"Texturizing process for proteins that are alternatives to animal proteins"

By controlling thiol sulfur groups with gas mixtures, the process forms stable protein networks in applications like thickening and 3D printing, overcoming the limitations of chemical additives.

FR3150932A1Active Publication Date: 2025-01-17LAIR LIQUIDE SA POUR LETUDE & LEXPLOITATION DES PROCEDES GEORGES CLAUDE
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Patent Information

Application Number
FR2023007480
Authority / Receiving Office
FR · FR
Patent Type
Applications
Current Assignee / Owner
Filing Date
2023-07-12
Publication Date
2025-01-17
Estimated Expiration
2043-07-12

AI Technical Summary

Technical Problem

Existing processes struggle to effectively control and modify the state of thiol sulfur groups in proteins, which is crucial for forming stable protein networks in various applications, often relying on chemical additives that are regulatory, sensory, and health-risk prone.

Method used

Utilizing specific gas mixtures such as oxygen, hydrogen, nitrogen, and carbon dioxide to control the redox state of thiol groups, promoting disulfide bridge formation or preventing it, thereby forming or avoiding protein networks without the need for chemical additives.

Benefits of technology

Enables the formation of desired protein structures and textures in applications like thickening, 3D printing, and viscosity control, while avoiding the drawbacks of chemical additives.

✦ Generated by Eureka AI based on patent content.

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Abstract

A method for producing or processing a protein medium of plant, dairy, animal, or microbial origin, characterized in that, during one or more phases of the production or processing method, the state of the sulfur-containing thiol groups in the medium is controlled or modified by injecting a chosen gas or gas mixture, the reducing or oxidizing nature of which produces a specific effect on said groups. Figure from the abstract: Fig. 1
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Description

Title of the invention: Texturizing process for proteins that are alternatives to animal proteins

[0001] The present invention relates to the field of processes for transforming alternative proteins, and in particular, but not exclusively, protein concentrates or isolates that are alternatives to animal proteins, and it is particularly concerned with proteins of plant origin, as well as with processes and devices for manufacturing processed food products based on such alternative proteins.

[0002] Proteins are composed of a set of amino acids, including cysteines. These contain sulfur atoms in the form of thiol / sulfhydril (-SH) groups. Through oxidation, these thiol groups can form disulfide (SS) bonds. The molecule resulting from the bonding of two cysteines is cystine. A disulfide bridge therefore consists of a bond between two sulfur atoms in a protein and contributes to the stabilization of its tertiary or quaternary structure. While disulfide bridges form within a protein, certain processes rely on the formation of disulfide bonds between two proteins to create a network.

[0003] Thus, for example, in breadmaking, during kneading, and in the presence of water, the protein chains in the flour (gliadins and glutenins) unwind and gradually align. The thiol groups of the different proteins become accessible and react in pairs, linking their sulfur atoms by covalent bonds to form disulfide bridges. This forms a protein complex called gluten, which will later be able to contain the gas produced during the rising of the bread, and which is therefore responsible for the bread's structure.

[0004] The present invention therefore relates to the processes of production or transformation of a protein medium, whether this medium is of plant, dairy, animal or microbial origin, this medium being able to be used in various products, and in particular food, pharmaceutical, cosmetic, hygiene products, etc.

[0005] As will be seen in more detail below, the process of the invention aims to enable, during one or more of the phases occurring during the production or transformation process, the control or modification of the state of the sulfur thiol groups of the medium by the injection of a chosen gas or gas mixture, the reducing or oxidizing character of which allows a given action to be obtained on said groups.

[0006] It is therefore desirable within the scope of the present invention to be able to propose a technical solution enabling the control of the state of sulfur groups (-SH / SS) in various applications requiring it, and thus control the formation of a network

[0007]

[0008]

[0009]

[0010]

[0011]

[0012] protein, this through the use of the oxidizing and reducing characteristics of certain chosen gases. Among the various transformation processes using such proteins, we can mention: - Thickening processes; - Texture reinforcement processes; - 3D printing; - Checking the viscosity of a liquid before its use (to facilitate transport, pumpability, etc.; or even - The creation of new textures. The present invention relates in particular to the following products: - matrices based on plant proteins, insect proteins or proteins of unicellular origin intended to produce meat analogues; - yogurts (cow's milk or plant-based milks) and other dairy products; - bread products. One of the objectives of the present invention is to propose a technical solution enabling control of the state of sulfur groups (-SH / SS) in various applications requiring it, and thus control the formation of a protein network, by using the oxidizing and reducing characteristics of certain chosen gases. The gases envisaged in the context of the present invention include: - oxygen, an oxidizing gas, which increases the redox potential of a medium, and which promotes the oxidation of thiols into disulfide bridges (air or enriched air can also fulfill this role); - hydrogen, a reducing gas, which in turn favors the reduced state (-SH) of sulfur molecules, which can bond to form an SS bridge when the environment becomes oxidizing again; - Nitrogen, although neutral from a redox potential point of view, can be used to remove oxygen from a liquid, paste or gaseous medium; it therefore indirectly reduces the redox potential of a medium, and promotes the reduced state (-SH) of thiol groups (argon can also fulfill this role). And we can also consider within the framework of the present invention mixtures with CO2 (O2 / CO2, N2 / CO2...) with the aim of being able to play on the pH which also plays a role on the state of the proteins. Therefore, the following gases and mixtures, included in the group consisting of:, may be considered within the scope of the invention: - oxygen, air or oxygen-enriched air, an oxidizing gas that increases the redox potential of a medium and promotes the oxidation of thiols in disulfide bridges; hydrogen, and gaseous mixtures containing hydrogen, a reducing gas, which favors the reduced state (-SH) of sulfur molecules, which can bond to form an SS bridge when the environment becomes oxidizing again; nitrogen or argon or mixtures thereof, which can be used to remove oxygen from a liquid, pasty or gaseous medium and which therefore indirectly reduces the redox potential of a medium, and promotes the reduced state (-SH) of thiol groups; gaseous mixtures containing CO2 such as: O2 / CO2 O2 / N2 / CO2 such as oxygen-enriched air containing CO2, n2 / co2, and Ar / CO2. gaseous mixtures containing nitrogen and / or argon and / or hydrogen.

[0013] When using oxygen-enriched air, more oxygen dissolves in the medium being treated compared to using plain air. This enhances the kinetics and intensity of the oxidation reactions. Furthermore, the use of oxidizing / reducing gases is preferable to the use of chemical additives because it is reversible. One gas can easily be replaced by another, thus switching a medium from one redox state to another.

[0014] Moreover, it is well known that, in comparison, additives are subject to very strict regulatory constraints, they must appear on the labelling of the finished product, they are not always sensorially neutral, and they can present (like sulfites for example) risks of intolerance and allergy, not to mention that they convey a negative image to the public, far from naturalness.

[0015] As described above, it is desired within the framework of the present invention to be able to propose a technical solution enabling the control of the state of sulfur groups (-SH / SS) in various applications requiring it and thus control the formation of a protein network, this by the use of the oxidizing and reducing characteristics of certain chosen gases.

[0016] Let us then exemplify in what follows different cases of implementation of the invention.

[0017] Let us examine in particular a first case of a "thickening" operation, where a medium A is to be thickened. A liquid B containing proteins including cysteines is bubbled with a reducing gas, or with nitrogen to expel the oxygen. It is then heated to denature the proteins, which unfold and expose their thiol groups because they are in a reducing medium. Liquid B is then added to liquid A under oxidizing conditions (by using oxygen by example) so that disulfide bridges form between proteins, creating a network that eventually traps other components of media A and B.

[0018] Liquid A can be any medium to be thickened, but which contains little or no protein, some of which will depend on the redox potential, for example a food or body cream, or for example a soup to be enriched with protein.

[0019] Liquid B is, for example, a suspension or solution of proteins whose state, structure, depends on the redox potential.

[0020] Depending on the industrial application considered, it is thus possible to create a desired texture without the addition of additives (such as thickeners of the gum, starch type, etc.).

[0021] The addition of a reducing or neutral gas such as H2 or N2 lowers the redox potential of the medium (protein B) and thus promotes the reduced state (-SH) of sulfur molecules, which can bind to form an SS bridge when the medium becomes oxidizing again.

[0022] Let us exemplify in what follows a second case of implementation of the invention, to produce a product, for example a food product, by 3D printing.

[0023] By using nitrogen (to displace oxygen) and / or hydrogen, a protein-based matrix is ​​heated under reducing conditions. It then feeds the nozzle(s) of a 3D printer to create a food product according to manufacturing procedures known to those skilled in the art. Since the nozzle has been placed in an oxygen-rich environment (for example, by placing the printer in an oxygen chamber), the thiol groups of the matrix oxidize and form disulfide bonds with the proteins of the surface layer of the product being formed, onto which the nozzle deposits the product. This creates a protein network and ensures the stability of the resulting product.

[0024] The attached [Fig.1] illustrates such a 3D printing installation where we can distinguish: - A deposition chamber 1 which is under an oxidizing atmosphere, for example under oxygen; - A work support 2; - A heating nozzle 3; - A line 4 in which the reduced liquid matrix circulates (arrival of a fluid matrix based on proteins which has been heated under reducing conditions and which feeds the nozzle 3 (it should be noted that the nozzle 3 can be a bi-fluid nozzle jointly injecting the protein fluid and an oxidizing gas)); - A pump 5; - 6: element constructed by 3D printing.

[0025] Let us exemplify in what follows a third case of implementation of the invention, to control the viscosity of a liquid before its implementation.

[0026] In certain manufacturing processes, it is desirable to maintain a low viscosity, which can to present several advantages for the industrial production site: facilitating transport, pumpability, cleaning, limiting losses during transfers, etc...

[0027] When it is desired to maintain a low viscosity of a matrix containing partially or totally denatured proteins whose thiol groups are exposed (denaturation is the loss of the native (original) structure of the protein by the action of a parameter such as, for example, temperature, pressure, a chemical compound... it may be reversible or not, in general it is described as a deployment of the structure, with loss of the quaternary and ternary structures, and in extreme cases the secondary structure), it is proposed to implement nitrogen and / or hydrogen in order to lower the redox potential of this matrix and avoid the formation of disulfide bridges which would create a structure increasing the viscosity.

[0028] It is then possible to switch, at the desired time in the process, to an oxidizing environment to create a protein network and thus structure its product.

[0029] By way of illustration, the following phases can be exemplified: - Phase 1: formulation of the liquid matrix, deoxygenated by nitrogen scanning or treated with hydrogen. - Phase 2: a heat treatment of the matrix. - Phase 3: transfer / transport / transferring of the medium according to the needs of the industrial process. - Phase 4: contacting the medium with an oxidizing gas (by bubbling, or mixing under an oxidizing atmosphere, etc.)

[0030] The desired moment mentioned above is typically the moment when the manufacturer has finished transferring his product and wishes to give the product its final texture.

[0031] The present invention relates to a process for the production or transformation of a protein medium, of plant, dairy, animal or microbial origin, characterized in that during one or more of the phases occurring during the production or transformation process considered, the state of the sulfur thiol groups of the medium is controlled or modified by the injection of a chosen gas or gas mixture, the reducing or oxidizing character of which allows a given action to be obtained on said groups.

[0032] According to one of the embodiments of the invention, the production or transformation process considered uses a medium or matrix which is, by its very composition, already naturally reducing.

[0033] By way of illustration, in these cases we find for example: - matrices naturally or not containing reducing molecules such as, for example, vitamin C or other antioxidants; - a matrix that has been deoxygenated by a vacuum process; - milk or other liquid whose redox potential has been lowered by an activity microbial, for example by lactic acid bacteria;

[0034] .etc.....

[0035] The present invention relates to a process for the production or transformation of a protein medium, of plant, dairy, animal or microbial origin, characterized in that during one or more of the phases occurring during the production or transformation process considered, the state of the sulfur thiol groups of the medium is controlled or modified by the injection of a chosen gas or gas mixture, the reducing or oxidizing character of which allows a given action to be obtained on said groups.

[0036] According to one of the embodiments of the invention, the process is one of the transformation processes of the group formed by: - ​​Thickening processes; - Texture reinforcement processes; - 3D printing; - Checking the viscosity of a liquid before its use, to facilitate transport, pumpability, etc...; - The creation of new textures.

[0037] According to one embodiment of the invention, the gas or gaseous mixture used is included in the group consisting of: - oxygen, air or oxygen-enriched air, an oxidizing gas which increases the redox potential of a medium, and which promotes the oxidation of thiols into disulfide bridges; - hydrogen, and gaseous mixtures containing hydrogen, a reducing gas, which favors the reduced state (-SH) of sulfur molecules, which can bond to form an SS bridge when the environment becomes oxidizing again; - nitrogen or argon or mixtures thereof, which can be used to remove oxygen from a liquid, pasty or gaseous medium and which therefore indirectly reduces the redox potential of a medium, and promotes the reduced state (-SH) of thiol groups; - gaseous mixtures containing CO2 such as: O2 / CO2, • O2 / N2 / CO2 such as oxygen-enriched air containing CO2, n2 / co2 , • and Ar / CO2. - gaseous mixtures containing nitrogen and / or argon and / or hydrogen.

[0038] According to one embodiment of the invention, the process is a process for thickening a medium, where: - We have a medium A which must be thickened; - We have a liquid B containing proteins including cysteines; - A bubbling step is carried out on liquid B using a reducing gas such as hydrogen or with the help of nitrogen to expel the oxygen; - We proceed with a heating step of this liquid B in order to denature the proteins which unfold and expose their thiol groups in such a reducing environment; - Liquid B is added to liquid A (or liquid A to liquid B) under oxidizing conditions, for example in the presence of oxygen, to allow disulfide bridges to form between the proteins, creating a network which can, if necessary, trap other components of media A and B.

[0039] According to one of the embodiments of the invention, the medium A to be thickened is a food cream or a body cream, or a soup to be enriched with proteins and in that the liquid B is a suspension or solution of proteins whose state, and structure, depends on the redox potential.

[0040] According to one embodiment of the invention, the process is a process for producing a food product by 3D printing, where: - A protein-based matrix is ​​heated under an atmosphere of nitrogen and / or argon and / or hydrogen or mixtures thereof; - Using this heated matrix, one or more nozzles of a 3D printer capable of building said product are fed; - The nozzle is placed in an oxygen-rich environment, for example under pure oxygen, for example by the fact that the printer is placed in an oxygen-enriched chamber; - The product is deposited onto a support using the nozzle;

[0041] and where said nozzle(s) are configured to inject the protein matrix alone or to inject jointly the protein matrix and an oxidizing gas.

[0042] According to one embodiment of the invention, the method is a method for controlling the viscosity of a liquid protein matrix before its implementation in an overall production process, for example to improve its pumpability, or to limit losses during transfers, etc., where the following measures are implemented: - Nitrogen and / or argon and / or hydrogen or a mixture thereof is introduced into the matrix in order to lower the redox potential of this matrix and avoid the formation of disulfide bridges which would create a structure increasing the viscosity; - Subsequently, at a desired point in the overall process, the following steps are taken: re-contacting the matrix with an oxidizing gaseous medium in order to create a protein network and thus structure the intended product.

[0043] According to one embodiment of the invention, the following phases are carried out: - A Nol Phase comprising the formulation of said liquid matrix, which is deoxygenated by scanning or bubbling with nitrogen and / or argon or treated with hydrogen. - A Phase No. 2 where the matrix undergoes heat treatment. - Phase 3, where the transfer, transport, or transshipment of said matrix within said overall process according to the needs of the producing industrial site. - A Phase No. 4 where the said matrix is ​​brought into contact with an oxidizing gas such as oxygen, for example by bubbling, or for example by a mixing action under the atmosphere formed by the said oxidizing gas.

[0044] According to one embodiment of the invention, the process uses a medium or matrix which, by its very composition, is already naturally reducing, such as: - a matrix naturally or not containing reducing molecules such as, for example, vitamin C or other antioxidants; - a matrix that has been deoxygenated by a vacuum process; - milk or other liquid whose redox potential has been lowered by an activity microbial, for example by lactic acid bacteria.

Claims

Claims

1. A process for producing or transforming a protein medium (4), of plant, dairy, animal or even microbial origin, characterized in that during one or more of the phases occurring during the production or transformation process in question, the state of the sulfur thiol groups of the medium is controlled or modified by the injection of a chosen gas or gas mixture, the reducing or oxidizing nature of which allows a given action to be obtained on the said groups.

2. Method according to claim 1, which is one of the transformation methods of the group formed by: - Thickening methods; - Texturing reinforcement methods; - 3D printing (3, 6); - Controlling the viscosity of a liquid before its use, for example to facilitate transport, pumpability, or to limit losses during transfers.

3. Method according to claim 1 or 2, characterized in that the gas or gas mixture used is included in the group formed by: - oxygen, air or air enriched in oxygen, an oxidizing gas which makes it possible to increase the redox potential of a medium, and which promotes the oxidation of thiols into disulfide bridges; - hydrogen, and gas mixtures comprising hydrogen, a reducing gas, which promotes the reduced state (-SH) of sulfur molecules, which can bond to form an SS bridge when the medium becomes oxidizing again; - nitrogen or argon or their mixtures, which can be used to eliminate oxygen from a liquid, pasty or gaseous medium and which therefore indirectly makes it possible to reduce the redox potential of a medium, and to promote the reduced state (-SH) of thiol groups; - gas mixtures comprising CO2 such as: O2 / CO2, O2 / N2 / CO2 such as air enriched with oxygen and containing CO2, • n2 / co2, • and Ar / CO2. - gas mixtures containing nitrogen and / or argon and / or hydrogen.

4. Method according to one of the preceding claims which is a method for thickening a medium, where: - A medium A is provided which is to be thickened; - A liquid B is provided containing proteins comprising cysteines; - A step of bubbling the liquid B is carried out using a reducing gas such as hydrogen or using nitrogen to expel the oxygen therefrom; - A step of heating this liquid B is carried out in order to denature the proteins which unfold and expose their thiol groups in such a reducing medium; - This liquid B is added to the liquid A (or liquid A to the liquid B) under oxidizing conditions, for example in the presence of oxygen, in order to allow disulfide bridges to form between the proteins, thus creating a network which can, if necessary, trap other components of the media A and B.

5. Method according to claim 4, characterized in that the medium A to be thickened is a food cream or a body cream, or a soup to be enriched with proteins and in that the liquid B is a suspension or solution of proteins whose state, and structure, depends on the redox potential.

6. Method according to one of claims 1 to 3 which is a method for producing a food product (6) by 3D printing, where: - A protein-based matrix (4) is heated under an atmosphere of nitrogen and / or argon and / or hydrogen or mixtures thereof; - One or more nozzles (3) of a 3D printer capable of constructing said matrix, thus heated, are fed with the aid of this matrix. product ; - The nozzle is placed in an oxygen-rich atmosphere, for example under pure oxygen, for example by the fact that the printer is placed in an enclosure (1) under oxygen; - The product is deposited using the nozzle on a support (2); and wherein said nozzle(s) are configured to inject the protein matrix alone or to jointly inject the protein matrix and an oxidizing gas.

7. Method according to one of claims 1 to 3, which is a method for controlling the viscosity of a liquid protein matrix before its implementation in an overall production process, for example to improve its pumpability, or to limit losses during transfers, where the following measures are implemented: - Nitrogen and / or argon and / or hydrogen or one of their mixtures is used in the matrix in order to lower the redox potential of this matrix and avoid the formation of disulfide bridges which would create a structure increasing the viscosity; - Subsequently, at a desired point in the said overall process, the matrix is brought back into contact with an oxidizing gaseous medium in order to create a protein network and thus structure the targeted product.

8. Method according to claim 7, characterized in that the following phases are carried out: - A Nol Phase comprising the formulation of said liquid matrix, which is deoxygenated by flushing or bubbling with nitrogen and / or argon or treated using hydrogen. - Phase No. 2 where heat treatment of the matrix is carried out. - Phase No. 3 where the transfer or transport or decanting of said matrix takes place within said global process according to the needs of the producing industrial site. - A Phase No. 4 where we proceed to put the said in contact

9. matrix with an oxidizing gas such as oxygen, for example by bubbling, or for example by a mixing action under the atmosphere formed by said oxidizing gas. Method according to one of the preceding claims, characterized in that it uses a medium or a matrix which is, by its very composition, already naturally reducing, such as: - a matrix naturally or not containing reducing molecules such as, for example, vitamin C or other antioxidants; - a matrix which has been deoxygenated by a vacuum process; - milk or other liquid whose redox potential has been lowered by microbial activity, for example by lactic acid bacteria.

Citation Information

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