WO2016184450A1

WO2016184450A1 - Alginate-based matrix membrane layer

Info

Publication number: WO2016184450A1
Application number: PCT/DE2016/000214
Authority: WO
Inventors: Amir Ibrahim
Original assignee: LÖSLER, Arnold
Priority date: 2015-05-21
Filing date: 2016-05-20
Publication date: 2016-11-24
Also published as: DE112016001911A5

Abstract

The present invention relates to a matrix membrane body comprising a liquid core medium (1) and a shell (2) which comprises one or more matrix membrane layers having alginate as the parent substance and which is suitable for consumption, wherein at least one matrix membrane layer contains between 1 and 20 percent by weight of irreversibly denatured protein. The present invention further relates to a method for producing the matrix membrane body according to the invention. The invention also relates to a device for producing the matrix membrane body according to the invention. The present invention therefore relates to a stable matrix membrane material containing between 1 and 20 percent by weight of irreversibly denatured protein and to a method for producing the matrix membrane material according to the invention. The present invention also relates to a method for coating solid media and surfaces with single- or multi-ply matrix membrane material having alginate as the parent substance, wherein at least one matrix membrane layer contains between 1 and 20 percent by weight of irreversibly denatured protein.

Description

Matrix membrane layer based on alginate

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. In particular, 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

Matrix membrane material. The present invention further relates to a method for

Coating of solid media and surfaces with a single or multi-layered

Matrix membrane with alginate as the basic substance, in particular by spraying, dipping and

Casting technique. The present invention also relates to other uses of

matrix membrane material of the invention in particular for preservation and

Preservation of food.

Microcapsules usually consist of a solid, liquid or gaseous

Nuclear material, which is surrounded by a solid shell, the capsule wall. Depending on

The capsule size may be in the size range from 1 to 5000 μm (Hobein, B., Lutz, B., Praxis Schriftenreihe Chemie, Mikroverkapselung, 2000, volume 49, Aulis Verlag Deubner & Co. KG, Cologne; Voigt, R ., Pharmaceutical Technology, For Study and Profession, 2000, Deutscher Apotheker Verlag).

From DE 33 19 181 A1 a process for the production of granules on a calcium alginate base is known, which can be filled with liquid food and beverages. According to the teaching there, 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.

From DE 600 37 302 12 a process for encapsulating long-chain alcohols is known, 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.

DE 690 00 229 T2 describes a process for the production of light on the skin

crushable alginate capsules, in particular for cosmetic use and an apparatus for carrying out this method. 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. In this case, 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.

While the presently used methods of encapsulating and enclosing liquids provide alginate-based microcapsules, they are not suitable for directly portioning the liquid suitable for consumption and wrapping it with an alginate matrix.

Instead, 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 achievable concentration of solutions and ingredients in the core is thus not freely selectable, but only the

subjected to osmotic pressure. Thus, the content is not freely selectable in the known alginate-based capsules.

Furthermore, 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. In addition, 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.

These objects are achieved by the features listed in claim 1.

Embodiments of the invention are illustrated in the figures and will be described in more detail below.

Show it:

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

Matrix membrane layer (3) with alginate as the basic substance and additionally irreversibly denatured protein and optionally adjuvants such as maltodextrin and sugar esters (Sucro, E473), and a coating layer (4) comprising, for example, shellac, copolymers, fats / oils,

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 media of different composition. The quantitative composition of layered membranes is thus controllable. Single-layer membrane bodies are produced and stirred in reaction medium 1 (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

Mass percent sugar ester (Sucro, E473) and 0.53 mass percent maltodextrin and additionally 16 mass percent protein (ovalbumin) and stirred for an additional 20 min. The treatment in reaction medium 2, a new membrane composition under

Formation of a layered membrane to be enforced. 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).

Figure 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

Mass percent sodium alginate, 0.3 mass percent maltodextrin, 16 mass percent protein (ovalbumin) and additionally 10 mass percent of a 2% chitosan solution and stir for a further 20 min. By treatment in reaction medium 2, a new

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. Under

Considering 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).

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

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 14: Direct comparison of samples d.P and n.p.H. as a drying curve

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.

It has surprisingly been found that 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. The obtained

Matrix membrane bodies can be stably stored for a long time in closed containers without liquid storage medium.

The preparation of 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. In addition to calcium, the polyvalent cations of the metals barium, strontium, iron, silver, aluminum, manganese, selenium, copper or zinc are also suitable for this purpose.

Subsequently, the water-insoluble gel with alginate as the basic substance as

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. Upon introduction into the alginate solution spontaneously forms on the surface of the drop of the solution of the polyvalent metal salt

water-insoluble gel, calcium alginate, which envelops the drop. As a result of the reaction between calcium lactate and nathum alginate, the drop is enveloped by a matrix membrane layer and can be removed as the matrix membrane body of the alginate solution. After

Formation of a matrix membrane sheath around the drop becomes the obtained one

Matrix membrane body then separated from the alginate solution. Optionally, the matrix membrane body obtained can be washed with water, dried and more

Treatments are subjected.

It was found that the use of 1 to 20% by mass of protein, which was polymerized in the linking of the polysaccharides with the aid of polyvalent cations in the forming alginate and then irreversibly denatured, particularly stable matrix membrane layers and thus stable matrix membrane body can be produced.

If more than 20% by weight of protein is used, an alginate matrix can still be formed, but this is due to the relatively lower proportion of the

Framework builder alginate structurally weakened. This is particularly disadvantageous in the production of matrix membrane bodies and sheaths, since they are difficult to handle and disintegrate easily. It will be apparent to those skilled in the art that the maximum mass fraction of protein of 20% (20% by mass of protein) is an approximate value and not an absolute value. It will also be apparent to those skilled in the art that the maximum protein content of 20% (20% protein by mass) depends on the protein used and differences may result from the use of different proteins or protein mixtures. Likewise, the alginate starting material used, in particular the

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. For example, 1 to 20 percent by mass of irreversibly denatured protein in the matrix membrane layer refers to the molar composition of

Matrix membrane layer.

Examples 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.

The present invention relates to a method for producing a matrix membrane body with alginate as the matrix matrix substance, comprising the steps:

Providing at least one reaction medium comprising dissolved alginate;

Providing a core medium comprising a solution of a salt of a polyvalent metal;

Single or multiple introduction of the core medium in a reaction medium, wherein by formation of one or more matrix membrane layers a

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; and

Denaturing the protein polymerized into the matrix membrane layer.

In this way one obtains 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

In the gelation of the alginate with polyvalent

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.

By means of the method according to the invention, it is possible to produce matrix membrane bodies of, in particular, spherical, spherical, elliptical, egg-shaped, oval, or otherwise oblong rounded shape.

For the preparation of the matrix membrane body according to the invention, 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. During the chaining of the polysaccharides, 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.

According to a preferred embodiment, 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. For example, 1 to 20% by mass of protein corresponding to the Reaction medium is added to the molar composition of the reaction medium.

Without being bound by theory, it is approximated that there is no dilution or concentration of protein in the formation of the protein

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.

According to the present invention, 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

Suspensions, dispersions or emulsions are used. A liquid

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. According to a particular embodiment, 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. According to the present invention, the soluble alginate in a liquid composition may preferably be selected from solutions, especially aqueous

Solutions, oily solutions, alcoholic solutions, colloidal solutions, as well

Suspensions, dispersions or emulsions are used. A liquid

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.

All suitable 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. Preferably, 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.

According to a particular embodiment, 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. As a result, the positioning and the location of dripping from the stirrer main axis is significantly independent compared to the formation of the spherical balls by the

Dropping from a height of, for example, 4.5 cm into a funnel-shaped flow, as described in "Bioactive Ingredients from Microstructured Multicapsule Systems, Central Results of the DFG / AiF Cluster Project of the Same Name" (Research Group of the

Food Industry e.V. (FEI), Bonner Universitats-Buchdruckerei, Bonn, ISBN 978-3-925032- 49-3).

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 use of a lance apparatus as described in Example 3, allows the standardized production of matrix membrane bodies up to a diameter of 25 mm.

The production quantities of known processes amount to 1-2 kilograms per hour and are only possible to a very limited extent due to many adjustments to the system. With the known methods only capsules with a maximum diameter of about 12 mm can be produced exclusively, which are limited in shape to spherical spherical membrane.

According to a particular embodiment, the reaction medium is stirred while the core medium is introduced. After introduction into the reaction medium, 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. Usually, the reaction medium is stirred for a further 35 minutes after introduction of the core medium. As the reaction time increases, the matrix membrane thickness increases. By extending the residence time of the matrix membrane body in the reaction medium, it is possible to increase the layer thickness of the matrix membrane. It is theoretically possible to make the layer thickness infinite, with the entire core medium reacting to the matrix membrane. 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

Stirred matrix membrane body about 35 min in the reaction medium and then removed, rinsed with water and dried. By the residence time of the matrix membrane body, the layer thickness of the respective matrix membrane layer can be influenced. In this way, 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

be different in thickness. For this purpose, various 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.

According to a particular embodiment, 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. By introducing the matrix membrane body in a further reaction medium is on the core medium enveloping the first

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.

According to a particular embodiment, the introduction of the core medium takes place in a reaction medium as introducing a core medium which is at least one

Is enveloped matrix membrane layer.

In this way, in addition to single-layer matrix membranes and matrix membrane sheaths (single-layer matrix membranes and matrix membrane sheaths), it is also possible to produce double- or multilayer matrix membranes and multi-layer matrix membrane sheaths. The 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.

According to a particular embodiment of the method according to the invention, the denaturation of the protein takes place after the last introduction into a reaction medium.

According to a further particular embodiment, 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. For thermal denaturation of the protein polymerized into the matrix membrane layer, 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.

If 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. In a special

Embodiment, 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

Concentration of Caiciumionen on how the core medium. In this way, Caiciumionen is prevented from being washed out of the matrix membrane. In the presence of compounds with increased calcium affinity, the concentration of Caiciumionen should be increased accordingly. 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

controlled accordingly.

It is advantageous in this case if 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. After the mixture of water and liquid medium to be encapsulated has reached the desired temperature, the container is removed from the heat bath.

Accordingly, the thermal treatment of the matrix membrane body means in one

Temperature range from 45 to 80 ° C, that the immediate environment of the

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. Such denaturation of the protein is irreversible, improves the pore characteristics and prevents leakage of the core fluid outside of a storage liquid. Advantageously, in a package with the least possible dead volume (for example, blistering, slim can), a thermodynamic equilibrium of the vapor pressure with the environment in which the vapor pressure is in equilibrium with the outflow of further liquid.

By denaturing the protein in the matrix membrane layer, the advantageous durability, mechanical stability and improved feel of the invention

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. In the matrix membrane layer cured protein also allows irreversible incorporation of dyes and colorants. The polymerized protein also improves the feel of the matrix membrane body.

By the heating step and the concomitant denaturation of the protein, a further advantageous novel improvement of the optical properties of the

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.

As a further advantage, 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.

The advantageous properties of the matrix membrane according to the invention or

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

Has mass fraction. This high constant mass fraction is surprising and can be observed only in matrix membranes according to the invention, wherein initially native protein with its native tertiary structure is copolymerized intermolecularly into the matrix membrane material during the concatenation of the polysaccharides with the aid of the polyvalent cations in the formation of the alginate matrix and the polymerized native Protein through a denaturation step in the matrix membrane to denatured secondary and

Tertiary stably cures and coagulates and creates its own structure in the

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.

In a preferred embodiment, 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%.

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

Heat treatment significantly lost less fluid.

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

Overall balance over the samples with pre-denatured protein and against all other samples showed a measurable and significant improvement in the retention capacity of the core fluid.

The matrix membrane according to the invention also matrix membrane material is characterized by

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

Polymerization and cross-linking of native protein into the matrix membrane

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.

In a preferred embodiment, the matrix membrane of the invention also reaches a release level of matrix material of 95% (= 95% of the final value of

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 change in conductivity between the media becomes pSiemens / cm, and a nonconductive medium, preferably distilled water and a conductive medium, may be, for example, core medium. 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. As 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. For this purpose, 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

encapsulating medium.

According to another particular embodiment, 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 of suitable acids are

Citric acid, malic acid and ascorbic acid, which may be used alone or in admixture. Preferably, a 20% ascorbic acid solution is used.

According to the invention, 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. Accordingly, 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

Total protein content of the respective molar composition. Thus, 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. In particular embodiments, 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.

If a certain liquid, for example an alcoholic liquid or beverage, is to be enveloped with a matrix membrane sheath according to the invention, this liquid, which is also referred to below as the liquid medium or fluid to be encapsulated, is added to the core medium. 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 medium and fluid are used identically herein and are therefore interchangeable. According to the invention, liquid media include solutions, in particular aqueous solutions, oily solutions, alcoholic solutions, colloidal solutions, and suspensions,

Dispersions and emulsions.

The invention has the advantage that the liquid medium to be encapsulated is freely selectable. For the first time, 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

Mixtures thereof. According to a particular embodiment, the liquid medium from a suitable liquid for consumption. According to the invention, 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. Furthermore, 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. Thus, 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

pharmaceutical, cosmetic, and technical and household sectors.

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

Encapsulation and coating of aqueous and alcoholic media with a lower density compared to the density of the reaction medium. By additions of said auxiliaries, the viscosity of the core medium is adjusted so that the core medium in the

Reaction medium sinks and can react to complete Matrixmembrankörpern. 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. The amount of maltodextrin, xanthan gum, xanthan gum and sugar accordingly depends on the viscosity of the

encapsulating liquid medium.

Maltodextrin can be used as a standard thickening agent in the core medium and

Reaction medium can be added. The core medium is preferably in a

Mass fraction of 0.2 - added 0.8%, which in 500 ml stirred solution 2 g (0.4

Percent by mass) of pure maltodextrin. It is preferably added to the reaction medium in a mass fraction of 0.8-1.2%, which in the case of 750 ml of stirred solution corresponds to 7 g (0.9% by mass) of pure maltodextrin.

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.

By incorporating non-gelatinizing and gelling gelatin into the core medium, the coating of lower viscosity aqueous and alcoholic media can be further optimized over the reaction medium. Gelatine can here the

Core medium to be added as a water binder in the core of the invention

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.

According to a particular embodiment, the core medium comprises 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

intended.

Haptic features such as bite, bumpiness, membrane properties as well

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.

By using suitable auxiliaries, the matrix membrane can additionally be stabilized. These 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. In particular, the admixture of the excipients in the reaction medium causes them to be polymerized into the matrix membrane in the respective proportions.

According to a particular embodiment, therefore, the 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. According to the invention, 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.

For example, 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.

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.

According to the invention, 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. For example, 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. By using maltodextrin and xanthan gum, the elasticity of the

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. For this purpose, 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. For this purpose, 5 g Natriumhydroxidplätzchen be dissolved in 95 ml of water. Subsequently, 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%.

By adding chitosan into the reaction medium, it is copolymerized into the matrix membrane. 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. For this purpose, a 1 - 2% acetic acid solution is first prepared. Subsequently, a 2% chitosan solution is prepared from it. This corresponds to 100 g of solution 2 g of pure chitosan. The 2% Chitosanlösung can then in a mass fraction of up to 10% of the

Reaction medium can be added.

According to a particular embodiment, the reaction medium or the alginate-containing solution comprises chitosan.

According to a further particular embodiment, the chitosan can be reacted with a suitable reaction medium and / or other suitable substances on the surface of the

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.

Examples of oils and fats include any fat or oil suitable for consumption, especially coconut oil, pumpkin seed oil, palmitin, grapeseed oil and olive oil.

In a particular embodiment, the reaction medium is mixed and prepared with coconut oil, as an emulsion with an aqueous alginate solution and suitable emulsifiers. There 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. In the reaction to the matrix membrane body, coconut fat is included in the matrix membrane. At the end of the reaction, 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.

If 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.

According to a particular embodiment of the present invention, the shape, size and shape of the matrix membrane bodies can be influenced by a cryogenic step (cryogenic or cold treatment). Here, 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. For the core medium, for example, 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

Dyes mixed. Subsequently, 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 ΔΤ> ~ 20 ° C, wherein the

Temperature of the reaction medium is preferably T <60 ° C. In the reaction medium, 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

Membrane thickness difference characterized by the onset and termination of dripping. Another advantage of the cryo-treatment of the core medium to be coated is that particularly large geometric bodies can be produced thereby. The

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. According to this particular embodiment, 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

Shock freezing done. It can also be used in large-scale processes. The cryogenic treatment converts the media into a solid state of aggregation.

The use of the 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.

In a particular embodiment, 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 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. Includes the

Matrix membrane layer additionally proteins and / or auxiliaries, this is referred to as multimatrix according to the invention. 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

food-grade paint particles and dyes such as all 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.

According to the known methods, coloring of alginate capsules is achieved only by suitable dyes and micro- and nanoparticle-based dyes in the

Core fluid can be given. After the formation of the spherical membranes, 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

different, are not possible.

Therefore, 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. During the heating step, the color particles and

Dyes involved in the structure of the alginate protein-polymer complex.

According to a particular embodiment of the present invention, 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

embedded color is not washed out by other aqueous media. In addition to the coloration and incorporation of dyes, 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.

According to a particular embodiment is based on the invention

Matrix membrane body applied an additional coating layer. According to a particular embodiment, the additional coating layer is on the outside

Matrix membrane layer applied. The coating layer may be applied before or after denaturing.

According to a further particular embodiment, 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. The

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.

By the coating process (coating) with suitable excipients, the

Membrane quality of the matrix membrane body according to the invention and matrix membrane layer additionally conserved. The coating of the matrix membrane body according to the invention with coating compositions or coatings can also improve the stability of the matrix membrane body

Increase matrix membrane bodies and reduce the permeability of the matrix membrane layer. 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.

The use of suitable 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

Damage can be used in conventional coating processes,

for example in a fluidized bed granulator or drum coater. In this case, 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. In an advantageous

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.

In a further advantageous embodiment, after the generation of the

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.

Examples of 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.

According to the invention, 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

To achieve thermodynamic equilibrium between the vapor pressure in the residual volume and the vapor pressure of the liquid medium in the core of the capsule, which with a

Fluid loss is prevented by the set back pressure.

The use of beeswax added to the packaging has been found to be advantageous.

However, 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. In another aspect, therefore, the present invention relates to a matrix membrane material containing alginate as a matrix containing 1 to 20% by mass of irreversibly denatured protein. During the chaining of the polysaccharides, 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

Storage liquid kept stable and over a longer period without

Impairment of quality are stored. This material is particularly suitable as a matrix membrane layer in one of the invention described herein

Matrix membrane body.

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.

The matrix membrane material may contain additional auxiliaries and dyes as used herein for the matrix membrane and membrane embodiments of the present invention

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.

According to a particular embodiment, 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.

According to the invention, the matrix membrane material is suitable for consumption

Components used. By using protein or protein mixtures, excipients, dyes, and coating compositions suitable for consumption, this produces matrix membrane material which is edible and excellently suited 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. Are two or more Matrix membrane layers present, these may be in terms of selection and

Different proportions by weight of the auxiliaries, colorants and preservatives used.

The preparation of the matrix membrane material according to the invention with alginate as

Ground substance takes place as follows:

Providing a liquid composition comprising a solution of a salt of a polyvalent metal;

Providing at least one reaction medium comprising a dissolved alginate;

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; and

- Denaturation of the protein polymerized into the matrix membrane material.

The denaturation treatment is carried out as described hereinbefore by a

Heat treatment or treatment with an acid solution. The treatment with the acid solution can be carried out by spraying, dipping, pouring or dripping the acid solution. Examples of suitable acids are citric acid, malic acid and ascorbic acid.

Preferably, a 20% ascorbic acid solution is used.

In a preferred embodiment, 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.

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. For this purpose, the already formed matrix membrane material is brought into contact once or more times with 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. Preferably, the mass fraction of sodium alginate in a reaction medium is 1 to 2 percent by mass. In a particular embodiment, 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.

Therefore, in a further aspect, the present invention relates to a method for

Coating solid media and surfaces with a matrix membrane material / matrix membrane containing alginate as a matrix containing from 1 to 20 percent by weight of irreversibly denatured protein.

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 at least one liquid reaction medium comprising a dissolved alginate;

- wetting a solid medium or surface with the liquid composition comprising a solution of a salt of a polyvalent metal;

- One or more contact with bringing the liquid

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; and

- Denaturing of the protein polymerized into the matrix membrane layer.

In a preferred embodiment of the process of the invention for coating solid media and surfaces, 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

Preferably, a 20% ascorbic acid solution is used.

The coating of solid media and surfaces with an advantageous matrix membrane layer with alginate as the basic substance is inventively characterized in that

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,

preserving properties, and significantly increased stability.

According to the invention, suitable components are used for coating the solid media and surfaces for consumption. The use of 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. Examples of 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, fragrances and / or flavorings, aromatics, hyaluronic acid,

Spices, spice concentrates and spice mixtures, chemically active substances such as detergents, catalysts and reagents. According to a particular embodiment, the solid media consist of it.

According to the invention, surface comprises any type of surface, including the surface of a liquid medium. In particular, 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

Food, to protect against external influences.

Surface also includes the inner (inner) surface of a container or

Container is. In a particular embodiment, 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.

Correspondingly, 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. In this case, 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. Another advantage is that the inventive

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

Coatings that are considered to be potentially carcinogenic. According to a particular embodiment, the matrix membrane layer may contain adjuvants, as herein for the matrix membrane layer according to the invention and all embodiments

described, in particular dyes and suitable preservatives, such as chitosan. According to a particular embodiment, 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.

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. For this purpose, 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.

Preferably, 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

Spraying or immersing the solid media or surfaces with or into the solution, or dripping or pouring the solution onto the solid media or surfaces. It is advantageous if suitable thickening agents, such as maltodextrin or xanthan, are added to the solution to ensure that the solution adheres to the solid medium or the surface. Subsequently, the wetted solid medium or the surface is wetted in the same manner with the alginate solution, which may additionally contain auxiliaries, in particular for additional stabilization of the matrix membrane layer. The

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. Examples of suitable acids are citric acid, malic acid and ascorbic acid. When coating food, for example meat, sausages and fish, the Denaturation with the aid of an acid solution, in particular citric acid or ascorbic acid against denaturation by means of heat of advantage, since a heating the

Food may affect undesirable. Preferably, a 20%

Ascorbic acid solution used.

By repeating the coating process can be double or multi-layered

Matrix membranes are generated. For this, the solid media or surfaces are contacted once or more times with 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.

Before applying a further matrix membrane layer, a denaturation step can take place. The inventive method for coating solid media and

Surfaces may be used in particular for the preservation of fruit, meat, fish,

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

Delay in perishability.

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.

In a particular embodiment, 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.

Examples

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 1 (Base for core medium, powdered): ω calcium lactate: 60 g / 100 g (± 20%) ω xanthan gum: 20 g / 100 g (± 20%) ω maltodextrin: 20 g / 100 g (± 20%) ( ω = mass fraction)

Composition 2 (basis for reaction medium, in powder form): ω sodium alginate: 60 g / 100 g (± 20%) ω maltodextrin: 35 g / 100 g (± 20%) ω sugar ester (Sucro, E473): 5 g / 100 g ( ± 20%)

Preparation of a standard core medium using Composition 1:

20 g of composition 1 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. Conversely, 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.

For subsequent investigations of density and viscosity, 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.

Preparation of a raspberry syrup core medium using 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. The

Mixing and mixing was completed when the solution had a high viscosity and no suspension was recognizable. Then 250 ml of raspberry syrup were added to the solution and stirred in with a hand blender so that even here little air bubbles were introduced. When using syrup or a sugar solution, it may be advantageous if they have a viscosity of 50-500 mPas at about 20 ° C. The mixture was mixed briefly with the hand blender and then allowed to stand for about 1 h.

Preparation of a core medium with 40% rum using 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.

Preparation of a standard reaction medium using Composition 2:

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.

For subsequent investigations of density and viscosity became the standard

Reaction medium diluted with water in the ratio 1: 1. For this purpose, 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 (oily):

In a beaker 250 - 300 ml of coconut fat were heated to the final melt. The temperature was kept small (T max. = 30 - 40 ° C). Subsequently, 5 g of commercial granulated lecithin were mixed with two tablespoons of water with a pestle and transferred to the heated Kokosfettbad. Subsequently, 20 g of composition 2 were transferred to the coconut fat bath and filled with continuous mixing with the hand blender with water to 750 ml. The result was a milky wise colloidal emulsion. The resulting emulsion was called a standard reaction medium (oily).

For subsequent studies on density and viscosity has become the standard

Comparison of density and viscosity of core media and reaction media:

Determination of density and viscosity was carried out by classical measurements according to the Archimedean principle of displacement of a body in a liquid with water as a reference at 20 ° C (density) and according to the Hagen-Poiseuille principle (viscosity), after which in a capillary through which defined volume of a liquid of known density flows laminar due to a hydrostatic pressure difference, shear forces on this

Liquid, which represent a measure of viscosity.

To determine the density according to the Archimedean principle of displacement, any body in a beaker of water was weighed. Subsequently, the same became Body dipped in the medium to be determined and weighed again. By the

Displacement of the volume, the density was calculated.

Table 1: Density of the standard nuclear medium at different dilution levels and standard reaction media (dilution 1: 1) at 20 ° C:

The determination of the viscosity was carried out according to the Hagen-Poiseuille principle, according to which the

Shearing forces of a medium which flows through a capillary is a measure of the viscosity. For this purpose, 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

° C:

Solution Dilution Viscosity [mPa-s] Deviation [%]

Sugar (40%) - 6.16 -

Sugar (50%) - 15.4 -

Sugar (60%) - 58.5 -

Sugar (70%) - 481 -

Sugar (75%) - 1100 -

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

Reaction medium (oily) 1 1 7200 ± 50

Reaction medium (oily) 28 ° C 1 1 1714 ± 50

Water (Reference) 1 1 1, 00 -

Example 2: Preparation of Matrix Membranes with Polymerized Protein

For the preparation of the matrix membranes according to the invention and matrix membrane bodies with copolymerized protein, it must be avoided that the protein used is denatured before processing. In the present example, 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. For this purpose, 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. To one

60 ml of an already stirred 750 ml reaction medium (aqueous or oily) were taken from the reaction medium with 8 mass percent protein and extracted with 60 g

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. 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. For this purpose, 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. When 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. Thereafter, 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.

Description of the lance apparatus:

Agitator: 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.

Lance made of stainless steel with defined geometry: 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

Dropping on the surface of the reaction medium prevented.

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

Core medium from the silicone tube, so that the portioning is done exclusively by the automatic opening of the valve.

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

Parameters of the reaction media (viscosity, density, surface tension).

Example 4: Matrix Membrane Body with Single-Layered Matrix Membrane (Single Layer)

A single matrix membrane layer was prepared by adding the reaction medium

(Standard, as described in Example 1) 1 to 20 percent by mass of protein as described in Example 2 were mixed. Optionally, 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%. Subsequently, matrix membrane bodies were produced according to Example 3. The protein and the used

Excipients were found after the reaction to matrix membrane bodies in the formed

Matrix membrane layer homogeneously distributed again. Decisive in the composition of the reaction medium is a sufficient proportion of sodium alginate from 1, 0 to 2.0

Percent by mass, which makes the formation of matrix membrane bodies possible in the first place. So it is therefore possible to vary the reaction medium and its original

To replace or supplement the composition with other aids.

Example 5: Matrix Membrane Body with Multilayer Matrix Membrane (Multi Layer)

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. In the choice of reaction media, it is of

Of crucial importance that a sufficient proportion of sodium alginate from 1.0 to 2.0 mass percent is always present as a scaffold. Examples of concentration gradients in a multi-layer matrix membrane body in sequential treatment in various reaction media are shown in FIG. 3 and FIG.

Example 6: Heat denaturation of matrix membrane bodies with protein

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

Warm mixture of 2-3 units of water and 1 unit of raspberry syrup or 40% rum is added, and the mixture is heated to 70 ° C. in a water bath.

Preferably, 2.0-3.0% by mass of calcium lactate may additionally be added to the mixture. For this purpose, 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.

By denaturation in a mixture of 2-3 units of water and 1 unit of the liquid medium to be encapsulated at 70 ° C matrix membrane body were obtained with a particularly pronounced metallic, pearl-like gloss effect. In this case, the use of smaller volumes has proved particularly advantageous, i. the use of 100 ml glass bottles. Cooling to room temperature was carried out in the mixture of 2-3 units of water and 1 unit of raspberry syrup or 40% rum

Contraction and dents of the matrix membrane body prevented. Example 7: Cryoprocessing of the core medium prior to the preparation of matrix membrane bodies

Raspberry syrup was treated with a calcium lactate solution as described in Example 1

Core medium mixed and frozen in a spherical shape of 5 cm (spherical

Ice cube shape with a diameter of about 5 cm). Subsequently, the frozen balls were placed in the slightly heated alginate-containing reaction medium (ΔΤ> = 20 ° C, T <60 ° C). As a result, the frozen round ball gradually melted on its surface through the heated reaction medium and reacted immediately at the thawed interface to form a matrix membrane layer. This ensured that the ball 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, 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. After a reaction time of 30 minutes, the initially introduced portions were stirred for 10 minutes longer than the matrix membrane bodies formed at the end of the introduction phase. In this case, a minimum membrane thickness difference of = 0.1-0.3 mm was observed.

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

Heat treatment in a dye mixture such as a coloring solution, colloidal

Suspension or other dye-particle-containing substance, the dye during the denaturation process in the new cured structure irreversibly firmly binds.

For this purpose, the matrix membrane body according to Examples 1 to 3 with 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. In this way 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. The bottles with the

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

To suffer quality loss. The resulting matrix membrane bodies were very stable and plump.

Example 9: Comparison of the amount of leaked liquid at various

Matrix membrane bodies during storage in hermetically sealed containers

Matrix membrane body with 0, 2, 4, 8 and 16 mass percent protein in the

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. In addition, 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. 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

Experiments not opened to ensure a constant vapor pressure in the bottles. Table 3: Semiquantitative comparison of the amount of leaked liquid at

various matrix membrane bodies during storage in hermetically sealed containers (average of 3 repetitions each)

Liquid has leaked.

In all samples, the leakage of liquid was observed, with the amount of leaked liquid being indirectly proportional to the mass fraction of protein in the sample

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.

It also investigated the composition and consistency of the leaked liquid. To this end, i.a. a taste test was performed to determine if the leaked liquid is core medium, i. is more viscous than water and tastes of apple weed syrup and all in all due to the sugar contained in the core medium, maltodextrin and xanthan sweet. It was found that with increasing mass fraction of protein in the matrix membrane layer and Denaturierungsbehandlung the macromolecules contained in the core medium are retained and the leaked liquid tasted less sweet and the viscosity decreased. Both

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

(Apple weed syrup), maltodextrin and xanthan were retained by the matrix membrane inside the body. The leaked water was used in particular to compensate for the vapor pressure in the glass bottles.

It was interesting that all matrix membrane bodies without denaturation treatment were already almost completely covered by leaked liquid after 5 to 10 minutes. The leaked liquid was more viscous than water and tasted sweet and after

Apfelalmkräutersirup.

It was also striking that in the matrix membrane bodies with protein in the

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

Matrix membrane bodies during storage in hermetically sealed containers

It should be shown that it is crucial to add native dissolved protein to the reaction bath or if the protein has been previously separated by a protein

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

Mass percent disaccharides added in the form of syrup. the

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.

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 in the composition of their shells are comparable to capsules with a shell of alginate and dispersed pre-denatured protein as described in WO

2012142153A1 are described. 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.

After preparation, 9 spheres each of the samples were blind, 16% d.P., 16% nP + H.

dried and stacked in a dry jar, in order to apply their own pressure on the balls. Recorded at time 0, 20h, 43h, 67h, 115h. At the end of the study, the liquid that leaked from the balls was collected in a container and photographed. Here a clear difference in quantity and color intensity is clearly visible.

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

Matrix membrane layer with alginate as the basic substance

A piece of pork loin was portioned into equal pieces of about 30 g and

then distributed on weighing dishes. The samples were then exposed to different reaction media so that a matrix membrane layer of different composition was formed around the piece of meat on each sample, with all samples initially in an aqueous solution comprising 2.0 to 3.0 mass% calcium lactate, 0.4 Mass percent maltodextrin and 1.2% by mass of xanthan were dipped as a thickener. The food was thereby enriched on the surface by diffusion and adhesion with calcium ions. The degree of enrichment and the quality are adjusted via the residence time, ion concentration and the admixed auxiliaries. In the present example, the pork loin sticks were dipped in the calcium lactate mixture for about 10 seconds. In the next step, 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. The

Heat treatment was in a heated bath at a temperature of 45-80 ° C

carried out. 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. The chitosan polymerized into the matrix membrane precipitated and hardened out.

All samples were photographed and weighed daily for a period of 11 days. Due to the decrease in weight and the drying speed, it was possible to conclude on the quality of the matrix membrane.

Table 5: Pork sirloin pieces were exposed to different reaction media. The matrix membrane layer of different properties produced thereby proved in all coated samples as a liquid barrier and as a barrier to yeasts, fungi and bacteria.

Sample Name: Treatment Method:

O: blank

F: Meat wrapped in cling film

Ca ²⁺ : soaked in calcium, maltodextrin, xanthan gum

A: Calcium alginate membrane without heat step

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

Mass percent without heat step

A + P + H: Calcium alginate coating and protein incorporation with protein

subsequent heat step 70 ° C.

A + H + Z calcium alginate membrane with additional sugar syrup followed by

Heat step 70 ° C

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 + C + H: Calcium alginate membrane and chitosan solution (10%) followed by

Heat step 70 ° C

A + P + C: calcium alginate membrane and incorporation of protein 16

Percent by mass and of chitosan solution (10%) without heat step

A + H + P + C: Calcium alginate membrane and incorporation of protein 16

Percent by mass and of chitosan solution (10%) followed by

Heat step 70 ° C

Table 6: Pork sirloin pieces are exposed to different reaction media. Treatment matrix of the respective sample

Name with with with with with alginate skin heatstep acid step protein chitosan sugar

Sample: (A) (H) (S) (P) (C) (Z)

O: without treatment (blank test)

F: only welded in foil

Ca ² *: only soaked in core medium

A: X - - - - -

A + H X X - - - -

A + S X - X - - -

A + P X X - X - -

A + P + H: X X - X - -

A + H + Z: X X - - X

A + P + S + Z: X - X X - X

A + C: X - - - X - A + C + H: XX - - X -

A + P + C: X - X X -

A + H + P + C: X X - X X -

It was found that all samples were excellent

Behavior of the liquid. Similarly, a lower weight loss was measured for all coated samples than for the blank. Surprisingly, it was also found that a fungus, mold, and yeast formation formed significantly later in all samples than in the blank. The blank sample showed on the 2nd day already the first moldings, all other samples had no infestation. From the 4th day mold and fungus formation started with other samples. On the 1st day, all samples were infested with fungi, mold and yeast. In a further analysis it was surprisingly found that in all coated samples or

Food after removal of the matrix membrane material on 1 1st day no fungal, mold, and yeast infection was recognizable.

Table 7: All samples were photographed daily, weighed and semi-sensitively examined for fungal and mold growth.

Day 1 2 3 4 5 6 7 8 11

O: - + + ++ ++ +++ ++++ +++++ +++++

F: - - - - - - - + ++

Ca: - - + ++ ++ +++ ++++ ++++ +++++

A: - - - - + ++ +++ ++++ +++++

A + H: - - - - - - - + ++

A + S: - - - - + ++ ++ ++ ++

A + P: - - - - - - + ++ ++

A + P + H: - - - - - - - + ++

A + H + Z: - - - - - + ++ n / a n / a

A + P + S + Z: - - - - - + ++ n / a n / a

A + C: - - - - - - - - X

A + C + H: - - - - - - - - +

A + P + C: - - - - - - - + ++

A + H + P + C: - - - - - - + + ++ The amount of fungi, molds and yeasts present on the surface of the coated food increases from + to +++++, "-" means that no mold was detectable.

Example 11: Comparison of weight loss by gravimetric measurements

The following matrix membrane bodies were generated:

Blind (B): Calcium alginate bead without protein

Blind (B.H): calcium alginate bead without protein with heat step

16% den.P. (d.P.): Calcium alginate bead with already disperse denatured protein

16% den.P. (d.P.H): Calcium alginate bead with already dispersed denatured protein with heat step

16% nat.P. (n.P.): Calcium alginate bead with originally native dissolved protein

16% nat.P + H. (n.P.H): Calcium alginate bead with originally native dissolved protein with heat step

Mass percent disaccharides added in the form of syrup. the

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.

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.

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.

For comparison of the weight loss, gravimetric measurements were carried out at defined times by placing different samples on weighing dishes for drying in air. Only the sample itself was weighed without taking into account the amount of spilled liquid. 4 samples of each variety were weighed. The raw data sets were normalized to their starting weight, ie each measured value was divided by the starting weight of the sample. Thus, the records were

comparable.

The gravimetric evaluations have shown that the samples with native protein and heat have lost significantly less liquid than the samples with already denatured protein without heat. This could be clearly seen on a small puddle below some samples.

The liquid leakage and the total mass balance can be explained as follows. The reformation of the structure, which is characterized by the sample with heat and native protein, the pores of the membrane are significantly smaller. That does not prevent that

seepage of low molecular weight components, but prevents higher molecular components, as with the example of an oligosaccharide such as xanthan, that can not pass through the membrane more. The samples with native protein and subsequent heat treatment (n.P.H) have a measurable and significant improvement in the overall balance compared to denatured protein (d.P.) and all other samples

Retention of the core liquid shown.

Table 8 shows the raw data of the sample Blind (B):

Time sample sample 1 sample 2 sample 2 sample 3 sample 3 sample 4 sample 4

(h) ¹ (R) normalized (R) normalized (R) normalized (R) 'normalized

0 4 1 3.24 1 3.47 1 3.48 1

1 3.87 0.9675 3.12 0.963 3.39 0.9769 3.36 0.9655 8 3.57 0.8925 2.89 0.892 3.12 0.8991 3.08 0.8851

19 3.17 0.7925 2.55 0.787 2.78 0.8012 2.72 0.7816

32 2.94 0.735 2.34 0.7222 2.61 0.7522 2.51 0.7213

48 2.53 0.6325 1.9 0.5864 2.15 0.6196 2.07 0.5948

79 1.91 0.4775 1.33 0.4105 1.45 0.4179 1.41 0.4052

105 1.67 0.4175 1.13 0.3488 1.23 0.3545 1.25 0.3592

127 1.45 0.3625 1.07 0.3302 1.15 0.3314 1.13 0.3247

145 1.41 0.3525 1.06 0.3272 1.15 0.3314 1.11 0.319

Sample Run 1-4 of Sample Blind (B), i. Caicium alginate bead without protein and without heat step, is shown graphically in FIG.

Table 9 shows the raw data of the sample blank with heat treatment (B.H):

Sample Run 1-4 of the Sample Blind with heat treatment (BH), ie Caicium alginate bead without protein with heat step, is shown graphically in FIG. Table 10 shows the raw data of the sample 16% den.P. (DP):

Sample Run 1-4 of the sample 16% den.P. (d.P.), i. Calcium alginate sphere with already disperse denatured protein without heat step, is shown graphically in FIG.

Table 11 shows the raw data of the sample 16% den.P.H (d.P.H):

Time trial; Sample 1 Sample 2 Sample 2 Sample 3 Sample 3 Sample * v. Sample4 (h) ^■ '(R) normalized' (8) normalized (R) fnorniert (R) normalized ■

0 2.57 1 2.2 1 2.26 1 2.82 1

1 2.5 0.9728 2.14 0.9727 2.2 0.9735 2.75 0.9752

8 2.25 0.8755 1, 95 0.8864 2.04 0.9027 2.53 0.8972

19 1, 99 0.7743 1, 72 0.7818 1, 8 0.7965 2.26 0.8014

32 1, 72 0,6693 1, 49 0,6773 1, 6 0,708 2,02 0,7163

48 1, 33 0.5175 1, 09 0.4955 1, 2 0.531 1, 6 0.5674

79 0.94 0.3658 0.78 0.3545 0.91 0.4027 1, 24 0.4397

105 0.92 0.358 0.73 0.3318 0.77 0.3407 1, 01 0.3582

127 0.89 0.3463 0.73 0.3318 0.77 0.3407 0.99 0.3511

145 0.89 0.3463 0.73 0.3318 0.77 0.3407 0.99 0.3511 Sample Run 1-4 of the sample 16% denatured protein and heat step (dPH), ie calcium alginate bead with already disperse denatured protein, is shown graphically in FIG.

Table 12 shows the raw data of the sample 16% native protein (n.P.):

Sample Run 1-4 of the sample 16% native protein (n.P.), i. Calcium alginate bead with originally native dissolved protein without heat step is shown graphically in FIG.

Table 13 shows the raw data of the sample 16% native protein with heat step (n.P.H):

Time Sample Sample 1 Sample 2 Sample 2 Sample 3 Sample 3 Sample 4 Sample 4 (h) (8) ^■ normalized (8) normalized (8) normalized (8) normalized

0 2.37 1 2.05 1 1, 98 1 2 1

1 2.35 0.9916 2.02 0.9854 1, 96 0.9899 2 1

8 2.1 0.8861 1, 84 0.8976 1, 77 0.8939 1, 8 0.9

19 1, 88 0.7932 1, 62 0.7902 1, 55 0.7828 1, 59 0.795

32 1, 61 0,6793 1, 38 0,6732 1, 3 0,6566 1, 36 0,68

48 1, 31 0.5527 1, 12 0.5463 1, 05 0.5303 1, 08 0.54

79 1, 02 0.4304 0.86 0.4195 0.83 0.4192 0.85 0.425 105 0.97 0.4093 0.81 0.3951 0.78 0.3939 0.81 0.405

127 0.95 0.4008 0.81 0.3951 0.78 0.3939 0.8 0.4

145 0.95 0.4008 0.81 0.3951 0.78 0.3939 0.8 0.4

Sample Run 1-4 of the sample 16% native protein with heat step (n.P.H), 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.

The direct comparison of the samples d.P and n.p.H. is shown in Figure 14 as a drying curve.

Example 12: Comparison of optical and physical properties by osmosis

Matrix membrane bodies were prepared as described in Example 11.

In each case three samples of a matrix membrane body were mixed with a defined amount of distilled water at the time after production in a cylindrical container. The samples were visually inspected and photographed at different times (see Figures 15-17). It can be shown that the dye incorporated in the sample core medium stains the solutions to different extents at different recorded times. While samples with native protein and heat have very little dye leakage, samples with the. Protein obtained a clear staining. Very strong is the dye from the alginate beads without protein (blind) leaked.

It can be assumed that 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

Nuclear medium quantities to later make statements as to whether the core medium could escape through the skin or not. In a special sample (nPH), it was noted that not only was the dye unable to escape, but it also lodged in the network of the protein-alginate membrane structure and was largely trapped there. Example 13: Comparison of the liquid exchange by conductivity measurements

Matrix membrane bodies were prepared as described in Example 11 and

Leifähigkeitsmessungen performed. This was done at different times

Measurements were carried out using a commercially available conductivity meter. 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).

Table 14 shows the measured conductivities:

Sample weight in n.P.H (red) 1.98 B.H. (green) 3.41 d.P.H (purple) 2.55 grams t = 0

N. P. 2.20 B. (black) 3.45 d.P. (blue) 2.46

(orange)

Time in h and min conductivity in 5ίειτιεη5 / αη (raw values)

Oh 1min n.P.H 10 B.H. 11 d.P.H 10

N. P. 16 B. 23 d.P. 21

Oh 2min n.P.H 23 B.H. 31 d.P.H 19

N. P. 26 B. 32 d.P. 26

Oh 3min n.P.H 31 B.H. 42 d.P.H 34

N. P. 39 B. 47 d.P. 39

Oh 5min n.P.H 31 B.H. 57 d.P.H 47

N. P. 48 B. 57 d.P. 48

Oh 10min n.P.H 51 B.H. 69 d.P.H 61

N. P. 62 B. 74 d.P. 64

Oh 20min n.P.H 71 B.H. 95 d.P.H 86

N. P. 84 B. 98 d.P. 87

Oh 30min n.P.H 90 B.H. 112 d.P.H 103

N. P. 102 B. 115 d.P. 107

Oh 50min n.P.H 110 B.H. 137 d.P.H 132

nP 125 B. 146 dP 136 2h 50min nPH 162 BH 202 dPH 202 nP 180 B. 214 dP 220

5h 45min n.P.H 292 B.H. 360 d.P.H 373

N. P. 334 B. 401 d.P. 411

16h 45min n.P.H 344 B.H. 418 d.P.H 438

N. P. 397 B. 466 d.P. 449

29h 45min n.P.H 346 B.H. 419 d.P.H 439

N. P. 403 B. 472 d.P. 449

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 recorded graphs follow a certain law. It can be said that the graphs in two different sections behave a little differently. Therefore, the separation in 0 - 300 min and 0 -2000 min. Overall, the formula for describing a best fit for all lines is:

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.

Since the equation is very difficult to resolve after time t, the time that 95% percent of the final conductivity value was reached was calculated computer-assisted with Maple. The values are in red or large format.

The calculation of the time at 95% with Maple gives the following values: 1491 min, 467 min, 943 min, 643 min, 722 min, 615 min. The time after which 95% of the final value of the

Conductivity reached is shown in FIG.

Example 14:

A manufacturing method for producing an alginate-based solid matrix membrane at the

Surface of solid water-soluble media and crystalline solids such as salts and minerals, preferably dehydrated malic acid in crystalline form, which makes it possible to protect the medium to be encapsulated against external influences such as moisture, air, mechanical stress and chemical environment and only under certain changed conditions To expose ingredients in a controlled manner to perform a desired function. 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.

We are looking for an extended and improved way of protecting substances or mixtures of substances (especially solid, granular or crystalline) intended for consumption against external influences such as moisture, air, mechanical stress and chemical environment. Only under certain altered conditions should these ingredients be exposed in a controlled manner to perform a desired function. For example, in conventional methods, sugary or other water-soluble coating material is used as the coating, as long as the ingredients themselves are not water-soluble. In contrast, water-soluble ingredients must be coated with oily (e.g., palm oil) or oily coatings. Increasingly, in particular, the increasing industrial use of palm oil for reasons associated with it

Environmental issues critically assessed. Therefore, suitable alternatives are sought, which are inexpensive and harmless to health and do not burden the environment. Objective of the coating

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)

• sustained release

• Overlapping an undesirable taste or smell

• Improved transport, storage and processing options; Protection of ingredients against air or moisture or protection against mechanical stress

Application areas and examples

Food and beverage:

• Excipients: sugars, sweeteners, salt, spices, acidulants (malic acid), flavor enhancers, preservatives, other additives and excipients

• coated ingredients are applied to the NM or integrated into the NM;

Taste experience (for example sour) should take place with a time delay when consumed

• Duration of an ingredient should be prolonged by protracted release

Physiological active substances:

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.

fertilizer

• Substances: phosphate and / or nitrogen containing natural and artificial fertilizers, minerals

• Duration of action should be prolonged by protracted release

In the following, a novel coating process with an alginate-based matrix membrane using the example of crystalline malic acid is described, which leads to surprising new solutions. Coated malic acid as a dehydrated salt is used, for example, in confectionery products. When consumed, a controlled release of the malic acid should take place, so that the acidic taste only becomes noticeable with a time delay. For this purpose, 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.

To solve this problem, the effect of solubility with other metal salts, for example with calcium as calcium malate (calcium salt of malic acid), is used in such a way that the salt formed in or around the food acts as an acidity regulator. Thus, 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.

Addition of malic acid with calcium lactate

Preparation of malic acid

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. In addition to the free 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

Add the malic acid with a protein alginate mixture

In a next step, in addition to the preparation 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. Likewise, instead of the reaction medium (aqueous), the reaction medium (oily) can be used. Alternatively, the standard reaction medium (oily) may contain other oils such as palm oil instead of coconut fat. Optionally, a defined amount of protein can be added as well. Both media have a certain viscosity, resulting in the

Merging with the modified malic acid because of the lower diffusion of the

Calcium by a viscous medium is crucial. In both media, however, a certain amount of water is required, which is the reaction, ie

Movement of ions, only possible. The reaction medium (following: aqueous or oily) is contacted with the modified malic acid. Conventional methods such as fluidized bed granulation are applicable. Here, the merger was achieved in that a small amount of the reaction medium to the modified

Apple acid particle drips. The freely available alginate now entrails the calcium from the calcium malate, which is partially bound in the malic acid, and forms at the interface between the reaction medium and the modified malic acid one

Calcium alginate layer with additional ingredients such as the polymerized protein, which readily denatured by the presence of the acid. The malic acid is re-formed by the lactic acid which is now freely available. After a further subsequent drying phase, 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.

Sequential coating with alginic acid and with calcium ions

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. Depending on requirements, 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.

In contact with viscous alginic acid

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. In a final step, 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. Example 15:

A process for producing edible shellac and alginate-based shellac matrix membranes and coating edible shellac and shellac matrix membranes on the surface of edible single or multilayer alginate matrix membranes for stabilizing and curing membrane properties of enclosed aqueous media for optical enhancement by mirror-like gloss effects on the surface of the edible single or multilayer alginate matrix membranes as well as for improving haptic and mechanical properties.

Preparation of solid shellac in and around matrix membranes

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.

The objective of a stable coating is realized taking into account the properties of shellac. What is new here is that the 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.

The reduction of the evaporation of the core medium takes place by the application of special shellac solutions and / or by incorporation of special shellac solutions on / into the matrix membrane. Surprisingly, various prototypes have been found to improve the optical properties of some coating forms characterized by the formation of a solid edible, glassy, translucent surface on the matrix membrane that is both slightly yielding and outstanding (sufficiently porous) is suitable for consumption. All new coating forms can be changed in taste by the addition of additives such as sugar. Furthermore, it could be observed in these prototypes that its haptic properties also improved by stability and hardness. Due to the new hard coating it is now possible to stack and store matrix membrane spheres without collapsing due to their own weight. Likewise it is possible the Unwrap hard stable skin from the matrix membrane ball (peel off, break away) so that the outer layer serves only as a biological and biodegradable transport or packaging medium.

Production of different coating media

There are different shellac solution äfiniert (ω = mass fraction):

Shellac solution 1 (10%): Shellac solution 6 (pH neutral):

ω ethanol 96%: 90 g / 100 g ω ammonia 25%: 75 g / 100 g

ella shellac: 10 g / 100 g ω shellac: 25 g / 100 g

Shellac Solution 2 (20%): Shellac Solution 7:

ω ethanol 96%: 80 g / 100 g ω Composition 2 aqueous: 75 g / 100 g ω shellac: 20 g / 100 g ω shellac solution 6: 25 g / 100 g

Shellac solution 3 (30%): shellac solution 8:

ω ethanol 96%: 70 g / 100 g ω Composition 2 aqueous: 50 g / 100 g ω shellac: 30 g / 100 g ω shellac solution 6: 50 g / 100 g

Shellac solution 4: (40%): shellac solution 9:

ω ethanol 96%: 60 g / 100 g ω Composition 2 aqueous ω shellac: 40 g / 100 g (+ 16% protein): 50 g / 100 g

ω shellac solution 6: 50 g / 100 g

Shellac solution 5: (50%):

ω ethanol 96%: 50 g / 100 g

ω shellac: 50 g / 100 g

Polymerization of the coating medium in the matrix membrane skin

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.

Applying the coating medium to the matrix membrane skin

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. For this purpose, 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.

Two prototypes turned out to be particularly surprising in their properties:

a. 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. b. 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.

Post-treatment of prototypes by quenching in solutions Each of the prototypes produced may optionally undergo further treatment after one of the shellac solutions 1-9 treatments by transferring and stirring in one of the following quench reaction baths. A treatment time of about 2 - 3 min proved to be sufficient:

Quenching Solution 1: Quenching Solution 3:

ω H 2 O: 90 g / 100 g ω oil (vegetable): 100 g / 100 g

ω citric acid: 10 g / 100 g

Quenching Solution 2: Quenching Solution 4:

ω ethanol 96%: 100 g / 100 g ω chitosan: 5 g / 100 g

ω acetic acid 25%: 95 g / 100 g

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. 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.

The preparation of matrix membrane and matrix membrane spheres so far aimed at a core medium such a stable encapsulation that leakage of the nuclear medium is prevented. However, in more than particular embodiments, it 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.

In the following example, an embodiment is described how the molecular sieve properties of the matrix membrane can be used in the enrichment of honey protein according to the invention. By varying 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.

125 ml honey 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 ). For the adjustment of a sufficient viscosity (honey dependent) 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. During transfer, the balls sink down due to the higher density of the honey. Ideally, one chose a long cylinder whose osmotic pressure at the bottom of the vessel is sufficiently high due to the high water column. Preferably, 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. Likewise, 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.

Example 17:

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.

It is not known that it is possible to incorporate 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)

• Ingredient should not be released in the mouth or stomach, but only in the small intestine (eg acid-sensitive substance or to protect the gastric mucosa) In the matrix membrane nanoparticles (eg copolymer Evonik) are polymerized, which are dissolved out in the basic environment of the small intestine and the allow delayed escape of the ingredient through the resulting pores of the membrane

• Substances: vitamins, amino acids, caffeine, taurine, minerals, pharmaceuticals

Composition 1 and composition 2 both as reaction medium (aqueous or oily) 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. For example, 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. Alternatively, it is also possible to use different reaction baths with different nanoparticle concentrations sequentially, so that nanoparticle gradients are found in the skin layers. In a particular embodiment, it is conceivable to apply a nanoparticle layer after the matrix membrane bodies produced have been separated from a reaction medium by being rolled into a nano-containing powder.

Special embodiments

In the following section, the present invention is characterized by particular

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.

2. Matrix membrane body according to the preceding embodiment, characterized

characterized in that 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%.

3. matrix membrane body according to one of the preceding embodiments, characterized

characterized in that the matrix membrane has a release level of 95% (= 95% of the Final value of the conductivity) based on the change in conductivity between two media at 20 ° C after more than 1000 minutes. Matrix membrane body according to the preceding embodiment, characterized

in that 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. Matrix membrane body according to one of the preceding embodiments, characterized in that 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. 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. Matrix membrane body according to one of the preceding embodiments, characterized in that the core medium comprises calcium lactate, preferably in a mass fraction of 2.0 - 3.0%. Matrix membrane body according to one of the preceding embodiments, characterized in that the core medium comprises at least one liquid suitable for consumption. Matrix membrane body according to one of the preceding embodiments, characterized in that the liquid suitable for consumption is preferably selected from aqueous, oily, sugary and alcoholic liquids. Matrix membrane body according to the preceding embodiment, characterized

characterized in that the 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

Sugar solutions, coffee and tea preparations or mixtures thereof. 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. A method of producing a matrix membrane body according to any one of the preceding embodiments, comprising the steps of:

Providing at least one reaction medium comprising dissolved alginate;

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; and

- Denaturing of the protein polymerized into the matrix membrane layer. 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. Method according to one of the preceding embodiments, characterized in that the protein comprises an animal or vegetable protein or a mixture thereof. Method according to one of the preceding embodiments, characterized in that the protein comprises soy protein or serum proteins, in particular albumins and globulins. Method according to one of the preceding embodiments, characterized in that the protein comprises ovalbumin, lactalbumin or bovine serum albumin, or mixtures thereof. Method according to one of the preceding embodiments, characterized in that the protein is ovalbumin. Method according to one of the preceding embodiments, characterized in that the reaction medium comprises 2 to 20% by mass of protein. Method according to one of the preceding embodiments, characterized in that the reaction medium comprises 4 to 20% by mass of protein. Method according to one of the preceding embodiments, characterized in that the reaction medium comprises 6 to 18 mass percent protein. Method according to one of the preceding embodiments, characterized in that the 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 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. Process according to one of the preceding embodiments, characterized in that the reaction medium comprises 16% by mass of protein and the denaturation takes place by thermal treatment at 70 ° C. Method according to one of the preceding embodiments, characterized in that the denaturation of the protein takes place by treatment of the matrix membrane body with an acid solution. Method according to one of the preceding embodiments, characterized in that the acid solution comprises citric acid, malic acid and / or ascorbic acid. Method according to one of the preceding embodiments, characterized in that the acid solution is a 20% ascorbic acid solution. Method according to one of the preceding embodiments, characterized in that the polyvalent metal is calcium. Method according to one of the preceding embodiments, characterized in that the salt of the polyvalent metal is calcium lactate. Method according to one of the preceding embodiments, characterized in that calcium lactate is contained in a mass fraction of 2.0 - 3.0%. Method according to one of the preceding embodiments, characterized in that the dissolved alginate is sodium alginate. 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%. Method according to one of the preceding embodiments, characterized in that 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,

Dispersions and emulsions. Method according to one of the preceding embodiments, characterized in that an oily solution comprises coconut fat. Method according to one of the preceding embodiments, characterized in that the basis for an oily solution is coconut fat. Method according to one of the preceding embodiments, characterized in that the core medium additionally contains at least one liquid medium to be encapsulated. Method according to one of the preceding embodiments, characterized in that the liquid medium to be encapsulated comprises at least one liquid suitable for consumption. Method according to the preceding embodiment, characterized in that 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. Method according to one of the preceding embodiments, characterized in that 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. Method according to one of the preceding embodiments, characterized in that 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,

Beeswax, wax, dyes, oils and fats, preferably coconut fat. Method according to one of the preceding embodiments, characterized in that 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. Method according to the preceding embodiment, characterized in that the geometric body has a diameter in the size range of 5-100 mm. Method according to the preceding embodiment, characterized in that the cryo treatment is effected by flash freezing with liquid nitrogen. Method according to one of the preceding embodiments, characterized in that the reaction medium additionally comprises one or more auxiliaries,

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. Method according to one of the preceding embodiments, characterized in that different reaction media are used, which differ in the selection and the mass fractions of the excipients and / or the mass fraction of protein and thereby a concentration gradient of the excipients and of the protein is formed over the superimposed matrix membrane layers , Method according to one of the preceding embodiments, characterized in that a coating layer is additionally applied to the matrix membrane body. Process according to the preceding embodiment, characterized in that the application of the coating layer as applying a coating layer on a

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. Method according to one of the preceding embodiments, 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

in that 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. Matrix membrane material according to one of the preceding embodiments, characterized in that 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.

75. Matrix membrane material according to one of the preceding embodiments, characterized

characterized in that 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. Matrix membrane material according to one of the preceding embodiments, characterized in that the matrix membrane material contains chitosan.

76. Matrix membrane material according to one of the preceding embodiments, characterized

characterized in that 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.

77. Matrix membrane material according to one of the preceding embodiments, characterized

characterized in that the matrix membrane material reaches a release level of 95% (= 95% of the final value of conductivity) relative to the change in conductivity between two media at 20 ° C after more than 1000 minutes.

78. Matrix membrane material according to one of the preceding embodiments, characterized

characterized in that 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.

79. Use of the matrix membrane material according to one of the preceding

Embodiment as a molecular sieve.

80. A process for the production of matrix membrane material with alginate as the basic substance according to one of the preceding embodiments, comprising the steps:

Providing at least one reaction medium comprising a dissolved alginate; Contacting the liquid composition one or more times with a reaction medium to form a matrix membrane material, wherein at least one reaction medium additionally contains from 1 to 20% by mass of protein which is copolymerized into the forming matrix membrane material; and

- Denaturation of the protein polymerized into the matrix membrane material.

81. The method of the preceding embodiment, characterized in that the bringing into contact of the liquid composition comprising a solution of a salt of a polyvalent metal, with a reaction medium as bringing a liquid composition takes place, already with a Reaction medium has reacted to a matrix membrane material.

82. 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

trained matrix membrane material takes place.

83. Method according to one of the preceding embodiments, characterized in that the denaturing takes place after the last contact with a reaction medium.

84. Method according to one of the preceding embodiments, characterized in that the denaturation is further brought into contact with a

Reaction medium connects.

85. The method according to any one of the preceding embodiments, characterized in that the reaction medium comprises 2 to 20 percent by mass of protein.

86. The method according to any one of the preceding embodiments, characterized in that the reaction medium comprises 4 to 20 percent by mass of protein.

87. The method according to any one of the preceding embodiments, characterized in that the reaction medium comprises 6 to 18 mass percent protein. 88. The method according to any one of the preceding embodiments, characterized in that the reaction medium comprises 14 to 17 percent by mass of protein.

89. 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.

90. Method according to one of the preceding embodiments, characterized in that the reaction medium comprises 16% by mass of protein and the denaturation is effected by thermal treatment at 70 ° C.

91. The method according to any one of the preceding embodiments, characterized in that the denaturation of the protein by treatment of the matrix membrane material is carried out with an acid solution.

92. Method according to the preceding embodiment, characterized in that the acid solution comprises citric acid, malic acid and / or ascorbic acid.

93. Method according to one of the preceding embodiments, characterized in that the acid solution is a 20% ascorbic acid solution.

94. The method according to any one of the preceding embodiments, characterized in that the polyvalent metal is calcium.

95. Method according to one of the preceding embodiments, characterized in that the salt of the polyvalent metal is calcium lactate.

96. Method according to one of the preceding embodiments, characterized in that calcium lactate is contained in a mass fraction of 2.0-3.0%.

97. Method according to one of the preceding embodiments, characterized in that the dissolved alginate is sodium alginate.

98. The method according to any one of the preceding embodiments, characterized in that sodium alginate is contained in a mass fraction of 1, 0 to 2.0%.

99. The method according to any one of the preceding embodiments, characterized in that the 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.

100. Method according to one of the preceding embodiments, characterized

characterized in that an oily solution comprises coconut fat.

101. Method according to one of the preceding embodiments, characterized

characterized in that the 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

Microparticles, gelatin, beeswax, wax, dyes, oils and fats, preferably coconut fat.

102. Method according to one of the preceding embodiments, characterized

in that the 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.

103. Method according to one of the preceding embodiments, characterized

in that a coating layer is additionally applied to the matrix membrane material.

104. Process according to the preceding embodiment, characterized in that the application of the coating layer takes place as immersion of the matrix membrane material in a coating composition, or as spraying of the matrix membrane material with a coating composition, or as dripping or pouring on

Coating composition on the matrix membrane material.

105. Method according to one of the preceding embodiments, 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.

106. Method according to one of the preceding embodiments, characterized

characterized in that various liquid compositions and reaction media be used, which differ in the selection and the mass fractions of the excipients and / or the mass fraction of protein and thus a concentration gradient of the excipients and the protein on the superimposed layers

Matrix membrane material is generated.

107. Method according to one of the preceding embodiments, characterized

characterized in that the reaction medium contains the excipient chitosan and the formed matrix membrane material is comminuted after the denaturation treatment.

108. Method according to the preceding embodiment, characterized in that the matrix membrane material is mechanically comminuted.

109. Use of the matrix membrane material according to one of the preceding

Embodiments for coating liquid media and solid media,

especially food.

110. Use of the matrix membrane material according to one of the preceding

Embodiments for preserving foods, characterized in that the matrix membrane material contains the excipient chitosan.

111. Use of the matrix membrane material according to the preceding embodiment, characterized in that 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.

112. Method for coating solid media and surfaces with

Matrix membrane material with alginate as the basic substance according to one of the preceding embodiments, comprising the steps:

Providing at least one liquid reaction medium comprising a dissolved alginate;

Wetting a solid medium or a surface with the liquid

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; and

- Denaturing of the protein polymerized into the matrix membrane layer.

113. 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.

114. Method according to one of the preceding embodiments, characterized

characterized in that the wetting is done by dipping, spraying, dripping, or pouring.

115. The method according to one of the preceding embodiments, characterized

characterized in that the contacting is done by dipping, spraying, dripping, or pouring.

116. Method according to one of the preceding embodiments, characterized

characterized in that the wetting and / or contacting is done by spraying.

117. Method according to one of the preceding embodiments, characterized

in that the denaturation takes place after the last contact with a reaction medium.

118. Method according to one of the preceding embodiments, characterized

characterized in that the denaturation is followed by further contacting with a reaction medium.

119. Method according to one of the preceding embodiments, characterized

in that 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.

121. Method according to one of the preceding embodiments, characterized

in that the protein comprises ovalbumin, lactalbumin or bovine serum albumin, or mixtures thereof.

122. Method according to one of the preceding embodiments, characterized

characterized in that the protein is ovalbumin.

123. Method according to one of the preceding embodiments, characterized

characterized in that the reaction medium comprises 2 to 20% by mass of protein.

124. Method according to one of the preceding embodiments, characterized

characterized in that the reaction medium comprises 4 to 20% by mass of protein.

125. Method according to one of the preceding embodiments, characterized

characterized in that the reaction medium comprises 6 to 18% by mass of protein.

126. Method according to one of the preceding embodiments, characterized

characterized in that the reaction medium comprises 14 to 17% by mass of protein.

127. Method according to one of the preceding embodiments, characterized

characterized in that the denaturing of the into the matrix membrane layer

polymerized protein by thermal treatment of the solid medium or the surface in a temperature range of 45 to 80 ° C.

128. Method according to one of the preceding embodiments, characterized

in that the reaction medium comprises 16% by mass of protein and the denaturation takes place by thermal treatment at 70 ° C.

129. Method according to one of the preceding embodiments, characterized

characterized in that the denaturation of the protein is carried out by treating the solid medium or the surface with an acid solution.

130. Method according to the preceding embodiment, characterized in that the acid solution comprises citric acid, malic acid and / or ascorbic acid. 131. Method according to one of the preceding embodiments, characterized in that the acid solution is a 20% ascorbic acid solution.

132. Method according to one of the preceding embodiments, characterized

characterized in that the polyvalent metal is calcium.

133. Method according to one of the preceding embodiments, characterized

characterized in that the salt of the polyvalent metal is calcium lactate.

134. Method according to one of the preceding embodiments, characterized

characterized in that calcium lactate is contained in a mass fraction of 2.0 - 3.0%.

135. Method according to one of the preceding embodiments, characterized

characterized in that the dissolved alginate is sodium alginate.

136. Method according to one of the preceding embodiments, characterized

characterized in that sodium alginate is contained in a mass fraction of 1, 0 to 2.0%.

137. Method according to one of the preceding embodiments, characterized

in that the 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.

138. Method according to one of the preceding embodiments, characterized

characterized in that an oily solution comprises coconut fat.

139. Method according to one of the preceding embodiments, characterized

characterized in that the liquid composition comprising a solution of a salt of a polyvalent metal additionally contains one or more auxiliaries,

preferably selected from maltodextrin, xanthan, emulsifiers, sugar esters,

Fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and

140. Method according to one of the preceding embodiments, characterized

Emulsifiers, proteins, shellac, glycerol, chitosan, gold, silver, nano and Microparticles, gelatin, beeswax, wax, dyes, oils and fats, polymers and copolymers.

141. Method according to one of the preceding embodiments, characterized

characterized in that on the solid medium or the surface in addition a

Coating layer is applied.

142. Process according to the preceding embodiment, characterized in that 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.

143. Traversing according to one of the preceding embodiments, characterized

characterized in that 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.

144. Method according to one of the preceding embodiments, characterized

145. Method according to one of the preceding embodiments, characterized

characterized in that different liquid compositions and different reaction media are used, which differ in the selection and the mass proportions of the excipients and / or the mass fraction of protein and thereby a

Concentration gradient of the excipients and the protein on top of each other

formed matrix membrane layers is generated.

146. Method according to one of the preceding embodiments, wherein 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.

147. Method according to one of the preceding embodiments, wherein the surface is the surface of a liquid medium, preferably yoghurt and other milk products or other viscous media.

148. The method of any one of the preceding embodiments, wherein the surface is the inner surface of a container.

149. Method according to one of the preceding embodiments, wherein 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.

150. Apparatus for carrying out the method according to one of the preceding

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.

151. Device according to the preceding embodiment, characterized in that the introduction lance has a widening towards an outlet cross-section.

152. Device according to one of the preceding embodiments, characterized

characterized in that the cross-section of the introduction lance is flared with an opening angle of 10 ° to 30 °, preferably 15 ° to 25 °.

153. Device according to one of the preceding embodiments, characterized

characterized in that the 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

characterized in that the conveyor is designed for intermittent promotion.

155. Device according to one of the preceding embodiments, characterized

in that the stirring device rotates at a speed of 5 to 30 l / min, preferably 15 to 25 l / min.

156. Device according to one of the preceding embodiments, characterized

characterized in that the outlet of the introduction lance is in a vertical distance of 1 to 5 mm above the liquid level in the mixing vessel.

Claims

claims

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% by mass of irreversibly denatured protein, the matrix membrane body after storage at a temperature of 20 ° C has a mass fraction of at least 35% after a period of 145 hours based on the starting mass of the matrix membrane body.

2. matrix membrane body according to claim 1, characterized in that the one or

a plurality of matrix membrane layers additionally comprise one or more excipients 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.

3. Membrane matrix body according to claim 1 or 2, characterized in that the

Nuclear medium at least any liquid suitable for consumption, preferably selected from alcoholic beverages, lemonades, dairy products, fruit or vegetable juices, fruit drinks, fruit syrups, coffee syrup, coffee or tea preparations, or

Mixtures of one or more representatives thereof, and / or at least one physiologically, physically, physically-chemically and / or pharmaceutically active compound or composition, and / or at least one cosmetic agent or cosmetic composition, and / or at least one ingredient selected from perfumes, aromatics .

Flavorings, hyaluronic acid, essential oils, spices, spice concentrates,

Spice mixtures, chemically active compounds, catalysts and / or reagents.

The matrix membrane body according to any one of claims 1 to 3, characterized in that the at least one matrix membrane layer containing 1 to 20 mass% of irreversibly denatured protein is obtained by bringing native protein, polysaccharide and at least one polyvalent cation into contact, and carrying out a denaturation step of the protein becomes.

5. A process for producing a matrix membrane body according to any one of claims 1 to 4, comprising the steps:

Providing at least one reaction medium comprising dissolved alginate;

Providing a core medium comprising a solution of a salt of a polyvalent metal;

- Single or multiple introduction of the core medium in a reaction medium, wherein by formation of one or more matrix membrane layers a

Matrix membrane body is formed, and wherein at least one reaction medium additionally contains 1 to 20 percent by mass of protein, which in the forming

Matrix membrane layer is polymerized;

- Denaturing of the protein polymerized into the matrix membrane layer.

6. The method according to claim 5, characterized in that the reaction medium contains 14 to 17 percent by mass of protein.

7. The method according to claim 5 or 6, characterized in that the reaction medium comprises 16 mass percent protein and denaturation by thermal treatment of the matrix membrane body is carried out at 70 ° C.

8. The method according to any one of claims 5 to 7, characterized in that the

Nuclear medium additionally at least one suitable for consumption liquid, preferably selected from alcoholic drinks, lemonades, dairy products, fruit or vegetable juices, fruit drinks, fruit syrups, coffee syrup, coffee or tea preparations, or mixtures of one or more representatives thereof, and / or at least one physiological , physically, physicochemically and / or pharmaceutically active compound or composition, and / or at least one cosmetic agent or cosmetic composition, and / or at least one ingredient selected from perfumes, aromatics,

Flavorings, hyaluronic acid, essential oils, spices, spice concentrates,

Spice mixtures, chemically active compounds, catalysts and / or reagents.

9. The method according to any one of claims 5 to 8, characterized in that the

Core medium additionally one or more excipients selected from maltodextrin, xanthan, emulsifiers, sugar esters, fatty acids, proteins, shellac, glycerol, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, oils and fats, and / or the reaction medium additionally one or more excipients selected from maltodextrin, xanthan, sugar esters, carbohydrates, emulsifiers, proteins, shellac, glycerol, chitosan, gold, silver, nano and microparticles, gelatin, beeswax, wax, dyes, Oils and fats, polymers and copolymers.

10. The method according to any one of claims 5 to 9, characterized in that the

Core medium is brought into the form of any geometric body before introduction into a reaction medium by cryo-treatment under conversion into a solid state of aggregation.

A matrix membrane material comprising alginate as a matrix, characterized in that the matrix membrane material comprises 1 to 20% by mass of irreversibly denatured protein, the matrix membrane material having a release level of 95% (= 95% of the final value of conductivity) relative to the change in conductivity between two media 20 ° C after more than 1000 minutes.

12. matrix membrane material according to claim 11, characterized in that further

Additives, preferably selected from maltodextrin, gelatin and protein are included.

The matrix membrane material according to claim 11 or 12, characterized in that 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.

14. Use of the matrix membrane material according to one of claims 11 to 13 as

Molecular sieve.

15. A process for the preparation of matrix membrane material with alginate as the basic substance according to one of claims 11 to 13, comprising the steps:

Providing at least one reaction medium comprising a dissolved alginate;

- contacting the liquid composition with a reaction medium several times or more to form a matrix membrane material, wherein at least one reaction medium additionally contains from 1 to 20 mass percent of protein which is copolymerized into the forming matrix membrane material; and

- Denaturation of the protein polymerized into the matrix membrane material.

16. A method for coating solid media and surfaces with matrix membrane material with alginate as a matrix according to any one of claims 11 to 13, comprising the steps:

Providing at least one liquid reaction medium comprising a dissolved alginate;

- One or more contact with bringing the liquid

Composition wetted solid medium or the surface with a reaction medium to form one or more

- Denaturing of the protein polymerized into the matrix membrane layer.

17. The method according to claim 16, characterized in that the solid medium is selected from foods, preferably fruits, vegetables, fish, meat and sausage products, nutritional supplements; and / or physiologically, physically or physicochemically active compounds, pharmaceutically active compounds or compositions, cosmetics or compositions, fragrances, aromatics, flavors, hyaluronic acid, essential oils, spices,

Spice concentrates, spice mixtures, chemically active compounds, catalysts and / or reagents.

18. The method according to claim 16 or 17, characterized in that the surface is the surface of a liquid medium, preferably yogurt and other milk products or other viscous media.

19. The method according to any one of claims 16 to 18, characterized in that the

Surface is the inner surface of a container, preferably the inner surface of a metal can, in particular an aluminum can, can, bottle, especially PET bottle and glass bottle, glass jars, or cups.

20. An apparatus for carrying out the method according to claim 4, 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) an introduction lance connected to the end of the delivery line, e) a stirring device for the contents of the mixing container.