WO2013187853A1

WO2013187853A1 - Encapsulated protein-containing product (variants)

Info

Publication number: WO2013187853A1
Application number: PCT/UA2013/000062
Authority: WO
Inventors: Павел Петрович ПИВОВАРОВ; Евгений Павлович ПИВОВАРОВ
Original assignee: Pyvovarov Pavel Petrovich; Pyvovarov Yevgeniy Pavlovich
Priority date: 2012-06-15
Filing date: 2013-06-14
Publication date: 2013-12-19
Also published as: RU130848U1

Abstract

The invention relates to the medical, chemical, pharmaceutical, and food industries, to animal husbandry, the fish industry, nutritional science and biotechnology, and can be used in creating encapsulated protein-containing products. The essence of the invention is the creation of an alginate shell with calcium salts, as a result of an exchange reaction taking place by virtue of the diffusion of Са²⁺ ions, the donor for which being water-soluble calcium salts found in the composition of the fill material of the encapsulated protein-containing product. This fill material is encapsulated through a 0.5 - 3.0% solution of sodium alginate, thereby forming an alginate shell with a fill material to shell ratio of 100:(20-50) (mass % / mass %) and an ionotropic nature inert to the effect of pepsin, gastric acids and environments with low pH values. The fill material of the encapsulated product ensures a pH of said fill material within a range of 7.5 to 8.5, neutralizing the effects of pepsin on the protein component of said fill material. The technical result of the claimed invention is the production of encapsulated protein-containing products, covered in an alginate shell with the pH of the fill material thereof ranging between 7.5 and 8.5, which are resistant to destruction in environments with low pH values and are impenetrable to enzymes of pepsinolysis.

Description

ENCAPSULATED WHITE PRODUCT (OPTIONS)

Technical field

The invention relates to medical, chemical, pharmaceutical, food industry, animal husbandry, fishing industry, dietetics and biotechnology, and can be used to create encapsulated protein-containing products, for example, therapeutic preparations, food products, feed, diet products, foods or special nutrition preparations, functional components of special purpose, protein and biologically active substances, drugs, bacteria and beneficial microorganisms.

The invention also relates to the production of encapsulated protein-containing products that are protected from the active action of pepsinolysis and low pH of the gastrointestinal tract, as a result of which the native properties of the protein substances contained in protein-containing products are preserved.

Prior art

A technical solution is known, namely, a method for manufacturing a Linex drug. According to it, dried bacterial strains are placed in a mechanically assembled gelatin-based suture capsule, which is a container for bacteria. The protein-containing product is ready for consumption. The disadvantage of this technical solution is that the thermotropic suture capsule for microbiological preparations is not hermetic, that is, it is permeable to gastric secretions to enzymes, the result of which is pepsinolysis, and by the production method it can open under the influence of body temperature and the environment of the stomach. Under such conditions, strains of bacteria of internal contents become unprotected from the effects of the environment (especially at low pH values), which significantly reduces the effectiveness of the drug. A technical solution is also known, namely, a method for producing granular food caviar from protein-containing raw materials of animal origin (Pat. RF 2035171 IPC6 A23L 1/328, Method for the production of granular food caviar from protein-containing raw materials of animal origin / Z.A. Yakovlena; Southern Scientific Research Institute Marine Fisheries and Oceanology. - N25015500 / Declared 12/09/91; Publish. 05/20/93), according to which, to obtain the caviar analogue, protein-containing raw materials in the form of a protein-containing mixture, which is obtained by mixing boiled up to 10 ... 20% bul it is made from mussels with a gel-forming agent gelatin and sodium caseinate, vegetable deodorized oil, a dye, extrusion at a temperature of 45 ... 50 ° C to oil cooled to 6 ... 10 ° C to obtain spherical forms - granules. After washing with water, the granules are treated with a 0.2% pectin solution and a 0.25% calcium acetate solution to obtain a surface shell, and then flavor and other substances are added.

A disadvantage of the known technical solution is that, despite the fact that the granules contain protein substances immersed in a gel and coated with a calcium-pectin shell, they are completely permeable to enzymes and obviously amenable to pepsinolysis, inactivating the species specification of proteins, depriving them of their nativeness, yielding denaturation. This is also facilitated by the fact that the thermotropic gelatin gel of the granule changes its colloidal state into a liquid under the influence of temperature, thereby contributing to changes in proteins that are undesirable from the point of view of native protein. Since the granules are permeable to pepsin and stomach acids, intensive hydrolysis of protein substances will take place at low pH values (pH = 1, 9-2.2), they will lose their species specificity and are converted to hydrolysis products.

A technical solution is also known, namely, an encapsulated protein-containing product (Pat. RF 94417 IPC A23L 1/328, publ. 05.27.2010), having an internal content and an alginic shell based on calcium, which is an analogue of fish caviar. According to A well-known technical solution analogue of fish caviar is a capsule, the shell of which contains calcium alginate. The encapsulated mixture includes fish solution (broth) - up to 30%, a thickener based on hydrocolloids and polysaccharides - not more than 20%, flavorings - 3%, dyes - 1%, calcium chloride - 2%.

A disadvantage of the known technical solution is that despite the fact that capsules are created containing protein substances and coated with a shell containing calcium alginate, they are easily permeable and are not protected from the action of pepsin in the stomach against a background of pH 1, 9-2.2 .

Also known is a technical solution selected as a prototype, namely an encapsulated protein-containing product having internal contents and an alginic shell based on calcium (see the description of RF patent 2413434, IPC A23L 1/328, publ. 03/10/2011 1). In a known solution, the internal content (encapsulant) contains 0.2 - 2.0% of a gel former melted at a temperature of 26-65 ° C, which creates a gel inside the capsule at lower temperature, and the alginic shell based on calcium is 10 wt.% With respect to 100 wt.% internal content.

A disadvantage of the known technical solution is that the capsules burst easily and are not protected from the action of pepsin in the stomach against the background of pH values of 1, 9-2.2. In addition, the use of temperatures of 26-65 ° C leads to irreversible changes in protein as a result of thermal coagulation and denaturation.

The disadvantages of analogues and prototype from the point of view of maintaining the native protein substances of the internal contents of the encapsulated product are eliminated when using the claimed invention.

The essence of the invention

The objective of the invention is to obtain encapsulated protein-containing products that are protected from the action of pepsin in the stomach against a background of low pH values (pH 1, 9 ... 2.2). Other objectives and advantages of the claimed invention will be discussed below as the present description is presented.

To achieve the task in a known encapsulated protein-containing product having an inner content and an alginic shell based on calcium, according to the first embodiment of the claimed invention, the ratio of the inner contents: shell is 100: (20 -50) (wt.% / Wt.%).

In a particular embodiment, the internal content of the encapsulated protein-containing product has a pH of 7, 5 ... 8, 5.

According to a second embodiment, in a known encapsulated protein-containing product having an inner content and a calcium based alginic shell, according to the claimed invention, the ratio of the inner contents: shell is 100: (20-N50) (wt.% / Wt.%), While the inner the content has a pH of 7.5 ... 8.5.

The essence of the invention is to create an alginic membrane with calcium salts, as a result of the exchange reaction, which occurs due to the diffusion of Ca ^{2+ ions} , the donor of which is water-soluble calcium salts, which are part of the internal contents of the encapsulated protein-containing product. At the same time, the indicated internal content, having a protein: salt ratio (1-I 1) :( 1, 0 -4) (wt.% / Wt.%), Is encapsulated through a solution of sodium alginate of 0.5 ... 3.0% As a result, an alginic membrane is formed (with a ratio of internal contents: membrane 100: (20–50) (mass% / mass%)) of an ionotropic nature, which is inert to pepsin, stomach acids, and low pH.

Due to the presence of pH correction salts, which ensure the pH of the internal content at the level of 7, 5 ... 8, 5, additional protection is created from the action (effect) of the low pH of the medium on the protein-containing product, and the effect of pepsin on the protein component of the internal content is neutralized encapsulated product.

The present invention makes it possible to obtain new forms of encapsulated protein-containing products that are protected from the action of pepsinolysis and low pH values of the alginic membrane (with the ratio of internal content: shell 100: (20 ^ -50) (wt.% / wt.%)), which is resistant to destruction in acidic environments at low pH and impermeable to pepsinolysis enzymes.

The feasibility of creating such protein-containing products is dictated in some cases by the need to overcome the barrier of the gastrointestinal tract, which is characterized by low pH 1, 9 ... 2, 2 and high pepsin activity and stomach acids - conditions that lead to the hydrolysis of unprotected proteins, to their inactivation and their loss of species specificity, functional properties. Based on these principles, a system for protecting the human body and a digestive system are built. But in some cases, it is necessary to overcome these body functions with the maximum preservation of the protein component (including proteins) of the native properties.

The invention is as follows.

The internal contents of the capsules of the other protein-containing product are prepared, for which the protein-containing component of the internal contents, including proteins, is dispersed in water in which calcium salts are previously dissolved to obtain a dispersion in the form of a solution, or a colloidal system in a sol or dispersion state. PH-correcting salts, for example, alkaline phosphates, carbonates or sodium bicarbonate, which convert the pH of the internal contents to 7, 5 ... 8, 5, are added to the dispersion. Other non-protein substances can be added to the internal content, for example: carbohydrates, vitamins , etc. The created aqueous dispersion (the internal contents of the encapsulated product) is introduced into a solution of sodium alginate of 0.5 ... 3.0%, in which the internal content is covered with an ionotropic alginic membrane, acquiring a micelle state in the colloidal state. The obtained micelles are isolated from excess sodium alginate solution and a protein-containing product coated with an alginic membrane is obtained ionotropic nature. The form of the encapsulated protein-containing product depends on the manner in which the internal contents are introduced into sodium alginate. When the internal contents are introduced through a tubular hole in the form of a continuous stream into a sodium alginate solution, a filamentous protein-containing product with a protected alginic shell of an ionotropic nature is obtained; when the internal contents are introduced in a drop mode into a sodium alginate solution, a spherical protein-containing product with a protected alginic shell of an ionotropic nature is obtained. But with any physical form, the protein component will be covered with an alginic membrane, which does not open at low pH values of 1, 9 ... 2, 2, characteristic of the pH of the gastrointestinal tract. At the same time, the presence of pH-correcting salts under the shell (which ensure the pH of the internal contents at the level of 7, 5 ... 8, 5), together with the protein component, creates a buffer capacity that will withstand doses of hydrochloric acid that accidentally fall under the alginic shell. At the same time, in alkaline solutions (pH 7, 5 ... 8, 5), pepsin becomes inactive. Under such conditions, the protein substance will be protected from the action of the secrets of the gastrointestinal tract. When it enters the small intestine, where the pH changes to slightly alkaline, the permeability of the alginic membrane changes, and the contents can be released from the membrane, fulfilling its functional purpose.

Coverage of the internal contents with an alginic membrane allows delivering, in an unchanged state, the protein-containing component of the internal contents to the intestinal tract.

More fully the essence of the invention is illustrated by the following examples.

Example 1. In 97.5 g of water, 1 g of egg albumin and 1.0 g of calcium pH bicarbonate salt-corrector and 0.5 g of calcium chloride are dispersed. 100 g of an aqueous albumin solution are obtained in which the protein: salt ratio is 1: 1, 5 and the pH value is 7.5, and the ratio of pH corrector salt to calcium salt is 2: 1. The solution was extruded through a syringe needle into a bath with a solution of 0.5% sodium alginate in a continuous stream and the formed filamentary structures were kept in the solution for 30 seconds. After that, they are removed from the solution, washed in water, and 120 g of filamentous polysaccharide-coated proteins are obtained, in which the ratio of internal content: membrane is 100: 20. When placing filamentous coated proteins in an aqueous solution of hydrochloric acid with a pH of 1, 9 containing pepsin, they remain unchanged for 4 minutes. The purpose of the invention is achieved.

Example 2. In 85 g of water, 1 1 g of milk casein is dispersed, 3.0 g of calcium lactate and 1.0 g of sodium phosphate pH corrector salt. 100 g of casein solution are obtained in the sol state, in which the protein: salt ratio is 1 1: 4 wt.% / Wt.%, And the ratio of pH corrector to calcium salt at pH 8.5 is 1: 3 wt.% / mass.%. The solution was extruded dropwise into a 3.0% sodium alginate solution through a needle of a syringe, capsules were prepared and kept in the solution for 30 minutes. 150 g of capsules are created in which the ratio of internal contents: shell is 100: 50 wt.% / Wt.%. When placing capsule-shaped coated proteins in an aqueous solution of hydrochloric acid with a pH of 2.2 containing pepsin, the capsules remain unchanged for 30 minutes, which indicates the protection of casein. The purpose of the invention is achieved. Example 3. In 90 g of water, 5.0 g of dried porcine insulin protein, 2.5 g of calcium citrate and calcium chloride are dispersed in equal proportions and 2.5 g of sodium bicarbonate pH corrector, in which the protein: salt ratio is 1: 1 wt.% / Wt.% When the ratio of calcium salt to salt corrector pH 1: 1 wt.% / Wt.%. A solution with a pH of 8.0 through the oval hole of the extruder is added to a 1.5% solution of sodium alginate and kept in the solution for 15 minutes. Formed 130 g of encapsulated oval product, in which the ratio of internal contents and shell is 100: 30 wt.% / Wt.%. Capsules placed in a solution of hydrochloric acid with a pH of 2.0, containing pepsin, and incubated for 15 minutes. Oval capsules do not change their shape, which indicates that insulin is in a protected state. The purpose of the invention is achieved.

Example 4. Everything is as in example 1, but differs in that 0.5 g of sodium bicarbonate is not added to the internal contents, and the concentration of sodium alginate is taken at 0.4% and held for 1 minute. When the ratio of the inner contents of the shell is 100: 10 wt.% / Wt.%, And in the absence of a pH corrector salt, a turbidity of the solution is observed in hydrochloric acid, which indicates the permeability of the shell. The goal is not achieved.

Example 5. Everything is as in example 4, but 0.5 g of sodium bicarbonate is added to the internal contents. Due to the thin shell, as a result of insufficient exposure in the forming solution over time, it is partially permeable to the substance of the stomach. Partial clouding of the contents is observed. The goal is not achieved.

Example 6. Everything is as in example 1, but differs in that they take calcium salts of 0.4%, sodium bicarbonate 0.4%, the concentration of sodium alginate 3, 1%, and the contents are kept in solution for 40 minutes. Get the ratio of the internal contents of the bog - 100: 10 wt.% / Wt.%, And the pH value of the contents of 7.2. Due to the fact that the ratio of protein is less than the specified, and the content of sodium alginate is higher than the specified, as a result of the exchange reaction, the required ratio of the internal contents does not arise: the shell and the encapsulated protein are modified in a solution of hydrochloric acid after 2 minutes. The goal is not achieved.

The data of examples 1-3 are shown in the table of examples to achieve the goal.

The implementation of the claimed invention allows to obtain a protein-containing product that delivers the internal contents to the intestinal tract is unchanged, which is necessary in some cases, special nutrition or consumption.

It is clear that the above are several possible examples of the implementation of the claimed invention. The invention is not limited to the foregoing examples.

Technical result

The technical result of the claimed invention is to obtain encapsulated protein-containing products that are resistant to destruction at low pH (pH 1, 9 ... 2.2) and impermeable to pepsinolysis enzymes.

Also the technical result of the claimed invention is the preservation of the nativeness of protein substances contained in protein-containing products, under the influence of pepsin and low pH values (pH 1, 9 ... 2, 2).

It should also be noted that the advantage of the invention is that it can be carried out at normal room temperature of 20-25 ° C, without additional heating.

Literature

1. Pat. RF 2035171, IPC A231-1 / 328, publ. 05/20/1993.

2. Pat. RF 94417, ΜΠΚ Α23Ι_ 1/328, publ. 05/27/2010.

3. Pat. RF 2413434, ΠΚ Α23Ι_ 1/328, publ. 03/10/2011 1.

Example Table for Achieved

Example 1 2 3

Protein 1 ^'11 ^* 5]

Calcium salt 0.5 _v2 j 1: 1.5 3.0 _3-1 | π: 4 2.5 ₁ , J 1: 1

Salt corrector 1, SG 1.0 ^' 2.5 ^"

Sodium 0.5 3.0 1.5

Inner 7.5 8.5 8.0 pH content

Content: Shell 100: 20 100: 50 100: 30

The exposure time is 4 minutes. 30 minutes. 15 minutes. aqueous solution

hydrochloric acid with pH

Claims

FORMULA OF THE INVENTION

one . An encapsulated protein-containing product having an internal content and an alginic shell based on calcium, characterized in that the ratio of internal content: shell is 100: (20 + 50) (wt.% / Wt.%).

2. The encapsulated protein-containing product according to claim 1, characterized in that the internal content has a pH of 7, 5 ... 8, 5.

3. An encapsulated protein-containing product having an internal content and an alginic shell based on calcium, characterized in that the ratio of internal content: shell is 100: (20 + 50) (mass% / mass%), while the internal content has a pH of level 7, 5 ... 8, 5.