Tussah pupa protein-based 3D / 4D printing slurry as well as preparation method and application thereof

By extracting tussah silkworm pupa protein through radio frequency and microfluidization treatment combined with protein precipitant, and adding annelid/arthropod protein, fungal polysaccharide and globular protein, a rheologically stable 3D/4D printing slurry is constructed, which solves the problems of difficult separation and low extraction efficiency of tussah silkworm pupa protein, and realizes efficient and stable food printing and intelligent changes.

CN120814647APending Publication Date: 2025-10-21SOUTHWEST UNIV
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Patent Information

Application Number
CN202511134929.8
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-08-14
Publication Date
2025-10-21

AI Technical Summary

Technical Problem

In the existing technology, the separation of tussah pupa protein is difficult and the extraction efficiency is low, which affects its application in 3D/4D printing. It also lacks rheological stability and dispersibility, which limits its functionality and intelligence in food production.

Method used

Tussah pupa protein was extracted by radio frequency and microfluidization combined with protein precipitant. Then, a rheologically stable tussah pupa protein-based 3D/4D printing slurry was constructed by adding annelid/arthropod protein, fungal polysaccharides and globular proteins. The intelligent changes of food were achieved by pH control and blue light irradiation.

Benefits of technology

The extraction efficiency and purity of tussah pupa protein have been improved, the stability and shape retention rate of printed food have been enhanced, controllable changes in food appearance and nutrition have been achieved, and the application scope of 3D/4D printing has been expanded.

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Abstract

The invention relates to the field of food processing, in particular to tussah pupa protein-based 3D / 4D printing slurry as well as a preparation method and application thereof, and the tussah pupa protein-based 3D / 4D printing slurry comprises the following components in percentage by mass: 5-20% of tussah pupa protein, 5-10% of link / arthropod protein, 0.1-10% of fungal polysaccharide, 0.1-10% of globular protein, 0-5% of nutritional natural colorant and the balance of water. The tussah pupa protein-based food produced by the 3D / 4D printer has the characteristics of individuation, functionalization, nutrition, innovation and the like, and can achieve special complexity and curved surface degree, so that the product is more attractive to consumers; in the transportation process, the unique shape can be effectively kept so as to reduce the risk of being damaged on a logistics chain line, and the application range is wide.
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Description

Technical Field

[0001] The present invention relates to the field of food processing, and in particular to a tussah pupa protein-based 3D / 4D printing slurry, a preparation method thereof, and applications thereof. Background Art

[0002] 3D printing, also known as "additive manufacturing," is a novel rapid prototyping technology based on digital model files. By gradually adding food ingredients layer by layer, it can be used to produce complex structures that are difficult to achieve using traditional manufacturing methods, reducing production costs and expanding the range of food ingredients used. By introducing dimensions like time into 3D printing, 4D printing, an emerging intelligent manufacturing technology, can emerge. Its intelligence lies in the self-responsiveness of 4D-printed products to external stimuli (temperature, light, pH), enabling controlled, dynamic, intelligent evolution of food products to improve food quality (such as color and shape), nutrition, and flavor. However, the range of food ingredients suitable for 3D / 4D printing is relatively narrow, limiting its application and requiring further expansion.

[0003] Tussah pupa protein, derived from the silkworm, boasts high nutritional value, is easily digested and absorbed, and has a high utilization rate in the human body, making it a promising candidate for the development of functional pulp systems. Tussah silkworms are diverse, reproduce rapidly, and have strong adaptability, surviving even harsh environments. Their pupae are high in protein, attracting widespread attention across various fields. As a novel protein resource, tussah pupa protein offers higher protein content, lower greenhouse gas emissions, higher feed conversion rates, lower water consumption, less space requirements, and shorter breeding cycles compared to other common animal proteins. It also contains a richer amino acid content than plant proteins and a higher protein content than mealworms, more closely matching human needs. This sustainable development strategy can meet the human demand for high-protein foods. With global population growth, food demand is expected to increase significantly, making it a potential alternative to traditional animal protein. However, tussah pupa protein is difficult to isolate and is tightly bound to substances such as fat and chitin, resulting in low extraction efficiency and impacting its functionality. Currently, there are no reports on the use of tussah pupa protein in 3D / 4D printing. More efficient methods are needed to extract tussah pupa protein. After extraction, 3D / 4D printing can efficiently enable the free design of the appearance of tussah pupa protein-based foods. It can also promote the digital and intelligent production of foods with controllable appearance, flavor, texture, or nutritional value. Therefore, this exploration is of great significance. Summary of the Invention

[0004] One of the purposes of the present invention is to provide a tussah pupa protein-based 3D / 4D printing slurry with the advantages of rheological stability, good dispersibility, safety and sustainability.

[0005] The second object of the present invention is to provide a method for preparing tussah pupa protein-based 3D / 4D printing slurry, which has a simple process and is easy to adjust.

[0006] A third object of the present invention is to provide an application of a tussah pupa protein-based 3D / 4D printing slurry, and to use the slurry to print food using a 3D / 4D printing device.

[0007] The technical solution adopted by the present invention to achieve one of the purposes is: a tussah pupa protein-based 3D / 4D printing slurry, which includes, by mass percentage, 5%~20% tussah pupa protein, 5%~10% segment / arthropod protein, 0.1%~10% fungal polysaccharide, 0.1%~10% globular protein, 0-5% nutritional natural colorant, and the balance is water.

[0008] Preferably, the method for extracting tussah pupa protein comprises the following steps: A1. Peeling, deveining, cleaning, drying, and then crushing tussah pupae to obtain tussah pupae powder; A2. adding water to the tussah pupa powder, stirring, and radio frequency treatment; then performing Soxhlet defatting; drying and crushing the obtained filter residue to obtain tussah pupa defatted powder; A3. Add water to the defatted powder of tussah pupa, and sequentially subject the powder to a first microfluidization treatment, a first radiofrequency treatment, a second microfluidization treatment, and a second radiofrequency treatment. Stir and centrifuge the mixture, and collect the supernatant. A4. Add a protein precipitant to the supernatant, centrifuge, dialyze the precipitate, and dry the product to obtain tussah pupa protein.

[0009] In step A2, radio frequency treatment is used to destroy the structure of the tussah silkworm pupa, forming gaps, promoting the removal of lipids, chitin and other substances, and initially helping to release proteins.

[0010] In step A3, the first microfluidization treatment, the first radiofrequency treatment, the second microfluidization treatment, and the second radiofrequency treatment are performed to uniformly destroy the intermolecular forces in the system, thereby further promoting the separation of lipids, chitin, and other substances.

[0011] In step A4, the protein precipitant is generally ammonium sulfate or sodium sulfate.

[0012] The extraction method of tussah pupa protein of the present invention overcomes the problems in the prior art of great difficulty in separating tussah pupa protein, close binding of tussah pupa protein with substances such as fat and chitin, low extraction efficiency, and impact on its functionality. The extraction of tussah pupa protein is promoted by radio frequency or microfluidization treatment, so that the extraction efficiency of tussah pupa protein is high and the purity is high. The tussah pupa protein extracted by the extraction method of the present invention has higher applicability, and the printed product has a lower loss factor, higher elasticity and mechanical strength; the thixotropy recovery rate of the three-stage thixotropy test (3ITT) is higher; 3D printed food has higher stability and higher shape retention rate; 4D printed food has high color evolution efficiency, etc.

[0013] Preferably, in step A2, the power of the RF treatment is 100-1100 W, and the treatment time is within 2 h. In step A3, the pressure of the first microjet and the second microjet treatment is 100-200 MPa, and the cycle is 2-10 times. The power of the first RF and the second RF treatment is 100-1000 W, and the treatment time is within 10 min.

[0014] Preferably, the annelid / arthropod protein comprises annelid or arthropod protein prepared using at least one of earthworms, wasps, bees, cicadas, grasshoppers, rice locusts, Polyrhachis tinctorius, Polyrhachis rubripes, Chikatana ants, and weaver ants as raw materials, and the average molecular weight of the tussah pupa protein and the annelid / arthropod protein are both 1000~300000 Da.

[0015] Preferably, the fungal polysaccharide is at least one of black truffle polysaccharide, tricholoma polysaccharide, Volvariella volvacea polysaccharide, Gallinarum polysaccharide, Boletus polysaccharide, and Chanterelle polysaccharide.

[0016] Preferably, the globular protein includes at least one of red bean globular protein, mung bean globular protein, buckwheat globular protein, oat globular protein, walnut globular protein, quinoa globular protein, and perilla seed globular protein.

[0017] Preferably, the nutritional natural colorant includes at least one of phycocyanin, cochineal red pigment, monascus red pigment, purple sweet potato red pigment, and radish red pigment.

[0018] The technical solution adopted by the present invention to achieve the second purpose is: a method for preparing the tussah pupa protein-based 3D / 4D printing slurry, comprising the following steps: B1, dissolving tussah pupa protein in water to obtain tussah pupa protein solution; B2. Add annelid / arthropod protein to the tussah pupa protein solution obtained in step B1, and then homogenize; add fungal polysaccharide and mix evenly to construct a rheologically stable tussah pupa protein system; B3, adding globular protein to the rheologically stable tussah pupa protein system obtained in step B2 and mixing uniformly to obtain a structure-enhanced tussah pupa protein-based food slurry; B4. Add a nutritional natural colorant to the structure-enhanced tussah pupa protein-based food slurry obtained in step B3 and mix evenly to obtain the tussah pupa protein-based 3D / 4D printing slurry.

[0019] Preferably, in steps B1-B4, the operating temperature is 25-55°C.

[0020] The technical solution adopted by the present invention to achieve the third purpose is: an application of the tussah pupa protein-based 3D / 4D printing slurry, using the tussah pupa protein-based 3D / 4D printing slurry to print food through a 3D / 4D printing device. During the printing process, 3D printing of personalized tussah pupa protein-based food can be achieved; 4D printing of tussah pupa protein-based food can also be achieved through pH control or blue light irradiation control.

[0021] When a sensitive nutritional natural colorant is added to the tussah pupa protein-based 3D / 4D printing slurry, the color of the printed tussah pupa protein-based food can have the characteristic of evolving over time.

[0022] The pH range was 3-10, 0-30 min; the blue light irradiation time was 0-1 h.

[0023] The beneficial effects of the present invention are as follows: In the tussah pupa protein-based 3D / 4D printing slurry of the present invention, the annelid / arthropod protein can assist the tussah pupa protein system, be distributed in the molecular network, promote the formation of molecular entanglement, and improve the network system of the tussah pupa protein solution; the fungal polysaccharide, with the help of its linear structure molecules and branched structure molecules, can promote the construction of an excellent viscoelastic and rheologically stable tussah pupa protein system through the "flexible metastable effect"; the globular protein can interact with the components in the tussah pupa protein system, and through the "heterogeneous symbiotic effect", produce performance complementarity and property synergy, which can further enhance the rheological structure of the tussah pupa protein system, so that the tussah pupa protein-based food slurry has better physical stability and 3D / 4D printability, reduces the loss of food slurry, and promotes the high-value utilization of tussah pupa protein.

[0024] The tussah pupa protein-based food produced using the 3D / 4D printer of the present invention has the characteristics of personalization, functionality, nutrition, and innovation. It can achieve special complexity and curvature, making the product more attractive to consumers. It can effectively maintain its unique shape during transportation to reduce the risk of damage in the logistics chain, and has a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of extraction of tussah pupae according to Example 1 of the present invention; Figure 2 Shown are the frequency sweep loss factor, 3ITT thixotropic recovery rate, and 3D printed food shape retention rate of the tussah pupa protein-based 3D printable food slurry prepared in Example 1 of the present invention; Figure 3 The figure shows the color reaction efficiency of the tussah pupa protein-based 4D printed food prepared in Example 2 of the present invention under the stimulation of a blue light system; Figure 4Shown are photos of tussah pupa protein-based 3D printing and 4D printing (after pH system stimulation for 10 minutes) prepared in Example 3 of the present invention. Figure 5 Shown are photos of commercial traditional tussah pupa protein-based 3D printing (A) and 4D printing (after pH system stimulation for 10 minutes) (B) foods prepared in Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0026] The present invention is described in detail below in conjunction with the embodiments and drawings. The following embodiments are implemented on the premise of the technical solution of the present invention, and provide detailed implementation methods and specific operating processes, but the protection scope of the present invention is not limited to the following embodiments.

[0027] In the following examples, unless otherwise specified, all methods are conventional methods; the reagents and materials described, unless otherwise specified, can be obtained from commercial sources.

[0028] The method of the present invention is summarized as follows: A tussah pupa protein-based 3D / 4D printing slurry comprises, by mass percentage, 5%-20% tussah pupa protein, 5%-10% annelid / arthropod protein, 0.1%-10% fungal polysaccharide, 0.1%-10% globular protein, 0-5% nutritional natural colorant, and the balance is water.

[0029] Green extraction of tussah pupa protein: (1) The tussah pupae were cleaned, dried, peeled, degummed, and cleaned again, followed by vacuum freeze drying (24 h-48 h), and pulverized by a planetary ball mill (100-500 r / min, 25°C) with a material-to-ball ratio of 0.005-0.500 to obtain tussah pupae powder; (2) Add water to the tussah pupa powder, mechanically stir (1000-1500 r / min, 40-50°C), and radio frequency treat (100-1100 W, treatment time within 2 h); then perform Soxhlet defatting; the obtained filter residue is vacuum freeze-dried and pulverized by planetary ball milling (100-500 r / min, 25°C) to obtain tussah pupa defatted powder; (3) Water was added to the defatted powder of tussah pupa, and the powder was treated with microfluidization (100-200 MPa, 2-10 cycles), radio frequency treatment (100-1000 W, treatment time within 10 min), microfluidization (100-200 MPa, 2-10 cycles), radio frequency treatment (100-1000 W, treatment time within 10 min) again to uniformly destroy the intermolecular forces in the system, and then mechanically stirred (1000-1500 r / min, 40-50 ℃), followed by centrifugation (5000-20000 r / min, 10-30 min), and the supernatant was collected; (4) Add ammonium sulfate or sodium sulfate to the supernatant, centrifuge (5000-20000 r / min, 10-30 min), and dialyze the precipitate to obtain the tussah pupa protein; (5) Finally, vacuum freeze-dry and store for later use.

[0030] The method for preparing the tussah pupa protein-based 3D / 4D printing slurry comprises the following steps: (1) dissolving tussah pupa protein in water to obtain tussah pupa protein solution; (2) Adding annelid / arthropod protein to the tussah pupa protein solution obtained in step (1) and then homogenizing (8000-20000 r / min, 1-3 min); adding fungal polysaccharide and mechanically stirring and mixing (800-1500 r / min, 10-30 min) to construct a rheologically stable tussah pupa protein system; (3) adding globular protein to the rheologically stable tussah pupa protein system obtained in step (2) and mechanically stirring and mixing uniformly (800-1500 r / min, 10-30 min) to obtain a structure-enhanced tussah pupa protein-based food slurry; (4) Adding a nutritious natural colorant to the structure-enhanced tussah pupa protein-based food slurry obtained in step (3) and mechanically stirring and mixing the mixture evenly (800-1500 r / min, 10-30 min) to obtain the tussah pupa protein-based 3D / 4D printing slurry.

[0031] A method for preparing 3D / 4D printed food based on tussah pupa protein comprises the following steps: using the 3D / 4D printing slurry based on tussah protein to print food through a 3D / 4D printing device, the main steps including: (1) Select a specific tussah pupa protein-based food slurry, load it into the material barrel, and select a suitable extrusion unit (screw type, plunger type or pneumatic type) for feeding and a suitable nozzle (square, round, diamond or flower shape) for extrusion according to the different properties of the slurry.

[0032] (2) In the digital display controller, further control the printing parameters and determine the model. Start to 3D print tussah pupa protein-based food.

[0033] (3) If the pH control system or blue light irradiation equipment is turned on during the printing process, 4D printing of tussah silkworm pupa protein-based food can be achieved, and its color can have the characteristics of evolving over time. The pH range is 3-10; the blue light irradiation time is within 1 h.

[0034] Example 1 (1) The tussah pupae were cleaned, dried, peeled, degummed, and cleaned again, and then vacuum-freeze-dried (24 h). They were then pulverized by a planetary ball mill (500 r / min, 25°C, material-to-ball ratio 0.08) to obtain tussah pupae powder ( Figure 1 ); (2) Water was added to the tussah pupa powder, and the mixture was mechanically stirred (1500 r / min, 45°C) and subjected to radio frequency treatment (1000 W, 3 min). The mixture was then Soxhlet defatted. The resulting filter residue was freeze-dried in a vacuum and pulverized by a planetary ball mill (100-500 r / min, 25°C) to obtain defatted tussah pupa powder. (3) Water was added to the defatted powder of tussah pupa, and the mixture was treated with microfluidization (200 MPa, 3 cycles), radio frequency treatment (power 1000 W, 3 min), microfluidization again (200 MPa, 3 cycles), and radio frequency treatment (power 1000 W, 3 min) to uniformly destroy the intermolecular forces in the system. The mixture was then mechanically stirred (1500 r / min, 40-50°C), and then centrifuged (15000 r / min, 25 min), and the supernatant was collected. (4) Add ammonium sulfate to the supernatant and centrifuge (15,000 r / min, 25 min). After obtaining the precipitate, dialyze to obtain the tussah pupa protein. (5) Finally, vacuum freeze-dry and store for later use.

[0035] A method for preparing tussah pupa protein-based 3D printing slurry, comprising the following steps: placing the tussah pupa protein prepared by the above method in water at 25 ℃ The mixture was dissolved under stirring to obtain an tussah pupa protein solution; then rice locust protein was added for homogenization (8000 r / min, 3 min), followed by adding boletus polysaccharide for mechanical stirring and mixing (1500 r / min, 15 min), and boletus polysaccharide was used to modify tussah pupa protein, and a rheologically stable tussah pupa protein system was constructed based on its "soft metastable effect"; finally, red bean globular protein was added and mixed evenly (1500 r / min, 15 min), and the "heterogeneous symbiotic effect" of red bean globular protein was used to regulate the system structure to obtain a structurally enhanced tussah pupa protein-based 3D printable food slurry. According to the mass percentage, the tussah pupa protein is 20%, the rice locust protein is 10%, the boletus polysaccharide is 10%, the red bean globular protein is 0.1%, the nutritional natural pigment is 0, and the balance is water. The tussah pupa protein-based food slurry can be used to prepare innovative food by 3D printing at 25°C. Based on its excellent rheological properties (such as Figure 2As shown, rice locust protein can improve the network system of tussah pupa protein solution by promoting the formation of molecular entanglement, and boletus polysaccharide can construct a rheologically stable tussah pupa protein system through the "soft metastable effect", reducing the loss factor of the food slurry and enhancing its elasticity and mechanical strength; red bean globular protein can further enhance the rheological structure of the tussah pupa protein system through the "heterogeneous symbiotic effect", producing complementary performance and synergistic properties, and improve its rheological 3ITT thixotropic recovery rate). The 3D printed food has a special texture, rich nutrition, strong stability, and high shape retention rate ( Figure 2 ).

[0036] Example 2 The tussah pupa protein used in this example was prepared in the same manner as in Example 1.

[0037] A method for preparing a tussah pupa protein-based 4D printing slurry comprises the following steps: dissolving tussah pupa protein in water at 55°C to obtain a tussah pupa protein solution; subsequently adding earthworm protein for homogenization (15,000 r / min, 1 min), adding black truffle polysaccharide and mixing evenly (1,000 r / min, 30 min), modifying the tussah pupa protein with the black truffle polysaccharide, and constructing a rheologically stable tussah pupa protein system based on its "compliant metastable effect"; finally, adding mung bean globular protein and mixing evenly (1,000 r / min, 30 min), regulating the system structure by utilizing the "heterogeneous symbiotic effect" of the mung bean globular protein to obtain a structurally enhanced tussah pupa protein slurry; and adding radish red pigment and mixing evenly for coloring (1,000 r / min, 10 min) to obtain a tussah pupa protein-based 4D printing slurry. Calculated by mass percentage, the ingredients include 5% tussah pupa protein, 5% earthworm protein, 5% black truffle polysaccharide, 2% mung bean globular protein, and 0.5% radish red pigment, with the balance being water. The tussah pupa protein-based food slurry can be used to prepare innovative foods using a 4D printing device at 25°C. The printed food containing 0.5% radish red pigment exhibits a high color reaction efficiency within 30 minutes under blue light stimulation ( Figure 3 ).

[0038] Example 3 The tussah pupa protein used in this example was prepared in the same manner as in Example 1.

[0039] A method for preparing a tussah pupa protein-based 4D printing slurry comprises the following steps: dissolving tussah pupa protein in water at 25°C to obtain a tussah pupa protein solution; subsequently adding wasp protein for homogenization (20,000 r / min, 2 min), adding Volvariella volvacea polysaccharide and mixing evenly (800 r / min, 45 min), modifying the tussah pupa protein with Volvariella volvacea polysaccharide (800 r / min, 45 min), and constructing a rheologically stable tussah pupa protein system based on its "compliant metastable effect"; finally, adding buckwheat globular protein and mixing evenly (800 r / min, 45 min), utilizing the "heterogeneous symbiotic effect" of the buckwheat globular protein to regulate and enhance the system structure, and adding cochineal red pigment and mixing evenly for coloring (800 r / min, 15 min) to obtain a tussah pupa protein-based 4D printing slurry. According to the percentage by mass, the tussah protein 20%, wasp protein 10%, straw mushroom polysaccharide 0.1%, buckwheat globular protein 10%, cochineal red pigment 5%, and the balance is water. At 25 ° C, the tussah protein-based food slurry can be 3D printed into shapes such as boats and gourds ( Figure 4 ); Innovative heart-shaped foods can also be prepared through 4D printing devices ( Figure 4 ), under the stimulation of the pH system, after 10 minutes, the food has a specific and obvious color change, which is more conducive to the innovative production of personalized and precise nutritional food.

[0040] Comparative Example 1 The traditional commercial tussah pupa protein was placed in water at 25 ℃ The mixture was dissolved at 1000 rpm to obtain a traditional commercial tussah pupa protein solution; then, rice locust protein was added for homogenization (8000 r / min, 3 min), followed by the addition of porcini polysaccharide and mechanical stirring for uniform mixing (1500 r / min, 15 min). The traditional commercial tussah pupa protein was modified with porcini polysaccharide to construct a traditional commercial tussah pupa protein system; finally, red bean globular protein was added and mixed uniformly (1500 r / min, 15 min) to obtain a traditional commercial tussah pupa protein-based 3D printable food slurry. According to the mass percentage, the traditional commercial tussah pupa protein was 20%, rice locust protein (10%), porcini polysaccharide 10%, red bean globular protein 0.1%, nutritious natural pigment 0, and the balance was water. The traditional commercial tussah pupa protein-based food slurry can be used to prepare innovative food by 3D printing at 25°C. The slurry had a loss factor of 0.6, a 3ITT thixotropic recovery rate of 85%, and a 3D shape retention rate of the printed product of 78%, which was comparable to the final slurry of Example 1. Figure 2 The results showed that the loss factor was high, the elasticity and mechanical strength were low; the 3ITT thixotropic recovery rate was low; the 3D printed food had low stability and low shape retention rate.

[0041] This indicates that the tussah pupa protein extracted by the method for extracting tussah pupa protein of the present invention has higher applicability.

[0042] Comparative Example 2 Soy protein isolate, silkworm pupa protein, or gelatin were dissolved in water at 55°C to obtain soy protein isolate, silkworm pupa protein, or gelatin solutions, respectively. Earthworm protein was then added to each protein solution and homogenized (15,000 r / min, 1 min). Black truffle polysaccharide was then added and mixed uniformly (1,000 r / min, 30 min). Earthworm protein was modified with black truffle polysaccharide to construct soy protein isolate, silkworm pupa protein, or gelatin systems. Finally, mung bean globular protein was added and mixed uniformly (1,000 r / min, 30 min). Radish red pigment was then added and mixed uniformly for coloring (1,000 r / min, 10 min). 4D printing slurries based on soy protein isolate, silkworm pupa protein, or gelatin were obtained, respectively. By mass percentage, the soy protein isolate, silkworm pupa protein, or gelatin solution comprised 5% soy protein isolate, 5% earthworm protein, 5% black truffle polysaccharide, 2% mung bean globular protein, and 0.5% radish red pigment, with the remainder being water.

[0043] Innovative foods can be prepared using a 4D printing device at 25°C using soy protein isolate, silkworm pupa protein, or gelatin protein-based food slurries. The 30-min color reaction efficiencies are 62%, 70%, and 65%, respectively. Compared with Example 2, the 30-min color reaction efficiencies of these protein slurry systems are all lower.

[0044] Comparative Example 3 The difference between this comparative example and Example 3 is that traditional commercial tussah pupa protein is used to replace the tussah pupa protein used in Example 3.

[0045] At 25°C, the slurry prepared in this comparative example was used to print products such as Figure 5 As shown in A; the product prepared by the slurry prepared in this comparative example through the 4D printing device is as follows after the pH system is stimulated Figure 5 As shown in B. Figure 4 By comparison, also through 3D printing, the boat and gourd printed in Example 3 are complete in shape and stable, while the heart shape printed in Comparative Example 3 is poorly formed, unstable, and easily collapsed. Similarly, through 4D printing, Example 3 has good color changes and uniform color distribution under different pH stimuli. Although Comparative Example 3 also has color changes under different pH stimuli, the 4D printed product has a weak structure and the pigment is not tightly bound to the matrix in the slurry. Under different pH stimuli, the color distribution of the 4D printed product is uneven. When the pH is 10, the sample suffers from severe floating color, indicating that the slurry of Comparative Example 3 has poor stability after 4D printing.

[0046] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent replacements and improvements made by any technician familiar with this technical field within the technical scope disclosed by the present invention should be included in the scope of protection of the invention.

Claims

1. A tussah pupa protein-based 3D / 4D printing slurry, characterized by: Calculated by mass percentage, it includes 5%~20% tussah pupa protein, 5%~10% segment / arthropod protein, 0.1%~10% fungal polysaccharide, 0.1%~10% globular protein, 0-5% nutritional natural colorant, and the balance is water.

2. The tussah pupa protein-based 3D / 4D printing slurry according to claim 1, characterized in that: The method for extracting tussah pupa protein comprises the following steps: A1. Peeling, deveining, cleaning, drying, and then crushing tussah pupae to obtain tussah pupae powder; A2. adding water to the tussah pupa powder, stirring, and radio frequency treatment; then performing Soxhlet defatting; drying and crushing the obtained filter residue to obtain tussah pupa defatted powder; A3. Add water to the defatted powder of tussah pupa, and sequentially subject the powder to a first microfluidization treatment, a first radiofrequency treatment, a second microfluidization treatment, and a second radiofrequency treatment. Stir and centrifuge the mixture, and collect the supernatant. A4. Add a protein precipitant to the supernatant, centrifuge, dialyze the precipitate, and dry the product to obtain tussah pupa protein.

3. The tussah pupa protein-based 3D / 4D printing slurry according to claim 2, characterized in that: In step A2, the power of the RF treatment is 100-1100 W, and the treatment time is within 2 h. In step A3, the pressure of the first and second microjet treatments is 100-200 MPa, and the cycle is 2-10 times. The power of the first and second RF treatments is 100-1000 W, and the treatment time is within 10 min.

4. The tussah pupa protein-based 3D / 4D printing slurry according to claim 1, characterized in that: The annelid / arthropod protein includes annelid or arthropod protein prepared using at least one of earthworms, wasps, bees, cicadas, grasshoppers, rice locusts, Polyrhachis tinctorius, Polyrhachis rubripes, Chikatana ants, and weaver ants as raw materials, and the average molecular weight of the tussah pupa protein and the annelid / arthropod protein is 1000~300000 Da.

5. The tussah pupa protein-based 3D / 4D printing slurry according to claim 1, characterized in that: The fungal polysaccharide is at least one of black truffle polysaccharide, tricholoma polysaccharide, Volvariella volvacea polysaccharide, Gallinarum polysaccharide, Boletus polysaccharide and Chanterelle polysaccharide.

6. The tussah pupa protein-based 3D / 4D printing slurry according to claim 1, characterized in that: The globular protein includes at least one of red bean globular protein, mung bean globular protein, buckwheat globular protein, oat globular protein, walnut globular protein, quinoa globular protein, and perilla seed globular protein.

7. The tussah pupa protein-based 3D / 4D printing slurry according to claim 1, characterized in that: The nutritional natural colorant includes at least one of phycocyanin, cochineal red pigment, monascus red pigment, purple sweet potato red pigment and radish red pigment.

8. A method for preparing a tussah pupa protein-based 3D / 4D printing slurry according to any one of claims 1 to 7, characterized in that: The following steps are involved: B1, dissolving tussah pupa protein in water to obtain tussah pupa protein solution; B2. Add annelid / arthropod protein to the tussah pupa protein solution obtained in step B1, and then homogenize; Add fungal polysaccharide and mix evenly to construct a rheologically stable tussah pupa protein system; B3, adding globular protein to the rheologically stable tussah pupa protein system obtained in step B2 and mixing uniformly to obtain a structure-enhanced tussah pupa protein-based food slurry; B4. Add a nutritional natural colorant to the structure-enhanced tussah pupa protein-based food slurry obtained in step B3 and mix evenly to obtain the tussah pupa protein-based 3D / 4D printing slurry.

9. The method for preparing the tussah pupa protein-based 3D / 4D printing slurry according to claim 8, characterized in that: In steps B1-B4, the operating temperature is 25-55°C.

10. An application of the tussah pupa protein-based 3D / 4D printing slurry according to any one of claims 1 to 7, characterized in that: By using the tussah pupa protein-based 3D / 4D printing slurry to print food through a 3D / 4D printing device, personalized tussah pupa protein-based food can be 3D printed during the printing process; 4D printing of tussah pupa protein-based food can also be achieved through pH control or blue light irradiation control.