. It has surprisingly been found that the calcium cations enclosed in the core medium of the respective matrix membrane layer are sufficient, as a result of diffusion through the first membrane layer, to form a further outer gel layer with the dissolved alginate.
  • the introduction of the core medium takes place in a reaction medium as introducing a core medium which is at least one
  • multi-layer matrix membranes and matrix membrane sheaths may be obtained by any means of introducing or contacting an already formed matrix membrane layer (s) with another dissolved alginate-comprising liquid composition
  • reaction medium in particular by immersing the already formed matrix membrane layer (s) in the reaction medium, or by spraying the already formed matrix membrane layer (s) with the reaction medium, or by dripping and pouring the reaction medium on the already formed
  • Matrix membrane layer (s). Accordingly, in addition to the at least one matrix membrane layer with alginate as the basic substance and 1 to 20% by mass of an irreversibly denatured protein, the matrix membrane body according to the invention can have one or more further matrix membrane layers, which for example can not contain any protein. In the case of sequential use of different reaction media, which differ in the selection and the mass fractions of excipients and / or the mass fraction of protein, a concentration gradient of the protein and optionally used adjuvants is thus produced via the superimposed matrix membrane layers. The sequence of
  • Matrix membrane layers are arbitrary.
  • the denaturation of the protein takes place after the last introduction into a reaction medium.
  • denaturation is followed by further introduction into a reaction medium.
  • the denaturation of the polymerized into the matrix membrane layer protein is carried out according to a particular embodiment by thermal treatment of the matrix membrane body in a temperature range of 45 to 80 ° C, more preferably in a temperature range of 60 to 75 ° C, more preferably in a temperature range of 65 to 75 ° C. It is known that proteins above a temperature of 45 ° C irreversibly denature. However, the temperature in the matrix membrane layer must not exceed the value of 70 ° C, since the calcium alginate above a temperature of 70 ° C would be irreversibly destabilized.
  • the matrix membrane layer is heated to a temperature of 45-70 ° C. This is preferably done in a heat bath with a temperature of 80-90 ° C, the
  • Matrix membrane layer is exposed until the temperature required for the denaturation of the proteins reached, the maximum temperature of 70 ° C, briefly 75 ° C, but not exceeded in the matrix membrane layer. Proteins which denature at a temperature of 70 ° C. are therefore preferred according to the invention.
  • the core medium additionally contains a liquid medium to be encapsulated, for example a liquid suitable for consumption, such as an alcoholic beverage or fruit syrup, it has proven advantageous if the denaturation or curing takes place in a mixture of water and the liquid medium to be encapsulated.
  • a liquid medium to be encapsulated for example a liquid suitable for consumption, such as an alcoholic beverage or fruit syrup
  • the denaturing or curing takes place in a mixture of water and the liquid medium to be encapsulated in a ratio of 2-3 units of water and 1 Unit of the medium to be encapsulated.
  • the mixture preferably has the same
  • the matrix membrane bodies and the mixture of water and liquid medium to be encapsulated are preferably placed in a container, for example a beaker or a closable bottle. Subsequently, the container with the matrix membrane bodies in the mixture of water and liquid medium to be encapsulated in a heat bath 80-90 ° C, e.g. Water bath, heated until the mixture in the container has a temperature of max. 70-80 ° C reached. This is usually done within a period of 3 to 6 minutes. The temperature of the mixture is
  • the mixture of water and liquid medium to be encapsulated has ambient temperature or room temperature before the start of the thermal treatment. This ensures that the mixture and the matrix membrane body contained therein warm slowly, which is beneficial to the
  • Crystallization process in the coagulation of proteins in this way, particularly advantageous optical and waterproof properties of the matrix membrane layers can be produced.
  • Matrix membrane body has a temperature of 45 to 80 ° C, i. e.g. the mixture of water and liquid medium to be encapsulated, in which the matrix membrane bodies are subjected to the thermal bath treatment. Because the surrounding mixture is limited to max. 80 ° C heated and the matrix membrane body are removed immediately after reaching the temperature of the heat bath, it is approximately assumed that the temperature in the matrix membrane layer itself does not exceed the critical value of 70 ° C.
  • the cooling of the cured matrix membrane body to room temperature is preferably carried out in the mixture of 2-3 units of water and 1 unit of medium to be encapsulated. It was found that the heating in a pure mixture of encapsulating medium proved to be not advantageous because the matrix membrane bodies have contracted on cooling. On the other hand, a mixture with water caused the water to flow slightly into the interior of the water due to its concentration balance direction Matrix membrane body diffuses and increases the osmotic pressure inside.
  • the protein which is built into the matrix membrane with its native tertiary structure, can stably cure and coagulate during heat treatment in a temperature range of 45 to 80 ° C (heat step) to denatured secondary and tertiary structures.
  • Matrix membrane body achieved that can be kept stable without liquid storage medium and stored for a longer period without affecting the quality.
  • Example 9 shows the improved stability of the matrix membrane body according to the invention in comparison to matrix membrane body without protein and without denaturation treatment.
  • Another advantage of using proteins as an additive in the matrix membrane layer is their antibacterial properties.
  • the incorporated protein forms after the
  • Heating step has its own structure and reduces the pore size of the alginate structure such that it acts as a barrier to liquids, macromolecules, yeasts, fungi and bacteria.
  • cured protein also allows irreversible incorporation of dyes and colorants.
  • the polymerized protein also improves the feel of the matrix membrane body.
  • Matrix membrane body can be achieved.
  • the formation of the secondary and tertiary structures of the protein can result in a metallically glossy and closed surface. It has surprisingly been found that in matrix membrane layers with a mass fraction of 14 to 17% protein and in particular in matrix membrane layers with 16 mass% protein, a particularly pronounced metallic pearl-like gloss effect on the
  • Matrix membrane is achieved.
  • An optimum metallic pearlescent gloss effect is achieved by using 16% by mass of protein and slowly heating the mixture to maximum 70 ° C.
  • the mixture in which the curing takes place is an ambient temperature-warm or room-temperature-warm mixture of 2-3 units Water and 1 unit of the liquid medium to be encapsulated into which the
  • Matrix membrane body are given and then heated in a 80-90 ° C water bath to a maximum of 70 ° C. Even at protein concentrations of less than 14 percent by mass, the metallic, pearl-like gloss effect decreases progressively.
  • the formation of the metallic shimmering membrane and the reflective surface with pearlescent gloss effect of the matrix membrane body according to the invention substantially improves this optically and for consumption.
  • the advantageous pearlescent effect arises here solely through the use of protein in the preferred mass fraction of 14 to 17% and the denaturation of the protein incorporated into the matrix membrane layer, i. without the use of additional dyes, especially pearl effect color particles.
  • the matrix membrane bodies according to the invention have an improved feel, since the matrix membrane layer has a firmer and more stable physical skin property as a result of the heating step. Likewise, this increases the bumpiness of the bodies, which is characterized by the fact that the bodies appear harder in their elasticity and, owing to the finer mesh structure and a lower permeability of the matrix membrane, there is a higher osmotic pressure in the interior of the bodies. Furthermore, the matrix membrane body according to the invention have a lower moisture content on the surface of the body, since the evaporation is significantly reduced by the protein content and the heat treatment.
  • Matrix membrane material containing 1 to 20% by mass of irreversibly denatured protein is evident by comparison of the weight loss of various matrix membrane bodies.
  • the gravimetric measurements according to Example 11 and FIGS. 7 to 14 clearly show that the matrix membrane body according to the invention has a significantly higher constant
  • Matrix membrane layer is formed, whereby the pore size of the alginate structure is reduced.
  • the matrix membrane layer according to the invention with 1 to 20 percent by mass of irreversibly denatured protein and the matrix membrane material according to the invention can be obtained by native protein, polysaccharide (alginate) and at least one polyvalent cation, and a denaturation step of the native protein is performed.
  • the matrix membrane body of the invention after storage at a temperature of 20 ° C after a period of about 145 h based on the initial mass of the matrix membrane body still a mass fraction (also referred to as a constant mass fraction) of at least 35%, for example 36%, for example 37%, for example 38% for example 39%.
  • a mass fraction also referred to as a constant mass fraction
  • the core medium is preferably an aqueous medium, preferably a core medium according to Example 1, more preferably a core medium according to Example 1 with 20-40
  • Mass percent disaccharides which are added for example in the form of syrup.
  • the gravimetric analyzes have shown that the samples with native protein and heat treatment compared to the samples with already denatured protein without
  • the liquid leakage and the total mass balance can be explained as follows.
  • the reformation of the structure which is characterized by the sample of native protein and heat treatment, significantly reduces the pore size of the membrane. This does not prevent low molecular weight components from seeping in, but prevents higher molecular weight components, such as the example of an oligosaccharide such as xanthan, that can not pass through the membrane.
  • the samples with native protein and heat treatment have in their
  • Conductivity measurements in Example 13 and Figures 18 to 20 characterized by diffusing a matrix membrane body with a certain core medium composition of disaccharide, citric acid, oligosaccharides and dyes with different osmotic pressures and molecular sizes different degrees from the interior of the matrix membrane body in a non-conductive aqueous solution to different Time to measure a release rate, which is due to the fact that by a
  • admixed amount of, for example, 16 percent by mass causes a reduction in the pore size of the matrix membrane according to the invention and thus components of the core medium which exceed the nominal pore size of the matrix membrane material, inside the Matrix membrane bodies remain while components smaller than the nominal pore size of the membrane can diffuse out.
  • Conductivity based on the change in conductivity between two media at 20 ° C after more than 1000 minutes, for example 1100 minutes, for example 1200 minutes, for example 1300 minutes, for example 1400 minutes.
  • the two media are separated by the matrix membrane.
  • the core medium is preferably an aqueous medium, preferably a core medium according to Example 1, more preferably a core medium according to Example 1 with 20-40% by mass of disaccharides, for example added in the form of syrup.
  • the electrolyte for example, citric acid may be used, preferably at a concentration of 1-10%.
  • the thermal denaturation of the protein polymerized into the matrix membrane layer can, according to a further particular embodiment, also take place in the absence of a surrounding liquid.
  • the matrix membrane body can be brought directly into contact with the heat source, for example in a pan at 70-75 ° C for about 3 min.
  • the cooling of the cured matrix membrane body to room temperature is preferably carried out in the mixture of 2-3 units of water and 1 unit
  • the denaturation of the protein incorporated into the matrix membrane layer takes place by treatment of the protein
  • Matrix membrane layer in an acid solution examples include:
  • Citric acid, malic acid and ascorbic acid which may be used alone or in admixture.
  • a 20% ascorbic acid solution is used.
  • denaturation of the protein means the conversion of native protein into irreversibly denatured protein. If the protein is present in a mixture of native and already denatured protein before denaturation, denaturation increases the proportion of irreversibly denatured protein in the mixture.
  • the protein added to the reaction medium may be native protein or a mixture of native and denatured protein. According to a particular embodiment that contains the Reaction medium added protein a predominant proportion of native compared to denatured protein, for example, 80 to 100% of native protein based on the
  • the 1 to 20 percent by weight of protein according to the invention added to the reaction medium contains, for example, 80 to 100% of native protein.
  • the proportion of native protein is 85 to 98%, in other particular embodiments 90 to 95%.
  • the matrix membrane sheath according to the invention is not limited in its application and is suitable for encapsulating and enveloping any liquids, in particular alcoholic liquids and drinks.
  • a certain liquid for example an alcoholic liquid or beverage
  • this liquid which is also referred to below as the liquid medium or fluid to be encapsulated
  • the core medium may accordingly additionally comprise a liquid medium.
  • the preparation of core media comprising raspberry syrup or 40% rum as the liquid medium to be encapsulated is described in Example 1.
  • liquid media include solutions, in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, and suspensions,
  • Dispersions and emulsions Dispersions and emulsions.
  • the invention has the advantage that the liquid medium to be encapsulated is freely selectable.
  • the desired composition and concentration of the core content can be achieved directly and definably.
  • the introduction of the desired content into the core requires no replacement of the production-related in the matrix membrane body fluids more and is therefore no longer dependent on the osmotic pressure of the fluids. This is a decisive criterion, in particular for bioactive components, in order to obtain a definable and reproducible product within narrow limits.
  • the liquid medium may therefore comprise any kind of foodstuff including dietary supplements.
  • examples include any type of liquid suitable for consumption, preferably alcoholic beverages including beer, wine, liquors, spirits and mixed drinks, dairy products, fruit or vegetable juices, fruit drinks including fruit juice drinks, fruit nectars and smoothies, syrups such as fruit and vegetable syrups or coffee syrup, and other sugar solutions, carbohydrates, or
  • the liquid medium from a suitable liquid for consumption.
  • the liquid medium may comprise spices, spice concentrates and spice mixtures, aromatics.
  • the liquid medium may also comprise at least one physiologically, physically or physico-chemically active substance, at least one dietary supplement, at least one pharmaceutically active compound or composition, at least one cosmetic agent or composition, and at least one constituent selected from fragrances and / or aromatics, flavors, hyaluronic acid, especially essential oils and volatile constituents.
  • the liquid medium may contain at least one chemically active compound, at least one catalyst, in particular enzymes, and reagents which can be used in particular as detergent-active substances.
  • the matrix membrane body according to the invention can be used as a detergent or added to a detergent.
  • the substances, compounds and compositions can be used independently or as a mixture.
  • the matrix membrane bodies according to the invention are not limited in their applicability and use. They can be used for example in the field of food and luxury foods, in the field of dietary supplements, in the medical and pharmaceutical sector, as a medical device, but also in the field of cosmetics and personal care, for example, as a shower gel, bathing ball, as well as in the household sector, for example, for washing-up liquid.
  • the inventive method is suitable for wrapping any liquid medium.
  • a particular advantage of the matrix membrane bodies according to the invention and the process for their preparation is that, for the first time, alcoholic liquids and drinks can also be directly portioned and coated.
  • the inventive method is particularly in the field of portioning and preservation of food and
  • Stimulants in the field of dietary supplements, in the medical and
  • the viscosity of the core medium when added dropwise to the reaction medium is significant. If the difference between the viscosity of the core medium and the reaction medium is too high, a thorough mixing of the two components in the stirred reaction medium is effected so that no formation of matrix membrane bodies is possible.
  • the densities of the reaction mixtures used also have an influence. Core medium droplets with too low a density float on the reaction medium and can not completely sink in, so no complete reaction is guaranteed to stable bodies, the droplets dissolve already during the dripping. If the density of the core medium is too high, the droplet sinks too quickly into the reaction medium, so that the droplet pulls threads behind it as a result of the rapid sinking. At the end of the reaction time, the matrix membrane bodies are no longer round but ellipsoidal or droplet-shaped or spheres with taillets. The shape is controllable.
  • the viscosity of the core medium can be increased by the addition of thickening agents such as maltodextrin and xanthan or by sugar. This is essential for the
  • Reaction medium sinks and can react to complete Matrixmembran analysesn. Too high a density of the core medium is to be avoided, because the droplets sink too fast and the formation becomes more difficult to spherical matrix membrane bodies.
  • Maltodextrin can be used as a standard thickening agent in the core medium and
  • the core medium is preferably in a
  • Xanthan gum is preferably added to the core medium at a mass fraction of 1.0-0.6%. This corresponds to 500 ml of stirred solution 6 g (1, 2 mass%) of pure xanthan.
  • the coating of lower viscosity aqueous and alcoholic media can be further optimized over the reaction medium.
  • Gelatine can here the
  • Matrix membrane body to act Gelatin is preferably added to the core medium and is also used as a gelling agent. In addition, it binds water contained in the core medium so that it reduces the fluid loss and at the same time the vapor pressure of the core medium. In addition, gelatin is also added to the reaction medium and is thereby also incorporated into the matrix membrane layer. As a result, the bite property additionally improved and the permeability of the matrix membrane layer opposite
  • Macromolecules are reduced. According to the invention gelatin is added to the core medium with a mass fraction of 2-4%. According to the invention, a mass fraction of 3% is gelatin, which corresponds to 15 g of pure gelatin per 500 ml of core medium.
  • the core medium comprises excipients which, independently of one another, can preferably be selected from maltodextrin, xanthan, sugar and gelatin.
  • excipients which, independently of one another, can preferably be selected from maltodextrin, xanthan, sugar and gelatin.
  • the use of mixtures of these excipients is the same
  • Moisture state are undefined in the known alginate capsules.
  • a change in the reaction liquids by addition of adjuvants change these properties.
  • the admixture of these auxiliaries in the reaction medium and / or in the core medium also changes the pore structure of the matrix membrane and thus the permeability to molecules and macromolecules.
  • the matrix membrane can additionally be stabilized.
  • excipients may be admixed with the reaction medium comprising a dissolved alginate and / or the core medium comprising a solution of a salt of a polyvalent metal.
  • the admixture of the excipients in the reaction medium causes them to be polymerized into the matrix membrane in the respective proportions.
  • reaction medium containing a dissolved alginate, and / or the core medium containing a solution of a salt of a polyvalent metal additionally include adjuvants for stabilizing the
  • Matrix membrane layers which may be preferably independently selected from gelatin, xanthan, maltodextrin, emulsifiers, sugar esters and sugar ester compounds, particularly sucrose, E473, unsaturated and saturated, long and short chain fatty acids, including fatty acid esters and mixtures thereof, proteins, shellac, glycerol, chitosan , Gold, silver, nano and microparticles, beeswax, wax, dyes, oils and fats, suitable polymers and suitable copolymers.
  • excipients suitable for consumption are preferably used.
  • the use of mixtures of said auxiliaries is also provided.
  • the use of UV radiation and chemically curing compounds and compositions is also provided according to the invention.
  • the adjuvants listed herein may be used in any embodiment and any aspect of the present invention for stabilizing a matrix membrane of the invention,
  • Matrix membrane layer or matrix membrane material can be used.
  • the adjuvants may accordingly be added to the respective reaction solutions, i. the reaction medium comprising a dissolved alginate or a liquid composition comprising dissolved alginate and / or the core medium comprising a solution of a salt of a polyvalent metal or a liquid composition comprising a solution of a salt of a polyvalent metal, be mixed.
  • the matrix membrane pore size which ultimately accounts for the permeability of aqueous media and macromolecules from the core, can be further controlled by the incorporation of gelatin as a water retention agent into the core medium.
  • gelatin Preferably, 1 to 20 percent by weight gelatin is added to the core medium.
  • Maltodextrin and xanthan can also be used to stabilize the matrix membrane layer.
  • Maltodextrin which is used as described above, can be used as a thickening agent by incorporation into the reaction medium and into the core medium. It provides improved bite resistance and improved elasticity when biting the matrix membrane bodies of the present invention over capsules based on pure alginate.
  • Xanthan is used as described above and improves as a thickening and gelling agent the haptic properties of the matrix membrane body in their bite and in the elasticity.
  • bite resistance means that the matrix membrane is bad to bite.
  • An improved bite resistance according to the invention means that the membrane is good to bite. The situation is similar with the elasticity of the invention
  • Matrix membrane Pure alginate membranes without additives have a very high elasticity.
  • spherical matrix membrane bodies which do not contain the auxiliaries mentioned in the matrix membrane are barely able to bite or barely burst in the mouth.
  • maltodextrin and xanthan gum By using maltodextrin and xanthan gum, the elasticity of the matrix membrane
  • Matrix membrane reduced By way of example, a spherical matrix membrane body can easily be bitten by it. According to the invention, the bite strength and elasticity of the matrix membrane can be influenced by the use of the auxiliaries mentioned.
  • Lecithin and sugar esters such as the emulsifier E473 (sucrose) are preferably used as emulsifiers.
  • the emulsifier E473 is additionally used to improve the flow properties of the reaction medium.
  • the emulsifier E473 the reaction medium with a mass fraction of preferably 0.05 to 0.5% added. This corresponds to a stirred mixture of 750 ml of solution 1 g of pure emulsifier E473 (0.13 mass percent).
  • Gold, silver nanoparticles and microparticles are used in particular as colloidal silver or gold solution.
  • Shellac can be dissolved in different media for use according to the invention.
  • Shellac is preferably dissolved in a 5% sodium hydroxide solution.
  • 5 g Natriumhydroxidplhackchen be dissolved in 95 ml of water.
  • 30 g of shellac are dissolved in 70 ml of 5% sodium hydroxide solution, which corresponds to a 30% shellac solution.
  • the shellac solution can be added to the reaction medium up to a mass fraction of up to 10%.
  • Chitosan acts as a barrier against liquid penetration due to its insolubility in water and has antibacterial properties which make it possible to remove the fluid
  • Matrix membrane layer of the body according to the invention and the coated core medium additionally protect against fungi, yeasts and bacteria and infestation.
  • Chitosan is used according to the invention as acetic acid chitosan solution.
  • a 1 - 2% acetic acid solution is first prepared.
  • a 2% chitosan solution is prepared from it. This corresponds to 100 g of solution 2 g of pure chitosan.
  • the 2% Chitosanaims can then in a mass fraction of up to 10% of the
  • Reaction medium can be added.
  • the reaction medium or the alginate-containing solution comprises chitosan.
  • the chitosan can be reacted with a suitable reaction medium and / or other suitable substances on the surface of the chitosan
  • Matrix membrane body are precipitated by wetting the matrix membrane body with a reaction medium or a solution containing chitosan and then exposed by dipping or spraying another reaction medium or chitosan-containing solution.
  • oils and fats include any fat or oil suitable for consumption, especially coconut oil, pumpkin seed oil, palmitin, grapeseed oil and olive oil.
  • the reaction medium is mixed and prepared with coconut oil, as an emulsion with an aqueous alginate solution and suitable emulsifiers.
  • coconut oil at room temperature has a solid state of aggregation, it is heated before use at a temperature of about 30-40 ° C maximum to the final melt.
  • coconut fat is included in the matrix membrane.
  • the coconut oil is cured at room temperature and appears to be suitable due to hydrophobic properties
  • Liquid barrier It improves the skin properties and protects against external influences.
  • beeswax is used as an excipient in the reaction medium, the beeswax is previously dissolved in a suitable oily medium and then added to the reaction medium. It can also be used subsequently for surface treatment.
  • Examples of suitable polymers and copolymers are Eudragit ® E-Po 100 and Eudragit ® L. There are, for example, 85.7 g of Eudragit ® E-Po with 8.6 g of sodium lauryl sulfate as an emulsifying agent, 12.9 g of stearic acid powder as the salt former and 42, Dissolve 8 g of Tale as anti-foaming agent in 850 ml of water. The stirred mixture can be added to the reaction medium after the dissolution process.
  • the shape, size and shape of the matrix membrane bodies can be influenced by a cryogenic step (cryogenic or cold treatment).
  • the core medium is prepared by freezing or flash freezing with e.g. liquid nitrogen in the form of any geometric body in the size range of 5 - 100 mm brought.
  • a liquid medium to be encapsulated a solution of a salt of a polyvalent metal, preferably
  • Calcium lactate and other excipients such as maltodextrin, xanthan, gelatin and / or
  • the frozen, i. the core medium transferred from a liquid to a solid state of aggregation is placed in a slightly heated reaction medium containing alginate and additionally adjuvants such as maltodextrin, xanthan,
  • Carbohydrates, emulsifiers, proteins, shellac, glycerol, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, oils and fats, polymers and copolymers may contain. The temperature difference between the frozen
  • Core medium and the reaction medium is preferably ⁇ > ⁇ 20 ° C, wherein the
  • Temperature of the reaction medium is preferably T ⁇ 60 ° C.
  • the frozen geometric body gradually melts on its surface and reacts at the thawed interface with the matrix membrane layer. This ensures that the body reacts in a fully concentrated state to the matrix membrane body, without deliquescing due to the interfacial tensions between the core medium and the reaction medium.
  • Such a procedure also has the advantage that the simultaneous addition of the amount to be produced guarantees a uniform reaction time of all matrix membrane bodies. All Matrix membrane bodies are exposed to the same reaction time and have the same membrane thickness. Sequential dripping or introduction brings about a low level of removal after a defined stay in the reaction medium
  • Core medium can thus be made into bodies of up to 100 mm in diameter, which can then be enveloped by the matrix membrane layer. This is particularly advantageous when larger volumes of core medium are to be portioned and wrapped.
  • matrix membrane bodies in the form of any geometric bodies in the size range of 5-100 mm can be produced, in particular in the form of cubes, cuboids, cylinders, pyramids and spheres.
  • the cryo treatment can be by freezing, treatment with liquid nitrogen or
  • the cryogenic treatment converts the media into a solid state of aggregation.
  • cryogenic treatment may be advantageous in the coating of liquid core media having a lower viscosity and density than the reaction medium, such as alcoholic liquids and beverages.
  • the present invention relates to a
  • a matrix membrane body characterized by a bilayer (double-layer) matrix membrane sheath wherein the core medium is enveloped by a first matrix membrane layer containing alginate and the excipients maltodextrin and xanthan, and a second matrix membrane layer is applied to the first layer;
  • Matrix membrane layer gelatin and maltodextrin as excipients and 1 to 20 mass percent irreversibly denatured protein.
  • An example of such a multi-layered matrix gelatin and maltodextrin as excipients and 1 to 20 mass percent irreversibly denatured protein.
  • Matrix membrane sheath is described in Example 5 and shown in FIG.
  • a matrix membrane layer which, in addition to calcium alginate, does not comprise any further auxiliaries or protein, is designated according to the invention as a singlematrix.
  • Matrix membrane layer additionally proteins and / or auxiliaries, this is referred to as multimatrix according to the invention.
  • color particles and dyes can be added to the core medium or reaction medium. Suitable colorant particles and dyes are all commercially available
  • E-dyes for example beta carotene (E160a), riboflavin (E101), anthocyanin, titanium dioxide (E171) and iron oxides (E172). If the dye riboflavin is used, the capsules fluoresce light green under UV radiation.
  • the color pigment components are added in the range of preferably 0.1 to 2.0% by mass, more preferably in the range of 0.5 to 1.0% by mass.
  • coloring of alginate capsules is achieved only by suitable dyes and micro- and nanoparticle-based dyes in the
  • Core fluid can be given.
  • the dye is then distributed homogeneously and stochastically again both in the core liquid and in the membrane.
  • Colored balls whose contents are color-coded by the shell
  • a further advantage of the present invention is that with the aid of a heating step and the concomitant denaturation of the protein polymerized into the matrix membrane subsequent coloration of the matrix membrane regardless of the color of the core medium and thus a color separation of matrix membrane and core medium is possible.
  • the heating step the color particles and
  • a coloring of the matrix membrane bodies takes place in that the spherical bodies are briefly washed with a sieve after the formation of the matrix membrane layer in the reaction medium and then filled into small bottles with a dyeing solution.
  • the color solution is preferably a mixture of 2-3 units of water and 1 unit of the liquid medium to be encapsulated, for example raspberry syrup, to which suitable color particles or dyes are added (dye-containing mixture).
  • the bottles are placed in a 80 - 90 ° C warm bath for about 3-6 minutes. The bottles are heated until the dye mixture has a temperature of max. 80 ° C reached.
  • the maximum temperature is crucial because the protein denatures above 45 ° C, but the calcium alginate becomes irreversibly unstable above a temperature of 70 ° C.
  • the temperature of the mixture is controlled. Subsequently, the bottles with the matrix membrane bodies and the color solution are gently cooled at room temperature. The presence of the dye-containing mixture with water in the bottles prevents the bodies from contracting during the cooling process and suffering a loss of quality. The resulting matrix membrane bodies are very stable and plump. The hardened matrix membrane is irreversibly colored by this process.
  • the heating step produces a lustrous metallic, opaque skin, which improves the matrix membrane body optically and for consumption enormously.
  • the matrix membrane bodies look like pearls.
  • Matrix membrane body applied an additional coating layer.
  • the additional coating layer is on the outside
  • the coating layer may be applied before or after denaturing.
  • the coating layer is applied by immersing the matrix membrane body in a coating composition, or by spraying the matrix membrane body with a coating composition, or by dropping or pouring the coating composition onto the matrix membrane body.
  • Coating composition according to a particular embodiment may comprise at least one adjuvant, which may preferably be selected from shellac, glycerin, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • adjuvant which may preferably be selected from shellac, glycerin, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • Coating may act as an additional barrier to outside influences such as fungi, yeast bacteria, carbohydrates, macromolecules, liquids, moisture, and conditioned air, as well as reducing the permeability of the matrix membrane layer to the core medium and macromolecules contained therein.
  • auxiliaries with a defined coating application causes a limited solubility with water, so that the release of the encapsulated core medium can be characterized and controlled by dissolving the matrix membrane in different pH media. This is particularly desirable and advantageous in the application in the medical field. In this way, for example, the release of the
  • Core medium are controlled in the digestive tract. Depending on the
  • Coating application may include dissolving the matrix membrane and releasing the matrix Core medium, without mechanically crushing them, for example by chewing in the mouth, thereby adjusted for medical purposes in the stomach and other regions (target).
  • the control of the release is particularly advantageous for the application of the matrix membrane body according to the invention in the field of cosmetics, fragrances and flavorings.
  • a further advantage of the matrix membrane body according to the invention is that, due to its considerably higher stability, it is for the first time without the risk of mechanical damage
  • the matrix membrane bodies can be coated with an additional preserving layer of water-insoluble polymers and / or copolymers.
  • Such a method also makes it possible to coat the matrix membrane body according to the invention by the choice of suitable polymers so that the release of the core medium can be controlled in a targeted manner.
  • Suitable auxiliaries of the coating composition are shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and suitable copolymers.
  • the adjuvants may be used independently or as a mixture in a coating composition. The use of commercially available and for consumption suitable coating materials or
  • Coating compositions is also provided.
  • the coating composition can be a solution, in particular aqueous solution, oily solution, alcoholic solution, colloidal solution, suspension, dispersion or emulsion which contains one or more of the abovementioned auxiliaries.
  • the coating composition may contain emulsifiers and defoamers as needed. According to the invention, suitable auxiliaries and coating compositions are used in particular for consumption.
  • Shellac is dissolved as described above.
  • Shellac shell is first admixed to the reaction medium, whereby it is polymerized in the formation of the matrix membrane body in the matrix membrane, and then applied in a coating step on the surface of the body.
  • the shellac copolymerized in the membrane acts here as a bridging agent to shellac applied externally.
  • Shellac works as a liquid barrier due to its water-insoluble properties and has an antibacterial and preserving effect.
  • Matrix membrane body this briefly subjected to a reaction medium and then soaked for about one minute in a 30% alcoholic shellac solution.
  • the shellac solution is absorbed by the reaction medium and falls on the surface of the
  • Matrix membrane body out After subsequent drying, a hard shellac coating was produced around the matrix membrane bodies.
  • Suitable polymers and copolymers are Eudragit® E-Po 100 and Eudragit® L.
  • Eudragit® L which can be used as described above in aqueous or alcoholic solution, causes solubility of the matrix membrane layer only in a strongly acidic medium (pH ⁇ 2) is possible, which, for example, allows only a targeted release of the nuclear medium in the stomach and otherwise acts as a protective coat.
  • Beeswax can also be used as a release agent and coating agent.
  • a coating process is carried out or several coating operations with different coating compositions are carried out successively.
  • the matrix membrane bodies of the present invention are superior in storability and durability, and can be stably held without storage liquid and stored for a prolonged period of time without impairing the quality. In addition, they are superior in size, shape, haptic properties such as bite, bumpiness, membrane hardness, humidity and also in optical properties.
  • the matrix membrane bodies according to the invention are preferably sealed in liquid and vapor pressure-tight storage containers such as blisters, metal cans, vessels and / or bottles so that the residual volume (air) in the enclosed medium is as low as possible relative to the volume of the contained bodies
  • the invention is not limited to the formation of stable matrix membrane bodies and matrix membrane envelopes for the encapsulation and encapsulation of liquid media, but generally to the production of stable matrix membranes and
  • Matrix membrane material with alginate as the basic substance applicable.
  • the present invention relates to a matrix membrane material containing alginate as a matrix containing 1 to 20% by mass of irreversibly denatured protein.
  • the protein is polymerized into the matrix membrane material with the aid of the polyvalent cations and formation of the alginate matrix (gel formation) and then irreversibly denatured.
  • the matrix membrane material is superior in stability and storage ability and can without
  • Impairment of quality are stored.
  • This material is particularly suitable as a matrix membrane layer in one of the invention described herein
  • the matrix membrane material of the invention comprises 1 to 20% by mass of irreversibly denatured protein, preferably 2 to 20% by mass of irreversibly denatured protein, more preferably 4 to 20% by mass of irreversibly denatured protein, still more preferably 6 to 18% by mass of irreversibly denatured protein, and most preferably 14 to 17% by mass of irreversibly denatured protein Protein.
  • Matrix membrane layers are described with alginate as the basic substance and matrix membrane body, in particular adjuvants for further stabilization of the matrix membrane material, dyes and suitable preservatives, such as chitosan.
  • the matrix membrane material comprises one or more excipients, preferably selected from maltodextrin, xanthan, emulsifiers, such as lecithin, sugar esters (eg Sucro, E473), fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, wax, dyes, oils and fats, preferably coconut fat, suitable polymers and copolymers.
  • excipients preferably selected from maltodextrin, xanthan, emulsifiers, such as lecithin, sugar esters (eg Sucro, E473), fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, wax, dyes, oils and fats, preferably coconut fat, suitable polymers and copolymers.
  • the matrix membrane material is suitable for consumption
  • the matrix membrane material according to the invention may be one-layered or multi-layered, ie it comprises one or more matrix membrane layers with alginate as the basic substance, which are formed one above the other and wherein at least one matrix membrane layer contains 1 to 20 percent by mass of irreversibly denatured protein.
  • matrix membrane layers with alginate as the basic substance, which are formed one above the other and wherein at least one matrix membrane layer contains 1 to 20 percent by mass of irreversibly denatured protein.
  • Providing a liquid composition comprising a solution of a salt of a polyvalent metal
  • One or more contacting the liquid composition comprising a solution of a salt of a polyvalent metal with a
  • Reaction medium to form a matrix membrane material wherein at least one reaction medium additionally contains 1 to 20 percent by mass of protein which is polymerized into the matrix matrix material forming;
  • the denaturation treatment is carried out as described hereinbefore by a
  • Heat treatment or treatment with an acid solution can be carried out by spraying, dipping, pouring or dripping the acid solution.
  • suitable acids are citric acid, malic acid and ascorbic acid.
  • a 20% ascorbic acid solution is used.
  • the reaction medium contains 2 to 20% by mass of protein, more preferably 4 to 20% by mass of protein, even more preferably 6 to 18% by mass of protein, and most preferably 14 to 17% by mass of protein.
  • a double or multi-layer matrix membrane material By contacting the liquid composition comprising a solution of a salt of a polyvalent metal several times with a reaction medium, a double or multi-layer matrix membrane material can be produced.
  • the already formed matrix membrane material is brought into contact once or more times with a reaction medium containing dissolved alginate.
  • a reaction medium containing dissolved alginate Various reaction media can be used, which differ in their composition, but a sufficient amount of alginate must be included.
  • the mass fraction of sodium alginate in a reaction medium is 1 to 2 percent by mass.
  • the matrix membrane material according to the invention is prepared using the excipient chitosan and according to the
  • Denaturation treatment which is preferably carried out by a heating step, is crushed the matrix membrane material.
  • the comminution is preferably carried out by grinding.
  • the resulting granules are then used as a preservative
  • composition such as yogurt or dairy products in general, or other foods added.
  • the chitosan contained in the matrix membrane material diffuses gradually by osmosis from the matrix membrane into the composition of the food.
  • the matrix membrane material serves as a vehicle for chemically active substances.
  • the comminuted matrix membrane material is suitable for preserving foods, as well as physiologically active compositions, pharmaceutically active compositions and / or cosmetic agents or compositions.
  • the matrix membrane material according to the invention or the matrix membrane is also suitable in particular for coating solid media and surfaces.
  • the present invention relates to a method for
  • the process according to the invention for coating solid media and surfaces with one or more matrix membrane layers with alginate as the basic substance comprises the following steps:
  • Providing a liquid composition comprising a solution of a salt of a polyvalent metal
  • liquid composition comprising a solution of a salt of a polyvalent metal
  • composition wetted solid medium or the surface with a reaction medium to form one or more Matrix membrane layers, wherein at least one reaction medium additionally contains 1 to 20% by mass of protein which is copolymerized into the forming matrix membrane layer;
  • the reaction medium contains 2 to 20 mass% protein, more preferably 4 to 20 mass% protein, even more preferably 6 to 18 mass% protein, and most preferably 14 to 17 mass%.
  • the denaturation treatment is carried out as described hereinbefore by a
  • Heat treatment or treatment with an acid solution can be carried out by spraying, dipping, pouring or dripping the acid solution.
  • suitable acids are citric acid, malic acid and ascorbic acid.
  • a 20% ascorbic acid solution is used.
  • Coating has at least one matrix membrane layer containing 1 to 20 mass percent of a protein that has been polymerized into the matrix membrane layer and then irreversibly denatured.
  • the membrane layer according to the invention has over the known alginate coatings advantageous haptic, optical, antibacterial,
  • suitable components are used for coating the solid media and surfaces for consumption.
  • suitable proteins or protein mixtures, excipients, dyes, and coating compositions produces a matrix membrane coating which is edible and excellently suited for consumption.
  • the process according to the invention is suitable for coating any solid media and solids as well as for coating any surface.
  • Solid medium and solid are used identically herein and are interchangeable.
  • Solid media also include liquid media at room temperature, which have been converted to a solid state by cooling, for example by freezing with liquid nitrogen.
  • solid media are foods such as fruits, vegetables, fish and fish products, meat and sausage products, dairy and cheese products.
  • Solid media may also include the following ingredients, which may be preferably independently selected from physiologically, physically or physico-chemically active substances, pharmaceutically active compounds or compositions, cosmetic agents and
  • compositions Compositions, fragrances and / or flavorings, aromatics, hyaluronic acid,
  • Spices, spice concentrates and spice mixtures chemically active substances such as detergents, catalysts and reagents.
  • the solid media consist of it.
  • surface comprises any type of surface, including the surface of a liquid medium.
  • the method is suitable for coating yoghurt, milk products and other media, which are preferably portioned in containers.
  • the matrix membrane layer acts as a seal of the solid media, for example
  • Surface also includes the inner (inner) surface of a container or
  • the container is a metal can, in particular an aluminum can, can, bottle, in particular PET bottle and
  • Glass bottle, glass jar, or mug especially plastic cups or paper cups.
  • the inventive method for inner coating of cans made of metal especially aluminum cans, metallic containers, cans, bottles, especially PET bottles and glass bottles, glass jars, or cups, especially plastic cups or paper cups.
  • the inner surface of the containers is wetted by pouring, dipping, spraying or dripping with the appropriate solutions to form a matrix membrane layer.
  • the matrix membrane layer acts as a seal on the inner surface of the container and forms a barrier to the contents of the container.
  • Metal-containing surfaces are thus protected against corrosion and the contact between the desired contents of the container and the metal surface is avoided.
  • Matrix membrane layer makes the container impermeable to gases, especially carbon dioxide, oxygen and UV radiation. This improves the preservation and storage time of the contents portioned in the containers. This is particularly advantageous in the field of beverage bottling and food industry. A special advantage of
  • Coating with the matrix membrane layer according to the invention is that it is suitable for consumption. This is particularly advantageous over the known
  • the matrix membrane layer may contain adjuvants, as herein for the matrix membrane layer according to the invention and all embodiments
  • the matrix membrane layer comprises one or more excipients, preferably selected from maltodextrin, xanthan, carbohydrates, emulsifiers, sugar esters (eg (Sucro, E473), fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, waxes, dyes, oils and fats, preferably coconut fat, suitable polymers and copolymers.
  • excipients preferably selected from maltodextrin, xanthan, carbohydrates, emulsifiers, sugar esters (eg (Sucro, E473), fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, waxes, dyes, oils and fats, preferably coconut fat, suitable polymers and copolymers.
  • the process of the invention for the coating of solid media and surfaces can be used in the field of preservation and preservation of food, in the field of
  • Nutritional supplements used in the medical and pharmaceutical sector, in the chemical sector and in the field of cosmetics.
  • the application of the coating to solid media or surfaces is preferably carried out by spraying, dipping and casting or by dripping.
  • the pouring and dripping is preferably carried out with the aid of a lance.
  • the solid media or surfaces are wetted with a solution comprising a salt of a polyvalent metal, which may additionally contain auxiliaries, in particular for stabilizing the matrix membrane layer.
  • the salt of a polyvalent metal calcium lactate is used, which is preferably added to the solution in a mass fraction of 2.0 - 3.0%.
  • the wetting with the solution comprising a salt of a polyvalent metal is carried out in particular by
  • Alginate solution must contain a sufficient amount of alginate. Preferably, from 1.0 to 2.0% by mass of sodium alginate is added to the solution. It forms one
  • Matrix membrane layer which is then subjected to a denaturation treatment.
  • the denaturation treatment is carried out as described hereinbefore by a heat treatment or an acid solution treatment.
  • the treatment with the acid solution can be carried out by spraying, dipping, pouring or dripping the acid solution.
  • suitable acids are citric acid, malic acid and ascorbic acid.
  • Matrix membranes are generated. For this, the solid media or surfaces are contacted once or more times with a reaction medium containing dissolved alginate.
  • a reaction medium containing dissolved alginate Various reaction media can be used, which differ in their composition, but a sufficient amount of alginate must be included.
  • the mass fraction of sodium alginate in a reaction medium is preferably 1 to 2% by mass.
  • Vegetable goods and other foods are used.
  • the formed matrix membrane around the food acts as a barrier between food and surrounding medium and is impermeable to fungi, yeasts, bacteria, carbohydrates and thus contributes to
  • Example 10 describes the coating of a solid medium with a matrix membrane layer with alginate as the basic substance by means of a food dipping technique.
  • the present invention relates to a
  • An alginate spray-based coating method which, by selecting suitable auxiliaries, makes it possible to delay the spoilage of fruit, meat, sausage, fish and vegetable products and other foods by coating the food to be preserved with the matrix membrane layer according to the invention and cured in a heating step and thus provides a barrier to media such as fungi, yeast bacteria, carbohydrates, macromolecules, liquids, moisture and conditioned air.
  • the application of spray methods can be advantageous in particular in the field of process technology compared to immersion techniques.
  • Example 1 Preparation of various core media and reaction media In the following two compositions are described for the preparation of a standard core medium and of standard reaction media (initially without protein). default
  • Core medium and standard reaction media are suitable to form matrix membranes with alginate as the basic substance in and around liquid and solid, aqueous, sugary, alcoholic and oily media, real solutions, emulsions, dispersions and suspensions.
  • Composition 2 (basis for reaction medium, in powder form): ⁇ sodium alginate: 60 g / 100 g ( ⁇ 20%) ⁇ maltodextrin: 35 g / 100 g ( ⁇ 20%) ⁇ sugar ester (Sucro, E473): 5 g / 100 g ( ⁇ 20%)
  • composition 1 20 g were quantitatively transferred in portions into a beaker with 250 ml of water during the treatment with a hand blender or mixer, so that as few air bubbles as possible were stirred into the solution as a result of the addition.
  • bubbles could also be deliberately stirred in so far as they can be found, for example, in the formed matrix membrane bodies. This effect can also be used to achieve a particular buoyancy of the matrix membrane body in a liquid medium.
  • the mixing and mixing was completed when the solution had a high viscosity and no suspension was recognizable. The resulting solution was called the standard core medium.
  • the standard core medium was diluted with water in the ratio 1: 1, 1: 0.75 and 1: 0.5625. This was the appropriate Quantity of water was added to the standard core medium and stirred in with a hand blender so that even here little air bubbles were entered. The mixture was mixed briefly with the hand blender and then allowed to stand for about 1 h.
  • composition 1 To prepare matrix membrane bodies with raspberry syrup (liquid medium to be encapsulated), 20 g of composition 1 were transferred quantitatively into a beaker containing 250 ml of water during the treatment with a blender or mixer, so that as few air bubbles as possible were stirred into the solution.
  • a blender or mixer To prepare matrix membrane bodies with raspberry syrup (liquid medium to be encapsulated), 20 g of composition 1 were transferred quantitatively into a beaker containing 250 ml of water during the treatment with a blender or mixer, so that as few air bubbles as possible were stirred into the solution.
  • composition 1 To prepare matrix membrane bodies with 40% rum (liquid medium to be encapsulated), 20 g of composition 1 were transferred quantitatively into a beaker containing 250 ml of 40% rum during treatment with a hand blender or mixer, so that as few air bubbles as possible were absorbed by the addition the solution was stirred. The mixing and mixing was completed when the solution had a high viscosity and no suspension was recognizable. Then 250 ml of 40% rum were added to the solution and stirred in with a hand blender so that even here little air bubbles were introduced. The mixture was mixed briefly with the hand blender and then allowed to stand for about 1 h.
  • Reaction medium (aqueous): 20 g of composition 2 were transferred in portions into a beaker with 750 ml of water and mixed vigorously with a hand blender. The mixing was completed when the solution had a high viscosity and no suspension was recognizable. The solution was allowed to swell for about 2 hours. The resulting solution was considered standard
  • Reaction medium (aqueous) called.
  • Reaction medium diluted with water in the ratio 1: 1.
  • the appropriate amount of water was added to the standard reaction medium and stirred in with a hand blender and the mixture then allowed to stand for about 1 h.
  • Reaction medium diluted with water in the ratio 1: 1.
  • the appropriate amount of water was added to the standard reaction medium and stirred in with a hand blender and the mixture then allowed to stand for about 1 h.
  • Liquid which represent a measure of viscosity.
  • Table 1 Density of the standard nuclear medium at different dilution levels and standard reaction media (dilution 1: 1) at 20 ° C:
  • Shearing forces of a medium which flows through a capillary is a measure of the viscosity.
  • a vessel which had an opening at the vessel bottom, to which a capillary was attached filled with a defined volume of a medium. Thereafter, the medium was drained into a measuring vessel, stopping the time taken for the medium to drain through the capillary. With the measurement data time and volume, the viscosity was determined by the known methods. Water was used as reference.
  • Table 2 Standard core medium viscosities at different dilution levels and standard reaction media (1: 1 dilution) and a sugar standard series at 20
  • Core medium 1 1 222 ⁇ 50
  • Core medium 1 0.75 41, 2 ⁇ 50
  • Core medium 1 0.5625 16.3 ⁇ 50
  • Reaction medium (aqueous) 1 1 852 ⁇ 50
  • ovalbumin was used as the protein.
  • the stirring of the powdery protein into the reaction medium according to Example 1 must therefore not take place with a mixer, which would cause foaming and thus denaturation. Therefore, commercially available ovalbumin was previously dissolved in a little water and stirred into a concentrated slurry, which was then added to the reaction medium.
  • aqueous and oily reaction media according to Example 1 were used. A spatula tip of salt can improve the solubility of the protein in water.
  • reaction medium aqueous or oily
  • Ovalbumin mush (mass fraction 8%) replaced.
  • the 8 mass% protein reaction medium was then used according to Example 3 to prepare matrix membrane bodies.
  • Raspberry syrup and 40% rum were used as the medium to be encapsulated and added to the core medium as described in Example 1. It is approximately assumed that the matrix membrane bodies obtained had a mass fraction of 8% ovalbumin in their matrix membrane layer. By correspondingly varying the amount of protein used, reaction media having a higher or lower mass fraction of protein were prepared. Overall, raspberry syrup and rum were included in this way
  • Matrix membrane body with a mass fraction of 2%, 4%, 8% and 16% ovalbumin produced in the matrix membrane layer was prepared.
  • Example 3 Preparation of matrix membrane bodies by a lance peristaltic pump method
  • a standardized preparation of matrix membrane body can be carried out with a lance peristaltic pump method.
  • core medium and reaction medium according to Example 1 were prepared in a 1000 ml beaker.
  • the core medium was aspirated by switching on the peristaltic pump with a volume flow of about 1, 6 cm 3 / s, while the reaction medium was operated by a stirring device at a speed of about 2 U / s.
  • the lance was adjusted so that it was positioned directly on the surface of the liquid of the reaction medium.
  • the pulse-pause encoder was switched on, the portion-wise feeding of the core medium started.
  • the dripping for small production quantities (about 0.5 - 1 kg) is completed after about 5 min.
  • the reaction medium is stirred for a further 35 minutes (increasing the reaction time increases the matrix membrane strength). This value was chosen so that a good feel and bite resistance of the formed
  • Matrix membrane body is given. Subsequently, the bodies are screened and rinsed briefly with cold water and then placed in the storage medium consisting of core medium and water in a mixing ratio 2-3: 1 and optionally subjected to further treatment as described in the following examples.
  • the agitator is needed to ensure a continuous mixing of the
  • Reaction medium is ensured so that the formed matrix membrane body does not adhere to each other during the reaction and stick to unwanted clusters.
  • the lance ensures a gentle, reproducible feed of the core medium to the surface and under the surface of the reaction medium. This is a bursting of the core medium in comparison to
  • Peristaltic pump unit The use of a peristaltic pump enables the portioning and reproducibility of larger quantities and volumes of core medium (production of
  • Matrix membrane body up to 20 mm in diameter
  • Valve control unit A reproducible portioning takes place by adjusting a small pulse and pause control unit of the valve. Matrix membrane bodies with exactly the same membrane diameters can be produced. Arrangement of the core media supply: The arrangement of the silicone hose (hydrostatic compensation of the liquid column in the hose) and the use of a peristaltic pump, which sucks the core medium independently, prevents unwanted leakage of the
  • Positioning of the lance The introduction of the core medium by the lance method enables a high production amount in a certain time unit with approximately the same physical properties of the formed matrix membrane body. It eliminates a complicated adjustment of the dripping height, stirring speed and physical adjustment
  • a single matrix membrane layer was prepared by adding the reaction medium
  • Example 1 Standard, as described in Example 1
  • 1 to 20 percent by mass of protein as described in Example 2 were mixed.
  • the auxiliaries xanthan and maltodextrin were admixed to the reaction medium, maltodextrin being added in a mass fraction of 0.8-1.2% and xanthan in a mass fraction of 0.1-0.6%.
  • matrix membrane bodies were produced according to Example 3. The protein and the used
  • Multi-layer matrix membranes were generated by sequential treatment in different reaction media, forming piled-up membranes. It was thus possible to form membranes which had a concentration gradient of the various excipients and thus characteristic functions in the individual layers were possible.
  • reaction media it is of
  • Matrix membrane bodies prepared according to Examples 1 to 3 with 16% by mass protein and raspberry syrup and 40% rum were used for the heat denaturation in a
  • the matrix membrane bodies were placed in a sealable 100 ml glass bottle with the ambient temperature-warm mixture of water and raspberry syrup or 40% rum and the glass bottle then placed in a 80-90 ° C water bath for about 2 min. The temperature of the mixture in the glass bottle was controlled. Immediately after the mixture of 2-3 units of water and 1 unit of raspberry syrup or 40% rum reached a temperature of 70 ° C, the bottle was removed from the water bath. The proteins polymerized in the matrix membrane layer could be hardened by treatment in a water bath in a stable crystalline pearly structure and the matrix membrane bodies were thereby strengthened and preserved in their entirety.
  • the maximum temperature of the mixture in which heat denaturation takes place is crucial because the protein denatures above 45 ° C, but the calcium alginate becomes irreversibly unstable above a temperature of 70 ° C.
  • Example 7 Cryoprocessing of the core medium prior to the preparation of matrix membrane bodies
  • Sequential dripping when taken at the same time after a defined residence in the reaction medium, causes a small difference in the membrane thickness, which is characterized by the beginning and ending of the dripping.
  • the dripping took 10 minutes.
  • Example 8 Treating matrix membrane bodies with a dye mixture
  • Matrix membrane bodies were subjected to staining for treatment with a dye mixture.
  • the example listed here describes a process which is characterized in that the protein polymerized in the alginate shell in a
  • Reaction medium prepared with 16 percent by mass of a protein and then washed with a sieve. Raspberry syrup was used as the liquid medium to be encapsulated. Approximately 8 matrix membrane bodies were filled into 100 ml vials with a dye mixture. The dye mixture was a 2-3: 1 water: wild berry syrup mixture consisting of the blue Dye of the forest berry. The bottles were then placed in a 80-90 ° C water bath for about 4-5 minutes. The bottles were heated until the
  • Dye mixture in the bottles a temperature of max. Reached 70 ° C.
  • matrix membrane bodies were obtained with a bluish metal shimmering shell (dye of wild berry syrup) and reddish content (raspberry syrup).
  • the maximum temperature is crucial because the protein denatures above 45 ° C, but the calcium alginate becomes irreversibly unstable above a temperature of 70 ° C.
  • Matrix membrane bodies and the dye mixture were then gently cooled at room temperature.
  • the presence of the diluted with water dye mixture in the bottles prevented by low osmosis of the water in the core medium that contract the matrix membrane body during the cooling process and a
  • Matrix membrane layer were prepared as described in Examples 1 to 3.
  • An apple weed syrup added to the core medium as described in Example 1 was used as the medium to be encapsulated.
  • the auxiliaries xanthan and maltodextrin were admixed with the reaction medium, maltodextrin being added in a mass fraction of 1.2% and xanthan in a mass fraction of 1.6%.
  • a part of the obtained matrix membrane bodies was subjected to a heat denaturation treatment according to Example 6.
  • the heat-treated and non-heat-treated matrix membrane bodies were washed in a sieve, dried and filled in each case 8 matrix membrane body stacked in empty 100 ml glass bottles, which were then hermetically sealed.
  • the matrix membrane body By stacking the matrix membrane body was exerted by its own weight, an additional pressure that promotes the leakage of liquid.
  • the bottles were stored for a period of 115 hours at room temperature. After 13 hours, 43 hours, 67 hours and 115 hours, the amount of leaked liquid in the individual glass bottles was semiquantitatively determined and compared with each other by comparing the level of leaked liquid in the individual glass bottles. Each time value was determined in triplicate and the results averaged. For this purpose, 3 separate samples (glass bottles) were used for each time value. The glass bottles were used during the
  • Matrix membrane layer was. The leakage of liquid was promoted by the stacking of the matrix membrane body, as by the weight of the body an additional pressure was exerted. No to little fluid was leaked from the matrix membrane bodies with 16 mass% protein in the matrix membrane layer and denaturation treatment.
  • Matrix membrane bodies with 16 mass% protein in the matrix membrane layer and denaturation treatment had no sweet taste in the leaked liquid and the viscosity of the liquid was comparable to that of water. So it can be assumed that the leaked liquid is mainly water acted, with the other components contained in the core medium such as sugar
  • Matrix membrane layer and denaturation treatment overall, the pomp and solid and optical properties were better compared to matrix membrane bodies without protein or denaturing treatment, respectively. This effect was particularly pronounced in the matrix membrane bodies with 16% by mass protein in the matrix membrane layer and denaturation treatment, where the bumpiness and solid and optical properties were retained over the entire 115 hour period and beyond.
  • Example 9A Comparison of the amount of leaked liquid at different
  • Heat step was denatured and then added to the reaction bath.
  • the following matrix membrane bodies were generated: blind (no protein, no heating step), 16% disperse denatured protein (d.P.), 16% native protein with subsequent heat step (n.P + H.).
  • the matrix membrane bodies without and with native protein were prepared as described in Examples 1 to 3 with a core medium according to Example 1 comprising 20-40
  • Reaction medium were additionally admixed with the adjuvants xanthan and maltodextrin, with maltodextrin in a mass fraction of 1.2% and xanthan in a mass fraction of 1.6% were added.
  • Matrix membrane bodies in the composition of their shells are comparable to capsules with a shell of alginate and dispersed pre-denatured protein as described in WO
  • WO 2014082132A1 also describes microparticles with alginate and dispersed pre-denatured protein.
  • a part of the obtained matrix membrane bodies was subjected to a heat denaturation treatment according to Example 6.
  • Table 4 Semiquantitative comparison of the amount of leaked core medium in different matrix membrane bodies during storage in hermetically sealed containers (average of 3 repetitions) after about 48h.
  • the amount of leaked core medium increases from + to +++++.
  • Example 10 Coating Solid Media and Foods with a
  • a piece of pork loin was portioned into equal pieces of about 30 g and
  • the fortified food was added to an aqueous solution comprising 1.0% to 2.0% by weight of sodium alginate, 0.9% by weight of maltodextrin, 0.1% by weight of sugar ester (Sucro, E473) and optionally 16% by weight of protein, sugar syrup and / or Adding about 100ml of a 10% chitosan solution, and finally subjected to a heat treatment or an acid treatment.
  • the reaction time in the reaction medium was 30 minutes in each case.
  • Heat treatment was in a heated bath at a temperature of 45-80 ° C
  • the acid treatment was carried out in a 20% ascorbic acid solution.
  • the heat step and treatment with the 20% ascorbic acid irreversibly denatured and cured the protein incorporated into the calcium alginate structures formed.
  • Table 5 Pork sirloin pieces were exposed to different reaction media.
  • a + H Calcium alginate membrane with subsequent heat step 70 ° C
  • a + S Calcium alginate membrane with subsequent ascorbic acid step (20%)
  • a + P Calcium alginate membrane and incorporation of protein 16
  • a + P + H Calcium alginate coating and protein incorporation with protein
  • a + P + S + Z Calcium alginate membrane with additional sugar syrup and incorporation of protein followed by ascorbic acid (20%)
  • a + C Calcium alginate membrane and chitosan solution (10%) without heat
  • a + P + C calcium alginate membrane and incorporation of protein 16
  • a + H + P + C Calcium alginate membrane and incorporation of protein 16
  • Table 7 All samples were photographed daily, weighed and semi-sensitively examined for fungal and mold growth.
  • the amount of fungi, molds and yeasts present on the surface of the coated food increases from + to +++++, "-" means that no mold was detectable.
  • nat.P. Calcium alginate bead with originally native dissolved protein
  • nat.P + H. Calcium alginate bead with originally native dissolved protein with heat step
  • the matrix membrane bodies without and with native protein were prepared as described in Examples 1 to 3 with a core medium according to Example 1 comprising 20-40
  • Reaction medium were additionally mixed with the adjuvants xanthan and maltodextrin, with maltodextrin in a proportion by mass of 1.2% and xanthan in a mass fraction of 1, 6% were added.
  • WO 2012/142153 For the matrix membrane body with disperse denatured protein already denatured protein was stirred into the reaction medium. For this purpose, ovalbumin was previously denatured by a heat step and only then added to the reaction bath.
  • the resulting matrix membrane bodies are in the composition of their shell comparable to capsules with an envelope of alginate and disperse, pre-denatured protein as described in WO 2012/142153.
  • WO 2014/082132 also describes microparticles with alginate and disperse, pre-denatured protein.
  • Example 6 A part of the obtained matrix membrane bodies was subjected to a heat denaturation treatment according to Example 6. It was found that all samples behave differently in their optical and watertight properties. Samples with already denatured protein are similar in their properties to those of the blank. It could be observed that a small amount of the denatured dispersed protein slightly clouds the skin (shell). A gloss effect was not observed. The two samples blended with native protein differ from Blind and 16% dP in total in the stronger milky and lustrous appearance due to the incorporation of the native protein.
  • the liquid leakage and the total mass balance can be explained as follows.
  • samples with native protein and subsequent heat treatment have a measurable and significant improvement in the overall balance compared to denatured protein (d.P.) and all other samples
  • Table 8 shows the raw data of the sample Blind (B):
  • Table 9 shows the raw data of the sample blank with heat treatment (B.H):
  • Table 11 shows the raw data of the sample 16% den.P.H (d.P.H):
  • Table 12 shows the raw data of the sample 16% native protein (n.P.):
  • Table 13 shows the raw data of the sample 16% native protein with heat step (n.P.H):
  • Sample Run 1-4 of the sample 16% native protein with heat step i. Calcium alginate bead with originally native dissolved protein with heat step is shown graphically in FIG.
  • the total mass balance constant mass fraction is shown in FIG.
  • Matrix membrane bodies were prepared as described in Example 11.
  • the amount, for example in the form of a dye, of the spilled medium is essentially determined by the pore size or quality of the membrane. It is assumed that each individual component of the core medium has its own osmotic pressure and that all components in the sum determine the total pressure from the inside of the ball. However, it is also possible that constituents not only escape through the osmotic pressure, but that their own molecular size and the pores of the membrane are decisive. So you can, for example, ingredients in the
  • Matrix membrane bodies were prepared as described in Example 11 and
  • the core medium was admixed with 1-10% citric acid as an electrolyte, which can thus be released gradually and simulate leakage of a core medium component with its own partial vapor pressure (due to osmotic pressure and concentration balance).
  • the raw data were normalized for the respective sample to the sample weight at time zero and referenced to the ideal final value, ie the period of time that must elapse to reach 100% of the final value conductivity.
  • the graphs normalized to the dead weight and the final value are shown in FIGS. 18 and 19.
  • the graph for the pre-denatured protein (d.Prot) sample in Figure 18 reaches 70% of the final conductivity after 220 minutes as compared to the native protein sample graph followed by heat treatment (n.Prot + H) containing the Value only reached at 270 min.
  • the graph for the pre-denatured protein (d.Prot) sample in FIG. 19 reaches 95% of the final conductivity after 467 minutes as compared to the native protein sample graph followed by heat treatment (n.Prot + H) using the Value only reached at 1490 min.
  • the first part e 11 ⁇ * is a short term up to 300 min, the range up to about 2000 min is determined by the second term '.
  • the constants m1, m2, m3 and m4 result from the equation of the fit straight, the error or standard deviation is given as 10% and can be taken from the ideal fit curves from the figures.
  • the deviations from the fit straight line ie how much does the ideal curve deviate through the Measured values from) R with the method of the least squares compared to the ideal curve is very good to measure.
  • the purpose of the new coating medium is to control the medium to be encapsulated in a controlled and / or time-delayed / prolonged manner, to mask certain tastes and odors, and to provide improved storage and transport possibilities.
  • Controlled release of controlled-release ingredients under certain changed external conditions e.g. Temperature change, change in pH, change in chemical environment (e.g., rotting, digestion, enzymatic), mechanical stress (e.g., chewing)
  • Excipients sugars, sweeteners, salt, spices, acidulants (malic acid), flavor enhancers, preservatives, other additives and excipients
  • Taste experience (for example sour) should take place with a time delay when consumed
  • Vitamins, amino acids, caffeine, taurine, minerals, pharmaceuticals, unpleasant taste or smell should be avoided (covered), biological half-life of an active substance should be prolonged by protracted release.
  • Coated malic acid as a dehydrated salt is used, for example, in confectionery products.
  • a controlled release of the malic acid should take place, so that the acidic taste only becomes noticeable with a time delay.
  • palm oil is applied by conventional methods such as fluidized bed granulation to crystalline malic acid in a layer thickness of a few hundred micrometers and serves in addition to the controlled release as a lipophilic protection against external conditions.
  • An alternative coating material must be chosen such that the malic acid which is readily soluble in alcohol and aqueous media does not dissolve but remains in crystalline form. It must also be ensured that the taste properties of malic acid are not adversely affected, for example, no other malic-acid metal salts should react with the malic acid and thereby precipitate as an alternative salt with undesirable taste properties.
  • solubility with other metal salts for example with calcium as calcium malate (calcium salt of malic acid)
  • calcium as calcium malate calcium salt of malic acid
  • the salt formed in or around the food acts as an acidity regulator.
  • it depends essentially on the stoichiometric ratios of calcium as calcium alginate and the calcium as calcium alginate, whether and with whom the calcium is formed as a metal salt. Due to the polymeric character of the alginate structure, the affinity of calcium for alginate is higher than that of calcium for malate. Due to the stability of the polymeric calcium alginate complex, the presence of alginate can break the calcium from the composite of calcium malate so that the removal of calcium again results in free malate.
  • a dried amount of malic acid in crystalline form is mixed with an approx. 10-20% aqueous calcium solution, preferably as lactate, in a ratio of 10: 1 (10 parts malic acid, 1 part aqueous calcium solution) and made into a pulp for approx. 2-3 min stirred.
  • the mixture is then dried in air or by other dehydrogenation methods. After the drying process, the clumped mixture is crumbled, so that the particle size of the mixture now again corresponds to the original crystalline form of malic acid.
  • malic acid also contains calcium bound calcium in the order of about 10%.
  • the originally used amount of malic acid (following: modified malic acid).
  • the mass fraction of calcium regulates / determines the thickness of the subsequent coating medium. The calcium is too at this time not freely present but involved in small amounts as Caiciummalat in the framework of the malic acid
  • the reaction medium (aqueous) is prepared taking into account the composition 2 (see Example 1).
  • An additional amount of protein can be chosen freely and is not limited exclusively to 16%, preferably 4-8% protein are used.
  • the reaction medium aqueous
  • the reaction medium oily
  • the standard reaction medium oily
  • a defined amount of protein can be added as well. Both media have a certain viscosity, resulting in the
  • reaction medium (following: aqueous or oily) is contacted with the modified malic acid.
  • Conventional methods such as fluidized bed granulation are applicable.
  • the merger was achieved in that a small amount of the reaction medium to the modified
  • the malic acid is re-formed by the lactic acid which is now freely available.
  • the calcium alginate is applied to the surface of the malic acid and takes over the desired properties of the coating medium; see FIG. 21.
  • the pure malic acid in crystalline form is not pretreated in this embodiment.
  • the treatment is carried out sequentially with calcium and with alginic acid, the order can be reversed.
  • the pure malic acid can be treated by a conventional method such as fluidized bed granulation. In contact with viscous calcium
  • a solution corresponding to composition 1 (see example 1) is prepared.
  • the viscosity of the solution can be adjusted by the two supplied media maltodextrin and xanthan gum. It must be noted that there should be a minimum level of viscosity as the aqueous calcium solution would otherwise dissolve the pure malic acid by the high level of water (a high viscosity reduces the diffusivity).
  • the method of direct treatment with calcium is based on the fact that the contact with the medium malic acid only takes place via adhesive properties of the viscous viscous composition 1 at the surface. The water bound in the composition 1 should as far as possible not diffuse into the malic acid medium and thereby dissolve the malic acid. A quick subsequent contact with viscous alginic acid is therefore imperative.
  • composition 2 A solution according to composition 2 (see example 1) is prepared.
  • the composition can be varied as needed for the properties of the controlled release. Likewise, an admixture of protein is recommended, preferably in a proportion of 4 - 8%.
  • the malic acid medium pre-treated with the composition 1 is now brought into contact with the composition 2.
  • a conventional method, such as fluidized bed granulation, is preferably used for this purpose. The spraying and bringing into contact should take place intermittently and in small quantities. The order of bringing together the pure malic acid with the compositions 1 and 2 can also be reversed.
  • the viscosity of the composition in the second merge need not be so high as in the composition of the first merge, because a quick Hininein diffusing and reacting in and with each other composition favors the formation process of the new coating medium.
  • the treatment takes place sequentially and optionally several times in succession.
  • the temperature at the end of the treatment can be slightly increased to about 65 ° C, so that a denaturation of the added protein can be enforced.
  • the matrix membrane framework In some application examples and embodiments for the encapsulation of aqueous media, it is necessary for the matrix membrane framework to prevent the escape of water even more. In addition, if necessary, the haptic properties (soft, elastic) to be changed and the mechanical stability can be increased.
  • shellac can be applied not only as a surface as a layer, but that a direct polymerisation takes place in that a pH-neutral solution is mixed directly into the alginate (reaction).
  • Shellac as a hard coating with polymeric water-insoluble properties as a further barrier to the escape of the aqueous core medium, for haptic stabilization of matrix membrane coatings and for improving deformation properties, as well as for optical enhancement by gloss effects, optionally polymerized into the matrix membrane or / and on the matrix membrane can be applied.
  • Shellac solution 1 (10%): Shellac solution 6 (pH neutral):
  • ella shellac 10 g / 100 g
  • shellac 25 g / 100 g
  • Shellac Solution 2 (20%): Shellac Solution 7:
  • Shellac solution 4 (40%): shellac solution 9:
  • ⁇ ethanol 96% 60 g / 100 g ⁇ Composition 2 aqueous ⁇ shellac: 40 g / 100 g (+ 16% protein): 50 g / 100 g
  • Shellac solution 6 can optionally and depending on the concentration requirement with composition 2 are mixed (shellac solutions 7 - 9).
  • a reaction to matrix membrane beads can be effected by first stirring the core medium with the pure composition 2 and, after a certain time of, for example, 10 to 15 minutes in one of the shellac solutions 7-9. The already formed matrix membrane beads are then stirred for a further 15-20 minutes, so that the shellac is polymerized into the alginate skin. After the reaction time, the matrix membrane beads can be subjected to a heat treatment and / or subjected to further treatments. Combinations and different sequences are also possible.
  • a special prototype has emerged when matrix membrane beads are first stirred in a reaction bath of composition 2 and a proportion of 16% protein for about 10 to 15 minutes and then transferred to shellac solution 8 and stirred there for a further 15 to 20 minutes , At the end of the reaction will be treated the prototype with citric acid to denature the shellac and the protein also contained.
  • any existing matrix membrane sphere based on alginate can be improved by further treatment with shellac solutions 1-7 and combinations thereof so that a glassy hard and stable coating is formed on the matrix membrane spheres.
  • the sample is optionally and optionally treated with combinations in the respective shellac solutions 1-7.
  • the matrix membrane spheres are exposed to different reaction times in the shellac solutions 1-7 by the sample either in the respective shellac solution stirred or the shellac solution is dropped onto the sample.
  • a prototype is first generated with the reaction medium composition 2 (aqueous) and 16% protein. After a heat treatment according to Example 6), the prototype is stirred for about 30 minutes in a shellac solution 6. The prototype is then dried. Another layer forms around the matrix membrane with the following properties: glass-like, transparent, specular, hard, stable, yielding and porous. In order to achieve the same properties, it was also possible to use the prototype after treatment with shellac solution 6 in one of the baths described in point d. are discouraged.
  • a prototype was first generated with the reaction medium composition 2 (aqueous) and 16% protein. On a purpose-built ball holder, the prototype was treated with shellac solution 5 by dropping the solution onto the prototype several times.
  • the alcoholic shellac solution enclosed the prototype, which is then subjected to drying.
  • Another layer formed around the matrix membrane with the following properties: hard, stable, porous and highly water-impermeable. It could be observed that the prototype suffered no quality and weight loss over a period of one week in air.
  • Quenching Solution 1 Quenching Solution 3:
  • citric acid 10 g / 100 g
  • Quenching Solution 2 Quenching Solution 4:
  • quench baths it is also possible to use combinations of the quench baths, so that the prototype produced after a 30 minute treatment with shellac solution 6 for about 2 min in the quenching solution 1 is added and then again for another 15 min in the shellac solution. 6 is stirred. The prototype is placed a second time in the quenching solution 1, the process could also be repeated several times. Afterwards the sample was dried.
  • quenching solutions There are also combinations of quenching solutions conceivable.
  • Each of the quench media may additionally contain additives such as sugars to improve the flavor properties.
  • Example 16 Production process for producing a matrix membrane and matrix membrane composition, which is characterized in that the admixture of additives such as maltodextrin, gelatin or protein influences the matrix membrane such that its pore size becomes controllable.
  • This controllable molecular sieve makes it possible that certain ingredients of the core medium, which are characteristic in size, can pass through the matrix membrane and others can not.
  • the idea according to the invention is described using the example of the isolation of a protein in honey.
  • a core medium such as a stable encapsulation that leakage of the nuclear medium is prevented.
  • the core medium may be desirable for the core medium to escape gradually, rapidly or slowly, as well as partially or completely in its composition.
  • the inventive concept is based on the properties of a molecular sieve, so that certain size-dependent substances can penetrate the pore size of the membrane and other substances are prevented.
  • the idea according to the invention describes a method which makes it possible to prepare foods, pharmaceuticals, encapsulate medical products, cosmetics, sanitary substances, bioactive substances (pesticides, etc.), oils / fats, etc., so that a targeted release and barrier of the nuclear medium can be used by controlling the matrix membrane as a molecular sieve.
  • the idea involves not only the release of a shrouded, encapsulated core medium, but also a barrier (matrix membrane) between two media, the partial and complete exchange of which can be forced or prevented. Examples include the coating of food, the separation of liquid, viscous, alcoholic, sugar-containing media, dispersions, emulsions through a matrix membrane and semipermeable or permeable behavior towards different macromolecules.
  • the molecular sieve properties of the matrix membrane can be used in the enrichment of honey protein according to the invention.
  • the composition for example by admixing maltodextrin or gelatin (and also protein) into the matrix membrane, the pore size thereof was changed in such a way that the matrix membrane prevents or forces an exchange of substances.
  • a determination of the authenticity of honey is usually made by determining its amino acids and proteins. For the isolation of a honey-specific protein to determine its amino acid sequence, it is necessary to isolate and enrich the honey protein as a sample preparation.
  • honey matrix membrane beads were optionally mixed with about 10 g of composition 1 with a hand blender (according to the instructions for the preparation of the core medium according to Example 1) or preferably with about 3 - 4 g of pure calcium and stirred for about 10 min (described below ).
  • a hand blender according to the instructions for the preparation of the core medium according to Example 1
  • a sufficient viscosity optionally dissolved gelatine as well as maltodextrin or other thickeners can be added (not used here).
  • the preparation of honey matrix membrane beads was carried out in a reaction bath having the composition 2 described (aqueous) for about 30 min. After preparation, the matrix membrane beads were isolated from the reaction medium and washed sufficiently. 10 balls were then placed in a dialysis bath containing about 2 liters of water.
  • the balls sink down due to the higher density of the honey.
  • one chose a long cylinder whose osmotic pressure at the bottom of the vessel is sufficiently high due to the high water column.
  • increased washout is enforced by gradually changing fresh water continuously or discontinuously.
  • the honeycomb mono- and in the core medium Oligosaccharides (molecular size few angstroms) were gradually washed away by escaping through the pores of the matrix membrane framework (approximately -4 nm), while the protein and amino acid clusters (> 5 nm) are held up by the mesh structure of the matrix membrane.
  • the matrix membrane it may be possible for the matrix membrane to bind and capture the protein directly in its skin. The samples are washed out when they float on the water surface. In a final step, the balls were dried.
  • a method of producing a matrix membrane and matrix membrane composition by admixing nanoparticles and nanostructures for gradual, rapid or slow partial or total release of encapsulated ingredients and bound substances and core media for food, pharmaceutical, medical, cosmetic and sanitary applications.
  • the nanoparticles segregated into the matrix membrane are pictorially in the form of plugs in the matrix membrane, which are pulled or dissolved under certain environmental changes, so that the core medium escapes in a targeted manner.
  • micro- and nanoparticles powdery substances, (co) polymers and colloidal polymer and copolymer solutions in an alginate skin.
  • a matrix membrane can be used as a scaffold for this purpose.
  • the nanoparticles are copolymerized in such a way that they are more or less dense in the alginate framework. Here they can perform their actual function. For example, one can think of the nanoparticles as stoppers in the skin that are pulled (released) when disturbed by external conditions such as pH change, temperature change, etc. This may, for example, play an important role in tabletting when tablets and other core media are coated with such a skin, so that a release of the ingredients, for example, in the small or duodenal intestine is desired.
  • Controlled release of controlled-release ingredients under certain changed external conditions e.g. Temperature change, change in pH, change in chemical environment (e.g., rotting, digestion), mechanical stress (e.g., chewing)
  • composition 1 and composition 2 both as reaction medium are prepared according to the instructions for the preparation of the core medium according to Example 1.
  • the addition of the microparticles and nanoparticles may be accomplished by admixture with one or more of these compositions.
  • various particles such as linseed, chia seeds and blue clay but also methylcellulose and other copolymers such as Evonik E Po can be used here.
  • the matrix membrane is described here.
  • Embodiments illustrate, but without limiting the scope of the invention.
  • a matrix membrane body comprising a core medium and a shell comprising one or more matrix membrane layers with alginate as the matrix, characterized in that at least one matrix membrane layer contains 1 to 20 mass percent irreversibly denatured protein.
  • Matrix membrane body according to the preceding embodiment, characterized
  • the matrix membrane body after storage at a temperature of 20 ° C after a period of about 145 h based on the starting mass of
  • Matrix membrane body still has a mass fraction of at least 35%.
  • the protein comprises an animal or vegetable protein or a mixture thereof.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the protein comprises soy protein or serum proteins, in particular albumins and globulins.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the protein comprises ovalbumin, lactalbumin or bovine serum albumin.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the protein is ovalbumin.
  • the matrix membrane layer contains 2 to 20 percent by mass of irreversibly denatured protein.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the matrix membrane layer contains 4 to 20 percent by mass of irreversibly denatured protein.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the matrix membrane layer contains 6 to 18 percent by mass of irreversibly denatured protein.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the matrix membrane layer contains 14 to 17 percent by mass of irreversibly denatured protein.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the matrix membrane layer contains 14 to 17 percent by mass irreversibly denatured protein and has a metallic, pearl-like gloss effect.
  • Matrix membrane body according to one of the preceding embodiments, characterized in that the matrix membrane layer contains 16 percent by mass of irreversibly denatured protein and has a metallic, pearl-like gloss effect.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the one or more matrix membrane layers additionally comprise one or more excipients, preferably selected from maltodextrin, xanthan, carbohydrates, emulsifiers, sugar esters, fatty acids, shellac, glycerol, chitosan, gold, silver, Nano- and microparticles, gelatin, beeswax, wax, dyes, oils and fats, suitable polymers and suitable copolymers.
  • excipients preferably selected from maltodextrin, xanthan, carbohydrates, emulsifiers, sugar esters, fatty acids, shellac, glycerol, chitosan, gold, silver, Nano- and microparticles, gelatin, beeswax, wax
  • Matrix membrane body according to one of the preceding embodiments characterized in that the core medium comprises the solution of at least one salt of a polyvalent metal, preferably calcium.
  • the core medium comprises calcium lactate, preferably in a mass fraction of 2.0 - 3.0%.
  • the core medium comprises at least one liquid suitable for consumption.
  • the liquid suitable for consumption is preferably selected from aqueous, oily, sugary and alcoholic liquids.
  • liquid suitable for consumption is preferably selected from alcoholic beverages, lemonades, dairy products, fruit or vegetable juices, fruit drinks, syrup, in particular fruit syrup or coffee syrup and others
  • Matrix membrane body according to one of the preceding embodiments, characterized in that the core medium comprises one or more physiologically, physically or physicochemically active compounds, pharmaceutically active compounds or compositions, cosmetic agents or compositions, fragrances, aromatics, hyaluronic acid, flavorings, in particular essential oils and volatile constituents, Spices, spice mixtures, spice mixtures, chemically active compounds, catalysts and / or reagents, especially washing-active substances comprises.
  • Matrix membrane body according to one of the preceding embodiments, characterized in that the core medium additionally comprises one or more excipients, preferably selected from maltodextrin, xanthan, gelatin, chitosan, shellac, glycerol, dyes and proteins.
  • Matrix membrane body according to one of the preceding embodiments characterized in that the matrix membrane body on the outer
  • Matrix membrane layer having at least one additional coating layer, wherein the coating layer comprises one or more adjuvants, preferably selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and suitable copolymers.
  • Matrix membrane body according to one of the preceding embodiments, characterized in that the at least one matrix membrane layer having 1 to 20
  • Percent of irreversibly denatured protein is obtained by contacting native protein, polysaccharide and at least one polyvalent cation and performing a denaturation step of the protein.
  • Providing a core medium comprising a solution of a salt of a polyvalent metal
  • Matrix membrane body is formed, and wherein at least one reaction medium additionally contains 1 to 20 percent by mass of protein which is copolymerized into the matrix matrix layer forming;
  • Method according to the preceding embodiment characterized in that the introduction of the core medium takes place in a reaction medium as introducing a core medium, which is enveloped by at least one matrix membrane layer.
  • Method according to one of the preceding embodiments characterized in that the matrix membrane bodies formed after introduction into a reaction medium are removed and introduced into another reaction medium.
  • Method according to one of the preceding embodiments characterized in that the denaturing takes place after the last introduction into a reaction medium.
  • Method according to one of the preceding embodiments characterized in that the denaturing is followed by a further introduction into a reaction medium.
  • the protein comprises an animal or vegetable protein or a mixture thereof.
  • the protein comprises soy protein or serum proteins, in particular albumins and globulins.
  • the protein comprises ovalbumin, lactalbumin or bovine serum albumin, or mixtures thereof.
  • the protein is ovalbumin.
  • the reaction medium comprises 2 to 20% by mass of protein.
  • the reaction medium comprises 4 to 20% by mass of protein.
  • the reaction medium comprises 6 to 18 mass percent protein.
  • reaction medium comprises 14 to 17 percent by mass of protein.
  • the denaturation of the polymerized into the matrix membrane layer protein by thermal treatment of the matrix membrane body in a temperature range of 45 to 80 ° C takes place.
  • the reaction medium comprises 16% by mass of protein and the denaturation takes place by thermal treatment at 70 ° C.
  • the denaturation of the protein takes place by treatment of the matrix membrane body with an acid solution.
  • the acid solution comprises citric acid, malic acid and / or ascorbic acid.
  • the acid solution is a 20% ascorbic acid solution.
  • the polyvalent metal is calcium.
  • the salt of the polyvalent metal is calcium lactate.
  • calcium lactate is contained in a mass fraction of 2.0 - 3.0%.
  • Method according to one of the preceding embodiments characterized in that sodium alginate is contained in a mass fraction of 1, 0 to 2.0%.
  • the core medium, the solution comprising a salt of a polyvalent metal and / or the reaction medium is selected from solutions, in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, suspensions,
  • an oily solution comprises coconut fat.
  • the basis for an oily solution is coconut fat.
  • the core medium additionally contains at least one liquid medium to be encapsulated.
  • the liquid medium to be encapsulated comprises at least one liquid suitable for consumption.
  • the liquid suitable for consumption is selected from alcoholic beverages, lemonades, dairy products, fruit or vegetable juices, fruit drinks, fruit syrups, coffee syrup, coffee and tea preparations or mixtures thereof.
  • the core medium additionally contains one or more physiologically, physically or physicochemically active compounds, pharmaceutically active compounds or compositions, cosmetic agents or compositions, fragrances,
  • Flavorings aromatics, hyaluronic acid, essential oils, spices, spice concentrates, spice mixtures, chemically active compounds, catalysts and / or reagents.
  • the core medium additionally contains one or more excipients, preferably selected from maltodextrin, xanthan, emulsifiers, sugar esters, fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin,
  • the core medium is brought into the form of an arbitrary geometric body prior to introduction into a reaction medium by cryo-treatment under conversion into a solid state of aggregation.
  • the geometric body has a diameter in the size range of 5-100 mm.
  • the cryo treatment is effected by flash freezing with liquid nitrogen.
  • the reaction medium additionally comprises one or more auxiliaries,
  • Matrix membrane body takes place, which comprises one or more matrix membrane layers.
  • Process according to one of the preceding embodiments characterized in that the application of the coating layer takes place as immersion of the matrix membrane body in a coating composition, or as spraying of the matrix membrane body with a coating composition, or as dripping or pouring of the matrix membrane body
  • Coating composition is carried out on the matrix membrane body.
  • the coating composition comprises at least one adjuvant, which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers , Matrix membrane material with alginate as the basic substance, characterized in that the matrix membrane material contains 1 to 20 percent by mass of irreversibly denatured protein.
  • Matrix membrane material according to the preceding embodiment characterized in that the coating composition comprises at least one adjuvant, which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers , Matrix membrane material with alginate as the basic substance, characterized in that the matrix membrane material contains 1 to 20 percent by mass of irreversibly denatured protein.
  • Matrix membrane material according to the preceding embodiment characterized
  • the matrix membrane material comprises one or more matrix membrane layers with alginate as base substance formed above one another, wherein at least one matrix membrane layer contains 1 to 20% by mass of irreversibly denatured protein.
  • Matrix membrane material according to one of the preceding embodiments characterized in that the protein comprises an animal or vegetable protein or a mixture thereof.
  • Matrix membrane material according to one of the preceding embodiments characterized in that the protein comprises soy protein or serum proteins, in particular albumins and globulins.
  • the protein comprises ovalbumin, lactalbumin or bovine serum albumin, or mixtures thereof.
  • Matrix membrane material according to one of the preceding embodiments, characterized in that the protein is ovalbumin.
  • Matrix membrane material according to one of the preceding embodiments characterized in that the matrix membrane material or a matrix membrane layer contains 2 to 20 percent by mass of irreversibly denatured protein. Matrix membrane material according to one of the preceding embodiments, characterized in that the matrix membrane material or a matrix membrane layer contains 4 to 20 percent by mass of irreversibly denatured protein. Matrix membrane material according to one of the preceding embodiments, characterized in that the matrix membrane material or a matrix membrane layer contains 6 to 18 percent by mass of irreversibly denatured protein. Matrix membrane material according to one of the preceding embodiments, characterized in that the matrix membrane material or a matrix membrane layer contains 14 to 17 percent by mass of irreversibly denatured protein. Matrix membrane material according to one of the preceding embodiments, characterized in that the matrix membrane material or a matrix membrane layer 16 Percent by mass contains irreversibly denatured protein and has a metallic pearlescent gloss effect.
  • Matrix membrane material according to one of the preceding embodiments, characterized
  • the matrix membrane material additionally comprises one or more excipients, preferably selected from maltodextrin, xanthan, emulsifiers, sugar esters, fatty acids, shellac, glycerol, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, Oils and fats, suitable polymers and suitable copolymers.
  • excipients preferably selected from maltodextrin, xanthan, emulsifiers, sugar esters, fatty acids, shellac, glycerol, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, Oils and fats, suitable polymers and suitable copolymers.
  • Matrix membrane material according to one of the preceding embodiments, characterized
  • the matrix membrane material is coated with at least one additional coating layer, wherein the coating layer comprises one or more excipients, preferably selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and suitable copolymers.
  • the coating layer comprises one or more excipients, preferably selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and suitable copolymers.
  • Matrix membrane material according to one of the preceding embodiments, characterized
  • Matrix membrane material according to one of the preceding embodiments, characterized
  • the matrix membrane material is obtained by bringing native protein, polysaccharide and at least one polyvalent cation into contact and performing a denaturation step of the protein.
  • Embodiment as a molecular sieve.
  • Providing a liquid composition comprising a solution of a salt of a polyvalent metal
  • reaction medium comprising a dissolved alginate
  • Method according to one of the preceding embodiments characterized in that the bringing into contact by spraying, dropping, laying a drop of the liquid composition on or under the surface of the reaction medium, spraying, including spraying an already formed matrix membrane material with a reaction medium, Immersing, including immersing an already formed matrix membrane material in a reaction medium, or dripping or infusing, including dropping or pouring reaction medium onto an already
  • Reaction medium connects.
  • reaction medium comprises 2 to 20 percent by mass of protein.
  • reaction medium comprises 4 to 20 percent by mass of protein.
  • reaction medium comprises 6 to 18 mass percent protein.
  • reaction medium comprises 14 to 17 percent by mass of protein.
  • Method according to one of the preceding embodiments characterized in that the denaturation of the protein polymerized into the matrix membrane material takes place by thermal treatment of the matrix membrane material in a temperature range from 45 to 80 ° C.
  • reaction medium comprises 16% by mass of protein and the denaturation is effected by thermal treatment at 70 ° C.
  • the acid solution comprises citric acid, malic acid and / or ascorbic acid.
  • liquid composition comprising a solution of a salt of a polyvalent metal and / or the reaction medium is selected from solutions, in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, suspensions, dispersions and emulsions.
  • an oily solution comprises coconut fat.
  • liquid composition comprising a solution of a salt of a polyvalent metal additionally comprises one or more excipients, preferably selected from maltodextrin, xanthan, emulsifiers, sugar esters, fatty acids, proteins, shellac, glycerol, chitosan, gold, silver , Nano and
  • reaction medium additionally comprises one or more excipients, preferably selected from maltodextrin, xanthan, carbohydrates,
  • Emulsifiers proteins, shellac, glycerin, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, oils and fats, suitable polymers and copolymers.
  • a coating layer is additionally applied to the matrix membrane material.
  • Coating composition on the matrix membrane material Coating composition on the matrix membrane material.
  • the coating composition comprises at least one adjuvant, which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • adjuvant which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • Matrix membrane material is generated.
  • reaction medium contains the excipient chitosan and the formed matrix membrane material is comminuted after the denaturation treatment.
  • Method according to the preceding embodiment characterized in that the matrix membrane material is mechanically comminuted.
  • Embodiments for coating liquid media and solid media are provided.
  • Embodiments for preserving foods characterized in that the matrix membrane material contains the excipient chitosan.
  • the matrix membrane material contains the excipient chitosan and the matrix membrane material in comminuted form, in particular as granules, a composition to be preserved, in particular yogurt, is admixed.
  • Matrix membrane material with alginate as the basic substance comprising the steps:
  • Providing a liquid composition comprising a solution of a salt of a polyvalent metal
  • a composition comprising a solution of a salt of a polyvalent metal; - One or more contacting the solid medium wetted with the liquid composition or the surface with a reaction medium to form one or more
  • Matrix membrane layers wherein at least one reaction medium additionally contains 1 to 20% by mass of protein which is copolymerized into the forming matrix membrane layer;
  • a method according to the preceding embodiment characterized in that contacting the solid medium wetted with the liquid composition or the surface with a reaction medium takes place as bringing into contact a solid medium or a surface containing at least one Matrix membrane layer are coated.
  • wetting is done by dipping, spraying, dripping, or pouring.
  • contacting is done by dipping, spraying, dripping, or pouring.
  • wetting and / or contacting is done by spraying.
  • the protein comprises an animal or vegetable protein or a mixture thereof. 120. Method according to one of the preceding embodiments, characterized in that the protein comprises soy protein or serum proteins, in particular albumins and globulins.
  • the protein comprises ovalbumin, lactalbumin or bovine serum albumin, or mixtures thereof.
  • the protein is ovalbumin.
  • reaction medium comprises 2 to 20% by mass of protein.
  • reaction medium comprises 4 to 20% by mass of protein.
  • reaction medium comprises 6 to 18% by mass of protein.
  • reaction medium comprises 14 to 17% by mass of protein.
  • polymerized protein by thermal treatment of the solid medium or the surface in a temperature range of 45 to 80 ° C.
  • reaction medium comprises 16% by mass of protein and the denaturation takes place by thermal treatment at 70 ° C.
  • the denaturation of the protein is carried out by treating the solid medium or the surface with an acid solution.
  • the acid solution comprises citric acid, malic acid and / or ascorbic acid.
  • the acid solution is a 20% ascorbic acid solution.
  • the polyvalent metal is calcium.
  • the salt of the polyvalent metal is calcium lactate.
  • calcium lactate is contained in a mass fraction of 2.0 - 3.0%.
  • dissolved alginate is sodium alginate.
  • sodium alginate is contained in a mass fraction of 1, 0 to 2.0%.
  • liquid composition comprising a solution of a salt of a polyvalent metal and / or the reaction medium is selected from
  • Solutions in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, suspensions, dispersions and emulsions.
  • an oily solution comprises coconut fat.
  • liquid composition comprising a solution of a salt of a polyvalent metal additionally contains one or more auxiliaries,
  • reaction medium additionally comprises one or more excipients, preferably selected from maltodextrin, xanthan, carbohydrates,
  • Emulsifiers proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, wax, dyes, oils and fats, polymers and copolymers.
  • Coating layer is applied.
  • the application of the coating layer is carried out as applying a coating layer on a solid medium or a surface which are coated with at least one matrix membrane layer.
  • the application of the coating layer takes place as immersion of the solid medium or the surface in a coating composition, or as spraying of the solid medium or the surface with a coating composition, or as dripping or pouring the coating composition onto the solid medium or the surface.
  • the coating composition comprises at least one adjuvant, which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • adjuvant which may preferably be selected from shellac, glycerol, beeswax, wax, dyes, sugar, chocolate, glaze, gelatin, silver particles, gold particles, suitable polymers and copolymers.
  • the solid medium is selected from foods, in particular fruits, vegetables, fish, meat and sausage products, food supplements; and / or physiologically, physically or physicochemically active compounds, pharmaceutically active compounds or compositions, cosmetic agents or compositions, perfumes, aromatics, aromatics, hyaluronic acid, essential oils, spices, Spice concentrates, spice mixtures, chemically active compounds, catalysts and / or reagents.
  • the container is selected from cans of metal, in particular aluminum cans, cans, bottles, in particular PET bottles and glass bottles, glass containers, and cups.
  • Embodiments comprising the following components a) a reservoir for receiving the core medium, b) a mixing vessel for receiving the reaction bath and for introducing the core medium, c) a delivery line between the reservoir and the mixing vessel with a conveyor for conveying the core medium, d) one with e) a stirring device for the contents of the mixing container.
  • the cross-section of the introduction lance is flared with an opening angle of 10 ° to 30 °, preferably 15 ° to 25 °.
  • outlet of the introduction lance has a diameter of 5 - 15 mm, preferably 6-10 mm. 154.
  • Device according to one of the preceding embodiments characterized in that the outlet of the introduction lance has a diameter of 5 - 15 mm, preferably 6-10 mm.
  • the conveyor is designed for intermittent promotion.
  • stirring device rotates at a speed of 5 to 30 l / min, preferably 15 to 25 l / min.
  • outlet of the introduction lance is in a vertical distance of 1 to 5 mm above the liquid level in the mixing vessel.

Abstract

La présente invention concerne un corps de membrane matricielle, comprenant un noyau liquide (1) et une enveloppe (2), laquelle comporte une ou plusieurs couches de membrane matricielle à base d'alginate et est propre à la consommation, au moins une couche de membrane matricielle renfermant entre 1 et 20% en masse d'une protéine irréversiblement dénaturée. La présente invention concerne également un procédé de fabrication du corps de membrane matricielle selon l'invention. L'invention se rapporte en outre à un dispositif pour la fabrication du corps de membrane matricielle selon l'invention. Par ailleurs, l'invention porte sur une matière de membrane matricielle stable renfermant entre 1 et 20% en masse d'une protéine irréversiblement dénaturée, ainsi qu'un procédé de fabrication de la matière de membrane matricielle selon l'invention. La présente invention concerne également un procédé de revêtement de milieux solides et de surfaces avec une matière de membrane matricielle monocouche ou multicouche à base d'alginate, au moins une couche de membrane matricielle renfermant entre 1 et 20% en masse d'une protéine irréversiblement dénaturée.
PCT/DE2016/000214 2015-05-21 2016-05-20 Couche de membrane matricielle à base d'alginate WO2016184450A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018115107A1 (de) 2018-06-22 2019-12-24 Spc Sunflower Plastic Compound Gmbh Mehrschichtig aufgebautes Kunststoffprodukt

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319181A1 (de) 1982-05-27 1983-12-01 Q. P. Corp., Tokyo Verfahren zur herstellung von nahrungsmitteln und getraenken in granulatform
WO1987001587A1 (fr) * 1985-09-17 1987-03-26 Biocompatibles Limited Microcapsules
DE69000229T2 (de) 1989-04-07 1993-03-18 Oreal Verfahren zur herstellung von alginatkapseln, insbesondere zur kosmetischen verwendung, vorrichtung zur ausfuehrung dieses verfahrens und kosmetisches mittel, das diese kapseln enthaelt.
EP0705541A1 (fr) * 1994-10-04 1996-04-10 Kraft Foods, Inc. Procédé pour la préparation de la pâte alimentaire contenant des herbes
EP1025869A1 (fr) 1999-02-05 2000-08-09 ZIMMERMANN, Ulrich Procédé pour la fabrication d'un matériau stable à base d'alginate
US6375985B1 (en) * 1995-06-07 2002-04-23 Sri International System and method for producing drug-loaded microparticles
US20040156977A1 (en) * 2001-06-22 2004-08-12 Gilles Bocabeille Method for production of food products coated in a material made from protein and hydrocolloid materials
DE60037302T2 (de) 1999-12-15 2008-10-30 Mcneil-Ppc, Inc. Eingekapselte langkettige Alkohole
WO2009024376A1 (fr) 2007-08-22 2009-02-26 Cavis Microcaps Gmbh Microcapsule et son procédé de production
DE102009038170A1 (de) 2009-08-11 2011-02-17 Barbara Herda Verfahren zur Portionierung von flüssigem Alkohol auf Basis einer vorzugsweise kugelförmigen Matrixverkapselung
WO2012142153A1 (fr) 2011-04-15 2012-10-18 Pepsico, Inc Système d'encapsulation pour la protection de probiotiques pendant un traitement
WO2014082132A1 (fr) 2012-11-29 2014-06-05 Progel Pty Ltd Microparticules comprenant un probiotique, un réactif de réticulation, une protéine dénaturée, un agent ramollissant à base de polyol et du tréhalose

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319181A1 (de) 1982-05-27 1983-12-01 Q. P. Corp., Tokyo Verfahren zur herstellung von nahrungsmitteln und getraenken in granulatform
WO1987001587A1 (fr) * 1985-09-17 1987-03-26 Biocompatibles Limited Microcapsules
DE69000229T2 (de) 1989-04-07 1993-03-18 Oreal Verfahren zur herstellung von alginatkapseln, insbesondere zur kosmetischen verwendung, vorrichtung zur ausfuehrung dieses verfahrens und kosmetisches mittel, das diese kapseln enthaelt.
EP0705541A1 (fr) * 1994-10-04 1996-04-10 Kraft Foods, Inc. Procédé pour la préparation de la pâte alimentaire contenant des herbes
US6375985B1 (en) * 1995-06-07 2002-04-23 Sri International System and method for producing drug-loaded microparticles
EP1025869A1 (fr) 1999-02-05 2000-08-09 ZIMMERMANN, Ulrich Procédé pour la fabrication d'un matériau stable à base d'alginate
DE60037302T2 (de) 1999-12-15 2008-10-30 Mcneil-Ppc, Inc. Eingekapselte langkettige Alkohole
US20040156977A1 (en) * 2001-06-22 2004-08-12 Gilles Bocabeille Method for production of food products coated in a material made from protein and hydrocolloid materials
WO2009024376A1 (fr) 2007-08-22 2009-02-26 Cavis Microcaps Gmbh Microcapsule et son procédé de production
DE102009038170A1 (de) 2009-08-11 2011-02-17 Barbara Herda Verfahren zur Portionierung von flüssigem Alkohol auf Basis einer vorzugsweise kugelförmigen Matrixverkapselung
WO2012142153A1 (fr) 2011-04-15 2012-10-18 Pepsico, Inc Système d'encapsulation pour la protection de probiotiques pendant un traitement
US20120263826A1 (en) * 2011-04-15 2012-10-18 Massey University Encapsulation system for protection of probiotics during processing
WO2014082132A1 (fr) 2012-11-29 2014-06-05 Progel Pty Ltd Microparticules comprenant un probiotique, un réactif de réticulation, une protéine dénaturée, un agent ramollissant à base de polyol et du tréhalose

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Forschungskreis der Ernährungsindustrie e.V. (FEI", BONNER UNIVERSITATS-BUCHDRUCKEREI
HOBEIN, B.; LUTZ, B.: "Mikroverkapselung", vol. 49, 2000, AULIS VERLAG DEUBNER & CO. KG, article "Praxis Schriftenreihe Chemie"
VOIGT, R.: "Pharmazeutische Technologie", 2000, DEUTSCHER APOTHEKER VERLAG

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018115107A1 (de) 2018-06-22 2019-12-24 Spc Sunflower Plastic Compound Gmbh Mehrschichtig aufgebautes Kunststoffprodukt

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