A method for compounding a protein film and a compounded protein film

Abstract

The application relates to the technical field of protein film preparation, in particular to a protein film compounding method and a compounded protein film. The method comprises the following steps: providing a first protein film and a second protein film; the first protein film is a protein film subjected to cross-linking treatment; one surface of the first protein film is attached to one surface of the second protein film to obtain an attached protein film; a protein solution is applied between the attached surfaces of the first protein film and the second protein film in the attached protein film; and cross-linking treatment is conducted on the attached protein film, so that the protein solution connects the first protein film and the second protein film together through a cross-linking reaction to obtain a compounded protein film. Through the attachment of two layers of protein films and the application of the protein solution between the attached protein films, multiple layers of protein films can be compounded together through secondary cross-linking, the water deformation performance of the compounded protein film is regulated, and therefore the application of the protein film is expanded.

Description

Technical Field

[0001] This application relates to the field of protein membrane preparation technology, and in particular to a composite method for silk protein membranes and a composite protein membrane. Background Technology

[0002] Protein membranes are highly biocompatible materials with advantages such as low susceptibility to immune responses, biodegradability, and drug delivery capabilities, making them an ideal choice for manufacturing medical devices. Furthermore, protein membranes can also serve as substrates for flexible electronic devices, such as those used in transient soluble electronic devices.

[0003] Currently, most protein films are monolayer films. However, monolayer protein films have limited mechanical properties and cannot control the internal stress, which limits their applications. Furthermore, in flexible electronic devices, monolayer protein films are often only used as substrates and cannot be used for encapsulation. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a method for compositing protein membranes and a composite protein membrane.

[0005] In a first aspect, embodiments of this application disclose a method for composite protein membranes, comprising:

[0006] A first protein membrane and a second protein membrane are provided; the first protein membrane is a cross-linked protein membrane.

[0007] One surface of a first protein membrane is attached to one surface of a second protein membrane to obtain an attached protein membrane; a protein solution is applied between the surfaces of the first and second protein membranes that are attached in the attached protein membrane.

[0008] The bonded protein membrane is cross-linked so that the protein solution links the first and second protein membranes together through a cross-linking reaction, resulting in a composite protein membrane.

[0009] In some optional embodiments, the second protein membrane is a cross-linked protein membrane, and both the first and second protein membranes are wetted protein membranes; bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes:

[0010] A protein solution is applied to one surface of the first protein membrane;

[0011] One surface of the second protein membrane is attached to the surface of the first protein membrane to which a protein solution has been applied, to obtain an attached protein membrane.

[0012] In some optional embodiments, the first protein membrane is a wetted protein membrane, and the second protein membrane is a dry protein membrane that has not undergone cross-linking treatment; bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes:

[0013] One surface of the first protein membrane is attached to one surface of the second protein membrane, so that the surface of the second protein membrane attached to the first protein membrane partially dissolves to form a protein solution, thus obtaining the attached protein membrane.

[0014] In some optional embodiments, the second protein membrane is a cross-linked protein membrane, and both the first and second protein membranes are dried protein membranes; bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes:

[0015] A protein solution is applied to one surface of the first protein membrane;

[0016] One surface of the second protein membrane is attached to the surface of the first protein membrane to which a protein solution has been applied, to obtain an attached protein membrane.

[0017] In some optional embodiments, the second protein membrane is a cross-linked protein membrane, and both the first and second protein membranes are dried protein membranes; bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes:

[0018] Plasma treatment was performed on one surface of the first protein membrane and one surface of the second protein membrane, respectively.

[0019] A protein solution is applied to the plasma-treated surface of the first protein membrane;

[0020] The surface of the second protein membrane, after being treated with plasma, is bonded to the surface of the first protein membrane to which a protein solution has been applied, to obtain a bonded protein membrane.

[0021] In some alternative implementations, the proteins in the protein solution, the proteins forming the first protein membrane, and the proteins forming the second protein membrane are of the same type.

[0022] In some alternative implementations, the protein in the protein solution is silk protein.

[0023] In some optional embodiments, the bonded protein membranes are cross-linked to allow the protein solution to link the first and second protein membranes together via a cross-linking reaction, resulting in a composite protein membrane, including:

[0024] The two sides of the bonded protein membrane are squeezed together and then dried.

[0025] The dried protein membrane is placed in a water vapor atmosphere for cross-linking treatment, so that the protein solution links the first and second protein membranes together through the cross-linking reaction to obtain a composite protein membrane.

[0026] In some optional embodiments, the dried laminated protein membrane is placed in a water vapor atmosphere for cross-linking treatment, so that the protein solution links the first and second protein membranes together through a cross-linking reaction to obtain a composite protein membrane, including:

[0027] The dried protein membrane was placed in a water vapor atmosphere for cross-linking treatment, so that the protein solution would link the first and second protein membranes together through the cross-linking reaction to obtain the combined protein membrane.

[0028] The combined protein membrane was dried to obtain a composite protein membrane.

[0029] Secondly, embodiments of this application disclose a composite protein membrane, which is prepared based on the protein membrane composite method described above.

[0030] The technical solution provided in this application has the following technical effects:

[0031] The protein membrane composite method and composite protein membrane described in this application embodiment can composite multiple protein membranes through secondary cross-linking by bonding two protein membranes together and applying a protein solution between the bonded protein membranes. This enables the control of the water deformation properties of the composite protein membrane, thereby expanding the application of protein membranes. Attached Figure Description

[0032] To more clearly illustrate the technical solutions and advantages in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 This is a schematic flowchart of a protein membrane composite method provided in an embodiment of this application;

[0034] Figure 2 This is a schematic diagram of a clamp structure for fixing a protein membrane provided in an embodiment of this application;

[0035] Figure 3 This is a schematic diagram of a protein solution coated on a first protein membrane according to an embodiment of this application;

[0036] Figure 4This is a schematic diagram of attaching a moistened second protein membrane to a first protein membrane according to an embodiment of this application;

[0037] Figure 5 This is a schematic diagram of a protein membrane fixed by a clamp according to an embodiment of this application;

[0038] Figure 6 This is a schematic diagram of another method of attaching a moistened second protein membrane to a first protein membrane, as provided in an embodiment of this application.

[0039] Figure 7 This is a schematic diagram of a second protein membrane after more protein membranes are attached to it, according to an embodiment of this application.

[0040] Figure 8 This is a schematic diagram of multiple sets of bonded protein membranes bonded together, provided in an embodiment of this application;

[0041] Figure 9 This is a schematic diagram of attaching a dried second protein membrane to a first protein membrane according to an embodiment of this application;

[0042] Figure 10 This is a schematic diagram provided in an embodiment of the present application, showing a protein solution coated on the surface of a first protein membrane after plasma treatment;

[0043] Figure 11 This is a schematic diagram of an embodiment of the present application showing how a dried second protein membrane is attached to a first protein membrane coated with a protein solution.

[0044] Figure 12 This is a schematic diagram of an extrusion-bonded protein membrane provided in an embodiment of this application;

[0045] Figure 13 This is a schematic diagram of a secondary cross-linking treatment of a bonded protein membrane provided in an embodiment of this application;

[0046] Figure 14 This is a schematic diagram of another secondary crosslinking treatment of the bonded protein membrane provided in the embodiments of this application;

[0047] Figure 15 This is a schematic diagram of the tensile test results of a composite protein membrane provided in an embodiment of this application.

[0048] The following is supplementary explanation of the attached figures:

[0049] 201-Ring component; 202-Protein membrane; 203-Protein solution; 204-First protein membrane; 205-Second protein membrane; 206-Clamping plate; 207-Silica gel block; 208-Vacuum vessel; 209-Water. Detailed Implementation

[0050] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0051] It should be noted that the term "an embodiment" or "embodiment" in the specification of the embodiments of this application refers to a specific feature, structure, or characteristic that can be included in at least one implementation of this application. It should be understood that in the specification, claims, and accompanying drawings of the embodiments of this application, the terms "upper," "lower," "top," "bottom," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first" and "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," etc., are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments of this application described herein can be implemented in orders other than those illustrated or described herein. Furthermore, in the description of this embodiment, unless otherwise stated, "a plurality of" means two or more. Additionally, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion, for example, a process, method, system, or product that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or devices.

[0052] To make the objectives, technical solutions, and advantages disclosed in the embodiments of this application clearer, the embodiments of this application will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the embodiments of this application and are not intended to limit the embodiments of this application.

[0053] Please see Figure 1 , Figure 1 This is a schematic flowchart of a protein membrane composite method provided in an embodiment of this application, as shown below. Figure 1 As shown, the method for composite protein membrane includes:

[0054] S101: Provide a first protein membrane and a second protein membrane; the first protein membrane is a protein membrane that has undergone cross-linking treatment.

[0055] In this embodiment, both the first protein membrane 204 and the second protein membrane 205 are prepared using a silk protein solution. The protein membrane prepared using a silk protein solution exhibits good structural strength and stretchability. As an optional implementation, when preparing the protein membrane using a silk protein solution, a certain amount of silk protein solution of a preset concentration can be obtained first, then degummed for a preset time. The degummed silk protein solution is then spread flat on a plane and air-dried to obtain a dry, uncrosslinked protein membrane. Optionally, the silk protein solution can be a fibroin solution, a sericin solution, or a mixture of both. The concentration of the protein solution and the degumming time can be selected as needed; for example, a 7% (w / w) silk protein solution can be degummed for 30 minutes. After obtaining the dry, uncrosslinked protein membrane, it can be crosslinked as needed.

[0056] In this embodiment, the first protein film 204 is a cross-linked protein film, which can be either dry or wet. The second protein film 205 can be either cross-linked or uncross-linked. By laminating one or more layers of the second protein film 205 onto the first protein film 204, the water-sensitive deformation properties of the composite protein film can be controlled, thereby expanding the applications of the protein film. Furthermore, when the first protein film 204 is a substrate for electronic devices, laminating the second protein film 205 onto the first protein film 204 can also achieve flexible packaging of the electronic devices, thereby improving the performance of the electronic devices.

[0057] It should be noted that the first protein membrane 204 and the second protein membrane 205 can be either dry or wet. However, uncrosslinked protein membranes are soluble in water 209 in a wet state. Therefore, wet protein membranes need to undergo crosslinking treatment first to maintain their shape.

[0058] S103: Adhere one surface of the first protein membrane to one surface of the second protein membrane to obtain an adhered protein membrane; a protein solution is applied between the adhered surfaces of the first and second protein membranes in the adhered protein membrane.

[0059] In this embodiment, when the first protein membrane 204 and the second protein membrane 205 are laminated, one surface of the first protein membrane 204 can be bonded to one surface of the second protein membrane 205 to obtain a laminated protein membrane. Since the first protein membrane 204 is a cross-linked protein membrane, it lacks a large number of active oxygen-containing groups (such as hydroxyl groups), resulting in insufficient group connections between the two protein membranes and poor adhesion. To achieve sufficient lamination of the two protein membranes, a protein solution 203 can be applied between the two protein membranes during lamination. Because the protein solution 203 contains a large number of free silk fibroin molecules, i.e., a large number of active oxygen-containing groups, indirect connections can be formed between the protein membranes, thereby ensuring the reliability of the protein membrane lamination. Optionally, the protein solution 203 applied between the first protein membrane 204 and the second protein membrane 205 can be applied to the surface of the first protein membrane 204 or the second protein membrane 205 before lamination. Optionally, the protein solution 203 applied between the first protein membrane 204 and the second protein membrane 205 can also be formed by attaching the dried, uncrosslinked second protein membrane 205 to the first protein membrane 204, and then allowing the second protein membrane 205 to absorb water and dissolve.

[0060] As an optional implementation, the second protein membrane 205 is a cross-linked protein membrane, and both the first protein membrane 204 and the second protein membrane 205 are wetted protein membranes. When both the first protein membrane 204 and the second protein membrane 205 are wetted cross-linked protein membranes, since neither layer of protein membrane has a large number of active groups after cross-linking, effective bonding cannot be achieved after lamination. Therefore, when laminating one surface of the first protein membrane 204 to one surface of the second protein membrane 205, a protein solution 203 can be applied to one surface of the first protein membrane 204 firstly, and then one surface of the second protein membrane 205 can be laminationed to the surface of the first protein membrane 204 to which the protein solution 203 is applied, to obtain an laminated protein membrane. Similarly, a protein solution 203 can be applied to one surface of the second protein membrane 205 firstly, and then one surface of the first protein membrane 204 can be laminationed to the surface of the second protein membrane 205 to which the protein solution 203 is applied, to obtain an laminated protein membrane. By applying protein solution 203, which contains a large number of active silk fibroin molecules (with oxygen-containing groups), these silk fibroin molecules will combine with the active groups in the solution and the active groups on the protein membrane during the secondary cross-linking process, thereby forming a large number of effective indirect connections, thus ensuring the reliability of the protein membrane composite.

[0061] In the above embodiments, both the first protein membrane 204 and the second protein membrane 205 are moist, cross-linked protein membranes. To facilitate the bonding of the first protein membrane 204 and the second protein membrane 205, a clamp can be used to fix the first protein membrane 204 and the second protein membrane 205. The clamp may include two annular members 201 of the same shape but different sizes that match. Optionally, the shape of the annular member 201 may be circular, triangular, quadrilateral, or other regular or irregular polygons. As an example, Figure 2 This is a schematic diagram of a clamp structure for fixing a protein membrane provided in an embodiment of this application, as shown below. Figure 2 As shown, the clamp includes two rings, one of which has the same outer diameter as the other. The edge of the protein membrane 202 can be held between the two rings, thereby fixing the protein membrane 202. In some embodiments, to facilitate the bonding of the protein membrane 202 with other protein membranes 202, the inner ring can protrude slightly outward, so that the surface of the protein membrane 202 protrudes beyond the outer ring, thus facilitating the bonding of the protein membrane 202 with other protein membranes 202. Furthermore, the clamp can also be used to pre-stretch the moistened cross-linked protein membrane, thereby controlling the expansion or contraction effect of the protein membrane during hydration. During the composite process of the first protein membrane 204 and the second protein membrane 205, since both protein membranes are fixed, the pre-stretching effect can be maintained during the composite process.

[0062] In the above embodiments, Figure 3 This is a schematic diagram illustrating the application of this application with a protein solution coated on a first protein membrane, as shown in the embodiments of this application. Figure 3 As shown, since both the first protein membrane 204 and the second protein membrane 205 are cross-linked, to achieve the composite of the first protein membrane 204 and the second protein membrane 205, a protein solution 203 can be applied to the surface of the first protein membrane 204 before bonding them. Optionally, the proteins in the protein solution 203, the proteins forming the first protein membrane 204, and the proteins forming the second protein membrane 205 are of the same type, thereby avoiding the introduction of impurities into the composite protein membrane and affecting its performance. Optionally, the proteins in the protein solution 203 are silk proteins, which can be fibroin, sericin, or a mixture of both. Silk has better film-forming properties and mechanical properties, thus resulting in a composite protein membrane with better performance. During the application of the protein solution 203 to the surface of the first protein membrane 204, air bubbles should be avoided in the coated protein solution 203.

[0063] In the above embodiments, Figure 4 This is a schematic diagram illustrating the bonding of a moistened second protein membrane to a first protein membrane, as provided in an embodiment of this application. Figure 4As shown, after coating a protein solution 203 onto one surface of the first protein membrane 204, a second protein membrane 205 can be attached to the first protein membrane 204. When attaching the second protein membrane 205 to the first protein membrane 204, the second protein membrane 205 should be slowly attached to the surface of the first protein membrane 204 coated with the protein solution to avoid air bubbles forming during the attachment process. After attaching the first protein membrane 204 and the second protein membrane 205, a clamp 206 can be used to fix the clamps that hold the first protein membrane 204 and the second protein membrane 205 in place. As an example, Figure 5 This is a schematic diagram of a bonded protein membrane fixed by a clamp according to an embodiment of this application, as shown below. Figure 5 As shown, when the first protein membrane 204 and the second protein membrane 205 are of the same size, the clamps for fixing the first protein membrane 204 and the clamps for fixing the second protein membrane 205 are of the same size. The clamp plate 206 can fix the two sets of clamps stacked together, thereby preventing the adhered protein membranes from separating during the transfer process. As another example, Figure 6 This is another schematic diagram provided in this application embodiment of attaching a moistened second protein membrane to a first protein membrane, as shown below. Figure 6 As shown, when the second protein membrane 205 is smaller than the first protein membrane 204, the clamp for fixing the first protein membrane 204 is larger than the clamp for fixing the second protein membrane 205. After the first protein membrane 204 and the second protein membrane 205 are bonded together, the two sets of clamps can be fitted together. The clamp plate 206 can fix the two sets of clamps fitted together, thereby preventing the bonded protein membranes from separating during the transfer process.

[0064] In some embodiments, after the second protein membrane 205 is attached to the first protein membrane 204, more protein membranes may be sequentially attached to the second protein membrane 205. As an example, Figure 7 This is a schematic diagram illustrating an embodiment of the present application showing the application of more protein membranes attached to a second protein membrane, as shown below. Figure 7 As shown, after the second protein membrane 205 is bonded to the first protein membrane 204, more protein membranes can be bonded to the second protein membrane 205. Optionally, the protein membranes bonded to the second protein membrane 205 are cross-linked, moistened protein membranes, and the protein types are the same as those in the second protein membrane 205. When bonding more protein membranes to the second protein membrane 205, the process is the same as bonding the second protein membrane 205 to the first protein membrane 204: first, a protein solution 203 is coated onto the protein membrane; then, the protein membranes to be bonded are bonded to the surface of the protein membrane coated with the protein solution 203; finally, the clamps 206 are used to fix all the protein membranes in place. In other embodiments, the protein membranes can be bonded in pairs before further bonding. Figure 8 This is a schematic diagram illustrating the bonding of multiple sets of adhesive protein membranes according to an embodiment of this application, as shown below. Figure 8As shown, the protein membranes to be bonded are bonded in pairs, and then the bonded protein membranes are bonded together. The specific bonding process is the same as that of the first protein membrane 204 and the second protein membrane 205, and will not be described again here.

[0065] In the above embodiments, when the protein membrane to be laminated is a moist, cross-linked protein membrane, a pre-stretching treatment can be performed on the protein membrane before laminating two or more protein membranes. Generally, a dry, cross-linked protein membrane that has not undergone stretching treatment will swell after absorbing water. After pre-stretching treatment, the protein membrane will exhibit different degrees of impact or shrinkage after absorbing water, depending on the degree of stretching. When laminating two protein membranes, because the two protein membranes have different degrees of stretching, i.e., different degrees of expansion or shrinkage after absorbing water, stress can be introduced when the composite protein membrane absorbs water, causing the final composite protein membrane to bend or curl. During the pre-stretching treatment of the protein membrane, it is usually necessary to use clamps to fix the protein membrane, such as… Figure 2 The clamp shown prevents the protein membrane from springing back.

[0066] As another optional implementation, the first protein membrane 204 is a wetted protein membrane, and the second protein membrane 205 is a dry protein membrane that has not undergone cross-linking treatment. Optionally, the first protein membrane 204 is a pre-stretched protein membrane. Optionally, to facilitate the adhesion of the protein membranes, the first protein membrane 204 can be fixed using a clamp.

[0067] When the first protein membrane 204 is a wet, cross-linked protein membrane and the second protein membrane 205 is a dry, uncross-linked protein membrane, when bonding one surface of the first protein membrane 204 to one surface of the second protein membrane 205, the two surfaces can be directly bonded together. After the second protein membrane 205 is bonded to the first protein membrane 204, the bonded surfaces of the second protein membrane 205 and the first protein membrane 204 will partially dissolve to form a protein solution 203, thereby obtaining the bonded protein membrane.

[0068] In the above embodiments, the first protein membrane 204 and the second protein membrane 205 contain the same type of protein, such as silk fibroin. Since the first protein membrane 204 is a moist, cross-linked protein membrane, and the second protein membrane 205 is a dry, uncross-linked protein membrane, the second protein membrane 205 will dissolve after absorbing water. Therefore, the second protein membrane 205 can be directly adhered to the first protein membrane 204 without needing to coat the first protein membrane 204 with the protein solution 203. As an example, Figure 9 This is a schematic diagram illustrating the process of attaching a dried second protein membrane to a first protein membrane, as provided in an embodiment of this application. Figure 9As shown, the second protein membrane 205 is directly attached to the first protein membrane 204. The surface of the second protein membrane 205 in contact with the first protein membrane 204 can absorb water and dissolve, thereby generating a protein solution 203 between the first protein membrane 204 and the second protein membrane 205, so as to facilitate the subsequent cross-linking of the first protein membrane and the second protein membrane 205 together.

[0069] In the above embodiments, a second protein membrane 205 may be attached to only one surface of the first protein membrane 204, or a second protein membrane 205 may be attached to both surfaces of the first protein membrane 204. This application does not impose excessive limitations on this aspect.

[0070] In the above embodiments, a pre-stretched protein membrane can be bonded together with one or two dry, uncrosslinked protein membranes. The pre-stretched protein membrane can maintain the control of its shrinkage rate by the pre-stretching, while the shrinkage properties of the dry, uncrosslinked protein membrane are consistent with those of ordinary protein membranes. That is, the protein membrane treated with the minimum pre-stretching rate swells by about 15% after absorbing water, which is a shrinkage rate of -15%.

[0071] As another optional embodiment, the second protein membrane 205 is a cross-linked protein membrane, and both the first protein membrane 204 and the second protein membrane 205 are dried protein membranes. Optionally, the first protein membrane 204 and / or the second protein membrane 205 are pre-stretched protein membranes. Optionally, the first protein membrane 204 and / or the second protein membrane 205 can be fixed to a fixture, or they can be unfixed protein membranes.

[0072] When both the first protein membrane 204 and the second protein membrane 205 are dry, cross-linked protein membranes, when bonding one surface of the first protein membrane 204 to one surface of the second protein membrane 205, it is necessary to first apply a protein solution 203 to one surface of the first protein membrane 204, and then bond one surface of the second protein membrane 205 to the surface of the first protein membrane 204 to which the protein solution 203 has been applied, to obtain a bonded protein membrane.

[0073] In the above embodiments, the first protein membrane 204 and / or the second protein membrane 205 can be a protein membrane fixed on a fixture, or it can be a protein membrane not fixed on a fixture. Optionally, when the first protein membrane 204 and / or the second protein membrane 205 are protein membranes that have undergone pre-stretching treatment, a protein membrane fixed on a fixture can be used to ensure that the protein membrane can maintain the corresponding pre-stretching treatment effect during the lamination process.

[0074] In the above embodiments, since both the first protein film 204 and the second protein film 205 are cross-linked dried protein films, to ensure the composite effect of the protein films, before coating the first protein film 204 with the protein solution 203, one surface of the first protein film 204 and one surface of the second protein film 205 can be subjected to plasma treatment, respectively, to hydroxylate the surfaces where the first protein film 204 and the second protein film 205 are bonded. By performing plasma treatment on the surfaces where the first protein film 204 and the second protein film 205 are bonded, surface activity can be improved, enabling the two protein films to achieve a better composite effect. After plasma treatment of the surfaces where the first protein film 204 and the second protein film 205 are bonded, the protein solution 203 can be applied to the plasma-treated surface of the first protein film 204. The free silk fibroin molecules in the protein solution 203 can bind to hydroxyl groups, thereby further improving the reliability of the protein film composite. That is, the surfaces of the first protein membrane 204 and the second protein membrane 205 that are bonded together are subjected to plasma treatment to hydroxylate the surfaces of the first protein membrane 204 and the second protein membrane 205 that are bonded together, thereby facilitating subsequent secondary crosslinking treatment. Figure 10 This is a schematic diagram provided in an embodiment of this application, showing a protein solution coated on the surface of a first protein membrane after plasma treatment. Figure 10 As shown, after plasma treatment of the surfaces on which the first protein membrane 204 and the second protein membrane 205 are bonded, a protein solution 203 can be coated onto the plasma-treated surfaces of the first protein membrane 204 or the second protein membrane 205. Optionally, the proteins in the protein solution 203, the proteins forming the first protein membrane 204, and the proteins forming the second protein membrane 205 are all of the same type, namely, silk protein. Figure 11 This is a schematic diagram illustrating how a dried second protein membrane is adhered to a first protein membrane coated with a protein solution, as provided in an embodiment of this application. Figure 11 As shown, after the protein solution 203 is coated, the surface of the second protein film 205 that has been plasma-treated can be bonded to the surface of the first protein film 204 to which the protein solution 203 has been applied, to obtain a bonded protein film.

[0075] In some embodiments, after the second protein membrane 205 is attached to the first protein membrane 204, more protein membranes identical to the second protein membrane 205 may be sequentially attached to the second protein membrane 205. Before attaching more protein membranes, the surfaces of each protein membrane to be attached to other protein membranes need to be plasma-treated, and a protein solution 203 needs to be applied between the two protein membranes.

[0076] It should be noted that air bubbles should be avoided in the protein solution 203 during the coating process described above. Furthermore, the protein membrane should be applied slowly during the bonding process to prevent air bubbles from forming. Additionally, the amount of protein solution 203 should be controlled to prevent significant deformation of the protein membrane, i.e., maintaining a water content of no more than 15%. Moreover, when bonding a dry protein membrane, the bonding speed should be as fast as possible to avoid the protein membrane absorbing excessive moisture and causing deformation.

[0077] S105: Cross-link the bonded protein membrane so that the protein solution links the first and second protein membranes together through a cross-linking reaction to obtain a composite protein membrane.

[0078] In this embodiment of the application, after the protein membrane is laminated to obtain the laminated protein membrane, a secondary crosslinking treatment can be performed on the laminated protein membrane to achieve the composite between different protein membranes.

[0079] In some embodiments, after obtaining the laminated protein membrane, excess protein solution 203 between the two protein membranes can be squeezed out first, then dried, and finally subjected to a secondary crosslinking treatment. Specifically, after obtaining the laminated protein membrane, the two surfaces of the laminated protein membrane are squeezed and dried, and then the dried laminated protein membrane is crosslinked to allow the protein solution 203 to link the first protein membrane 204 and the second protein membrane 205 together through a crosslinking reaction, thereby obtaining a composite protein membrane.

[0080] When pressing the two sides of the protein membrane, this can be achieved by placing relatively soft weights on both sides of the membrane. Using soft weights for pressing avoids damage to the protein membrane. Optionally, the soft weights can be silicone blocks 207, rubber blocks, water bags, etc. As an example, Figure 12 This is a schematic diagram of an extrusion-bonded protein membrane provided in an embodiment of this application, as shown below. Figure 12 As shown, the protein membrane is placed on a soft, flat silicone block 207, with both sides of the protein membrane in contact with the silicone block 207. Different weights of soft, flat silicone blocks 207 are selected based on the required amount of protein solution. These blocks are placed on the upper and lower surfaces of the assembled protein membrane, and any residual air bubbles inside the protein membrane are squeezed to the edges during placement. The protein membrane placed between the silicone blocks 207 is then placed in a dry environment for approximately 24-48 hours until completely dry.

[0081] In this embodiment, when performing a secondary crosslinking treatment on the dried protein membrane, different crosslinking methods can be used for the protein membrane in different states. Specifically, for protein membranes not fixed by clamps, they can be placed under dry room temperature conditions for natural crosslinking. For protein membranes fixed by clamps, a steam crosslinking method can be used for secondary crosslinking.

[0082] As an optional implementation, when both the first protein membrane 204 and the second protein membrane 205 are wet, cross-linked protein membranes, since the first protein membrane 204 and the second protein membrane 205 are usually fixed by a clamp in this case, a steam cross-linking method can be used to perform a secondary cross-linking treatment on the bonded protein membranes to improve the cross-linking efficiency. Of course, in this case, the bonded protein membranes can also be placed in dry room temperature conditions for natural cross-linking.

[0083] As another alternative implementation, when the first protein membrane 204 is a moist, cross-linked protein membrane and the second protein membrane 205 is a dry, uncross-linked protein membrane, since the first protein membrane 204 is usually fixed by a clamp in this case, a steam cross-linking method can be used to perform a secondary cross-linking treatment on the bonded protein membrane to improve the cross-linking efficiency. Of course, in this case, the bonded protein membrane can also be placed under dry room temperature conditions for natural cross-linking.

[0084] As another optional implementation, if both the first protein membrane 204 and the second protein membrane 205 are dry, cross-linked protein membranes, and if both the first protein membrane 204 and the second protein membrane 205 are fixed by a fixture, then to improve the cross-linking efficiency, a steam cross-linking method can be used to perform a secondary cross-linking treatment on the bonded protein membranes. If the first protein membrane 204 and the second protein membrane 205 are not fixed by a fixture, to prevent the first protein membrane 204 and the second protein membrane 205 from deforming after absorbing water, the bonded protein membranes can be placed under dry room temperature conditions for natural cross-linking.

[0085] It should be noted that the crosslinking method can also be selected based on whether the protein membrane has undergone pre-stretching treatment. Pre-stretched protein membranes tend to shrink after absorbing water, affecting stress control within the composite protein membrane. To prevent shrinkage of pre-stretched protein membranes after water absorption, one approach is to use clamps to fix the pre-stretched membrane, allowing for the selection of any crosslinking method for secondary crosslinking. Alternatively, secondary crosslinking can be achieved under natural conditions.

[0086] In this embodiment, the dried laminated protein membrane is cross-linked so that the protein solution 203 links the first protein membrane 204 and the second protein membrane 205 together through a cross-linking reaction to obtain a combined protein membrane. Then, the combined protein membrane is dried to obtain a composite protein membrane.

[0087] As an example, Figure 13 This is a schematic diagram of a secondary cross-linking treatment of an adhesive protein membrane provided in an embodiment of this application, as shown below. Figure 13 As shown, each protein membrane in the laminated protein membrane is fixed by a clamp, thus allowing for secondary crosslinking using a steam crosslinking method. Specifically, the dried laminated protein membrane is placed in a vacuum vessel 208 with water 209 at the bottom, and a secondary crosslinking treatment is performed using a steam crosslinking method. This steam crosslinking method avoids the risks and costs associated with using chemical crosslinking agents. Furthermore, this method allows for control over the degree and duration of the crosslinking reaction, thereby obtaining the desired properties of the protein composite material.

[0088] Vacuum reactor 208 is evacuated to maintain a certain degree of vacuum inside. Under these conditions, the reactor 208 can be filled with water vapor to create a relatively humid atmosphere. When proteins are placed in a water vapor atmosphere, the water vapor interacts with the polar groups on the surface of protein molecules, causing the protein molecules to approach and aggregate, thus achieving cross-linking. The bonded protein membrane is then reacted in the vacuum reactor 208 for 24-48 hours at room temperature. The reacted protein membrane is then removed from the vacuum reactor 208 and placed in a dry environment for approximately 24-48 hours until completely dry. Finally, the central region of the protein membrane is removed using a blade, yielding the desired composite protein membrane.

[0089] As another example, for dried cross-linked protein membranes, if the protein membrane is a pre-stretched protein membrane and is not fixed after cutting, in order to prevent the protein membrane from absorbing water and causing the control of protein membrane deformation through pre-stretching to fail, the surface of the protein membrane can be plasma-treated to hydroxylate the protein membrane surface. A small amount of protein solution is then added to bind with the hydroxyl groups in the protein membrane. Figure 14 This is a schematic diagram of another secondary crosslinking treatment of the bonded protein membrane provided in the embodiments of this application, as shown below. Figure 14 As shown, after obtaining the bonded protein membrane, a soft weight, such as a silicone block 207, is used to press the bonded protein membrane tightly. After drying for a period of time, such as 24-48 hours, the bonded protein membrane undergoes a cross-linking reaction, thereby achieving secondary cross-linking between the bonded protein membranes to obtain a composite protein membrane.

[0090] The protein membrane composite method described in this application embodiment can achieve multilayer composites of wet protein membranes with each other, wet protein membranes with dry, uncrosslinked protein membranes, and dry, crosslinked protein membranes with each other. When composited with multiple wet protein membranes, the wet protein membranes are bonded while fixed in a fixture, thus preserving the control effect on deformation during the protein membrane hydration process. Furthermore, by using a specific weight of silicone block 207, the amount of protein solution between the protein membranes can be controlled, avoiding excessive protein solution 203 in the bonded protein membranes. When bonding dry, crosslinked protein membranes together, the bonding effect between the protein membranes is improved by using plasma treatment to hydroxylate the surfaces to be bonded. Moreover, by reducing the amount of protein solution used and accelerating the bonding speed, the control effect on deformation during the protein membrane hydration process is preserved as much as possible.

[0091] The above composite method can achieve reliable composite of protein membranes. Figure 15 This is a schematic diagram of the tensile test results of a composite protein membrane provided in an embodiment of this application, as shown below. Figure 15 As shown, the protein membrane composite method described in this application is used to composite two protein membranes in a staggered manner. After the composite is completed, an ultimate tensile test is performed. According to the test results, the protein membrane fracture occurs in the uncomposite area. It can be seen that the composite protein membrane obtained by the above method has good composite reliability.

[0092] This application also provides a composite protein membrane, which is prepared based on the protein membrane composite method described above.

[0093] In this embodiment, the composite protein film obtained by the above method can be used for protein film encapsulation. For example, an electrode with a protein film as a substrate and conductive lines fabricated on its upper surface can be protected from external environmental influences (such as those within the body) by using another layer of protein film bonded to its upper surface, thus isolating the conductive structure from the outside world. Moreover, multiple multilayer protein films with deformation effects can be composited together using the above method to achieve more complex deformation effects. In addition, two wetted protein films fixed on a fixture can be used to bond two pre-stretched protein films together, wherein the two protein films can retain the pre-stretching control over their shrinkage rate. As an example, a bilayer film is formed by composited a protein film with unidirectional shrinkage during hydration and a protein film with unchanged deformation during hydration using the above-described protein film composite method. When the bilayer film is exposed to water, it curls with the inner side facing inward, and the final degree of curling and helix angle can be controlled by adjusting the film thickness, stretching, and cutting angle.

[0094] It should be noted that the order of the embodiments described above is merely for descriptive purposes and does not represent the superiority or inferiority of the embodiments. Furthermore, specific embodiments have been described above. Other embodiments are within the scope of the appended claims. In some cases, the actions or steps described in the claims can be performed in a different order than that shown in the embodiments and still achieve the desired result. Additionally, the processes depicted in the drawings do not necessarily require a specific or sequential order to achieve the desired result. In some embodiments, multitasking and parallel processing are also possible or may be advantageous.

[0095] The various embodiments in this specification are described in a progressive manner. Similar or identical parts between embodiments can be referred to mutually. Each embodiment focuses on describing the differences from other embodiments. In particular, the device embodiments are basically similar to the method embodiments, so the description is relatively simple; relevant parts can be referred to the descriptions of the method embodiments.

[0096] Those skilled in the art will understand that all or part of the steps of the above embodiments can be implemented by hardware or by a program instructing related hardware. The program can be stored in a computer-readable storage medium, such as a read-only memory, a disk, or an optical disk.

[0097] The above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for composite protein membranes, characterized in that, include: Provide a first protein membrane and a second protein membrane; The first protein membrane is a cross-linked protein membrane; One surface of the first protein membrane is attached to one surface of the second protein membrane to obtain an attached protein membrane; A protein solution is applied between the surfaces of the first protein membrane and the second protein membrane that are bonded together in the adhesive protein membrane; The bonded protein membrane is subjected to a cross-linking treatment so that the protein solution links the first protein membrane and the second protein membrane together through a cross-linking reaction, thereby obtaining a composite protein membrane.

2. The method for composite protein membranes according to claim 1, characterized in that, The second protein membrane is a cross-linked protein membrane, and both the first protein membrane and the second protein membrane are wetted protein membranes; The step of bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes: A protein solution is applied to one surface of the first protein membrane; The second protein membrane is bonded to the surface of the first protein membrane to which a protein solution has been applied, to obtain the bonded protein membrane.

3. The method for composite protein membranes according to claim 1, characterized in that, The first protein membrane is a wet protein membrane, and the second protein membrane is a dry protein membrane that has not undergone cross-linking treatment; The step of bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes: One surface of the first protein membrane is attached to one surface of the second protein membrane, so that the surface of the second protein membrane attached to the first protein membrane partially dissolves to form a protein solution, thereby obtaining the attached protein membrane.

4. The method for composite protein membranes according to claim 1, characterized in that, The second protein membrane is a cross-linked protein membrane, and both the first protein membrane and the second protein membrane are dried protein membranes; The step of bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes: A protein solution is applied to one surface of the first protein membrane; The second protein membrane is bonded to the surface of the first protein membrane to which a protein solution has been applied, to obtain the bonded protein membrane.

5. The method for composite protein membranes according to claim 1, characterized in that, The second protein membrane is a cross-linked protein membrane, and both the first protein membrane and the second protein membrane are dried protein membranes; The step of bonding one surface of the first protein membrane to one surface of the second protein membrane to obtain a bonded protein membrane includes: Plasma treatment was performed on one surface of the first protein membrane and one surface of the second protein membrane, respectively. A protein solution is applied to the plasma-treated surface of the first protein membrane; The surface of the second protein membrane that has been treated with plasma is bonded to the surface of the first protein membrane to which a protein solution has been applied, to obtain the bonded protein membrane.

6. The method for composite protein membranes according to any one of claims 1 to 5, characterized in that, The proteins in the protein solution, the proteins that form the first protein membrane, and the proteins that form the second protein membrane are all the same type.

7. The method for composite protein membranes according to claim 6, characterized in that, The protein in the protein solution is silk protein.

8. The method for composite protein membranes according to claim 1, characterized in that, The process of cross-linking the bonded protein membrane to link the first protein membrane and the second protein membrane together through a cross-linking reaction to obtain a composite protein membrane includes: The two sides of the bonded protein membrane are squeezed and the bonded protein membrane is dried. The dried protein membrane is placed in a water vapor atmosphere for cross-linking treatment, so that the protein solution links the first protein membrane and the second protein membrane together through a cross-linking reaction to obtain a composite protein membrane.

9. The method for composite protein membranes according to claim 8, characterized in that, The process of placing the dried, laminated protein membrane in a water vapor atmosphere for cross-linking treatment, so that the protein solution links the first protein membrane and the second protein membrane together through a cross-linking reaction, to obtain a composite protein membrane, includes: The dried laminated protein membrane is placed in a water vapor atmosphere for cross-linking treatment, so that the protein solution links the first protein membrane and the second protein membrane together through a cross-linking reaction to obtain a combined protein membrane. The combined protein membrane is dried to obtain the composite protein membrane.

10. A composite protein membrane, characterized in that, The composite protein membrane is prepared by the composite method of the protein membrane according to any one of claims 1 to 9.

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