Preparation Method and Application of a Composite Surimi 3D Printing Ink

Abstract

The present invention discloses a preparation method and application of a composite surimi 3D printing ink. The present invention provides a composite surimi 3D printing ink composed of surimi, antifreeze peptides and food gum. The composition and preparation method of the composite surimi 3D printing ink are simple. After being formed by 3D printing and repeatedly frozen and thawed, the product is not easy to collapse and has good stability, overcoming the deficiencies of poor freeze-thaw stability of the surimi structure in existing 3D printing and poor rheological properties of the surimi ink containing antifreeze peptides and being not easy to be formed by 3D printing. It can be used to prepare 3D printed frozen products. The present invention not only enriches the sources of materials that can be used as 3D food printing materials, but also can open up a new path for the processing of traditional surimi products and promote the development of the surimi processing industry.

Description

Technical Field

[0001] The present invention belongs to the technical field of 3D printing. More specifically, it relates to a preparation method and application of a composite surimi 3D printing ink. Background Art

[0002] 3D printing technology, also known as additive manufacturing, is a rapid prototyping technology that uses computer-aided design to convert a virtual digital model into a three-dimensional entity. Since 3D printing technology can meet the highly specialized requirements of model design and rapid prototyping, a large number of applied researches have been carried out in the fields of biomedicine, construction manufacturing, aerospace, etc. At the same time, as a rapidly developing new technology, due to its advantages such as customization, personalized nutrition, easy swallowing, utilization of plant-based "meat" and real meat, reduction of food waste, unconventional food consumption, and space travel, it has also been widely applied in the food field.

[0003] Currently, meat-based inks have become one of the most prominent research hotspots in 3D printing because they can replace traditional kitchen processing methods and have practical application value in the 3D printing of fish, chicken, beef, cultured meat, etc. 3D printed meat is rich in protein and moisture, and it is prone to deterioration due to microbial growth at room temperature. With the maturity of 3D printing technology based on meat-based inks, the storage problem of 3D printed meat products is becoming a bottleneck for emerging hotspots (prepared foods).

[0004] Freezing storage technology has been widely used because it can inhibit the reproduction of microorganisms. However, during the storage and transportation of 3D printed meat, freeze-thaw (F-T) cycles are inevitable, which will cause serious frostbite and juice loss in 3D products, reduce the shape retention ability of 3D products, and greatly limit the development of 3D printing technology. Because 3D printing, as a new type of personalized customization technology, having a high-quality structure is one of its highlights. Therefore, preventing and solving the reduction of shape retention in 3D printed meat products during frozen storage is an urgent task.

[0005] Silver carp is a freshwater fish widely distributed in the world. It has a delicious taste and high nutritional value, and is deeply loved by consumers. Products made from silver carp have also been recognized by consumers for their flavor and nutrition. Obviously, silver carp as a raw material for 3D printing has great commercial prospects. Antifreeze peptides (AFPs) can inhibit the growth of ice crystals by controlling the arrangement of water molecules through hydrogen bonds, showing good antifreeze effects of inhibiting ice crystal growth and recrystallization. Now it has become an effective antifreeze agent for frozen foods and is used in frozen vegetables, frozen meats, ice cream, etc. In our previous research, AFPs that can protect surimi from freezing damage were screened from food-derived proteins by enzymatic hydrolysis. Adding AFPs to surimi may be a better strategy to solve the problem that 3D-printed surimi products are not conducive to frozen storage. However, through our experiments, it was found that the rheological properties of surimi ink added with antifreeze peptides were significantly reduced, which could not meet the requirements of 3D printing, and the formed shape of the printed structure was poor and easy to collapse. Therefore, it is necessary to explore and prepare a composite surimi 3D printing ink suitable for 3D printing and with high shape retention after the products are stored frozen to promote the development of the surimi processing industry. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects and deficiencies of the above-mentioned prior art and provide a preparation method and application of a composite surimi 3D printing ink.

[0007] The first object of the present invention is to provide a composite surimi 3D printing ink suitable for 3D printing.

[0008] The second object of the present invention is to provide a preparation method of the composite surimi 3D printing ink.

[0009] The third object of the present invention is to provide an application of the composite surimi 3D printing ink in the preparation of frozen storage products requiring 3D printing.

[0010] The above objects of the present invention are achieved by the following technical solutions:

[0011] The present invention provides a composite surimi 3D printing ink suitable for 3D printing, which is composed of 92.0 - 99.5 parts by weight of surimi, 0.1 - 5.0 parts by weight of antifreeze peptide, and 0.5 - 3.0 parts by weight of food gum.

[0012] Preferably, the composite surimi 3D printing ink suitable for 3D printing is composed of 93.0 - 96.0 parts by weight of surimi, 1.0 - 4.0 parts by weight of antifreeze peptide, and 0.5 - 2.5 parts by weight of food gum.

[0013] Further preferably, the composite surimi 3D printing ink applicable to 3D printing is composed of 95.0 parts by weight of surimi, 3.0 parts by weight of antifreeze peptide, and 2.0 parts by weight of food gum.

[0014] Specifically, the surimi is silver carp surimi, the antifreeze peptide is an antifreeze peptide extracted from silver carp scales, and the food gum is selected from one or more of xanthan gum, carrageenan, locust bean gum, and konjac gum.

[0015] The preparation method of the surimi is as follows: Remove the internal organs, skin, and bones of fresh silver carp, wash with pre-cooled water, and grind with a colloid mill (equipped with a -4 °C cooling circulation device) at -4 °C for 10 - 30 min; its water content is 80 - 92.5 wt%.

[0016] The preparation method of the antifreeze peptide is as follows: Add deionized water to silver carp scales and ultrasonicate for 80 - 100 min, then perform high-temperature and high-pressure treatment for 20 - 40 min. After cooling, adjust the pH to 7.8 - 8.2, add trypsin and enzymatically hydrolyze for 3 - 4 h. After inactivating the enzyme, centrifuge and take the supernatant, and freeze-dry to obtain the antifreeze peptide.

[0017] More specifically, extract 260 - 300 g of deionized water per 15 g of silver carp scales by ultrasonic extraction. The high-temperature and high-pressure conditions are 120 - 122 °C, 0.11 - 0.13 MPa. The enzymatic hydrolysis temperature is 36 - 38 °C. After inactivating the enzyme for 10 - 15 min, freeze-centrifuge and take the supernatant, and freeze-dry the supernatant to obtain the antifreeze peptide.

[0018] Specifically, the food gum is selected from one or more of xanthan gum, carrageenan, locust bean gum, and konjac gum.

[0019] Preferably, the food gum is selected from one or two of carrageenan, xanthan gum, locust bean gum, and konjac gum.

[0020] Further preferably, the food gum is a combination of carrageenan and xanthan gum, locust bean gum and xanthan gum, konjac gum and xanthan gum, locust bean gum and carrageenan, or konjac gum and carrageenan.

[0021] Further preferably, the food gum is a combination of carrageenan and xanthan gum, locust bean gum and xanthan gum, konjac gum and xanthan gum.

[0022] Further preferably, the food gum is carrageenan and xanthan gum.

[0023] Specifically, when the food gum is a compound of two colloids, the mass ratio of the compounded colloids is 3:1 - 1:3.

[0024] Preferably, when the food gum is carrageenan and xanthan gum, the mass ratio of carrageenan to xanthan gum is 2:1 to 1:1.5; when the food gum is locust bean gum and xanthan gum, the mass ratio of locust bean gum to xanthan gum is 2:1 to 1:2; when the food gum is konjac gum and xanthan gum, the mass ratio of konjac gum to xanthan gum is 1:1 to 1:1.5.

[0025] More preferably, when the food gum is carrageenan and xanthan gum, the mass ratio of carrageenan to xanthan gum is 1:1; when the food gum is locust bean gum and xanthan gum, the mass ratio of locust bean gum to xanthan gum is 1.2:1; when the food gum is konjac gum and xanthan gum, the mass ratio of konjac gum to xanthan gum is 1:1.4.

[0026] The present invention also provides a method for preparing the composite surimi 3D printing ink, comprising the following steps:

[0027] S1. Preparation of silver carp surimi: The fresh silver carp is gutted, skinned and boned, then washed with pre-cooled water, and ground with a colloid mill at -4 °C for 10 - 30 min; its water content is 80 - 92.5 wt%.

[0028] S2. Preparation of antifreeze peptide: Add deionized water to silver carp scales and ultrasonicate for 80 - 100 min, then perform high-temperature and high-pressure treatment for 20 - 40 min. After cooling, adjust the pH to 7.8 - 8.2, add trypsin and enzymolyze for 3 - 4 h. After inactivating the enzyme, centrifuge and take the supernatant, and then freeze-dry to obtain the antifreeze peptide.

[0029] S3. Preparation of composite surimi 3D printing ink: Add the antifreeze peptide prepared in step S2 to the surimi obtained in step S1 and disperse it at a stirring speed of 2500 - 3500 r / min in a cold water bath. Add the food gum and stir for 3 min, then place it in a vacuum drying oven and incubate at 25 °C and -0.08 MPa for 30 min to remove the bubbles generated by stirring.

[0030] Specifically, in step S2, every 15 g of silver carp scales are added with 260 - 300 g of deionized water for ultrasonic extraction. The high-temperature and high-pressure conditions are 120 - 122 °C and 0.11 - 0.13 MPa. The enzymolysis temperature is 36 - 38 °C. After inactivating the enzyme for 10 - 15 min, freeze-centrifuge and take the supernatant, and then freeze-dry the supernatant to obtain the antifreeze peptide.

[0031] In view of the fact that the structure printed by the composite surimi 3D printing ink applicable to 3D printing according to the present invention has the characteristic of high shape retention after repeated freeze-thaw cycles, the present invention also claims the application of the composite surimi 3D printing ink in the preparation of frozen storage products that need to be 3D printed.

[0032] Specifically, the storage temperature of the frozen storage product is -25 to -15 °C.

[0033] Specifically, the storage time of the frozen storage product is 1 to 180 days, and the number of freeze-thaw cycles does not exceed 6 times.

[0034] The present invention also provides a method for preparing a 3D printed product using the composite surimi 3D printing ink, comprising the following steps:

[0035] S1. Prepare the composite surimi 3D printing ink;

[0036] S2. Build a model: Build a model through 3D Max, and then output an STL file; the STL file is recognized and sliced (layer thickness 1.2 mm) by Repetier-Host software, and a G code is output; a 3D printer using syringe extrusion is used to print the model;

[0037] S3. 3D print surimi products: Cure step S2 and perform printing; the rated extrusion pressure, nozzle length, diameter, filling density, and printing speed parameters for 3D printing are 71 N, 3.0 cm, 1.2 mm, 100%, and 30.0 mm / s, respectively.

[0038] The present invention has the following beneficial effects:

[0039] The present invention discloses a method for preparing a composite surimi 3D printing ink and its application. The present invention provides a composite surimi 3D printing ink composed of surimi, antifreeze peptides, and food gums. The composition and preparation method of the composite surimi 3D printing ink are simple. After 3D printing and repeated freeze-thawing, the product is not easy to collapse and has good stability, overcoming the deficiencies of poor freeze-thaw stability of the surimi structure in existing 3D printing, poor rheological properties of surimi ink containing antifreeze peptides, and difficulty in 3D printing and forming. It can be used to prepare 3D printed frozen products. The present invention not only enriches the sources of materials that can be used as 3D food printing materials, but also can open up a new path for the processing of traditional surimi products and promote the development of the surimi processing industry. Description of the Drawings

[0040] Figure 1 Isolation columns built by 3D Max for printing.

[0041] Figure 2 For the rheological properties of surimi ink (in the figure, SI represents surimi ink, A is the result of amplitude scanning, B and C are the results of shear thinning tests, and D is the result of frequency scanning).

[0042] Figure 3 3D structure directly printed from surimi ink.

[0043] Figure 4Texture test results of the 3D structure directly printed with surimi ink (SI in the figure represents surimi ink).

[0044] Figure 5 Picture of the 3D structure directly printed with surimi ink after 4 freeze-thaw cycles. The circle markings in the figure indicate obvious juice loss on the surface of the 3D structure, and the line markings in the figure indicate significant collapse of the 3D structure.

[0045] Figure 6 Rheological properties of antifreeze peptide-based surimi ink (ASI in the figure represents antifreeze peptide-based surimi ink, A is the result of amplitude sweep, B and C are the results of shear thinning test, and D is the result of frequency sweep).

[0046] Figure 7 3D structure directly printed with antifreeze peptide-based surimi ink.

[0047] Figure 8 Texture test results of the 3D structure directly printed with antifreeze peptide-based surimi ink (ASI in the figure represents antifreeze peptide-based surimi ink).

[0048] Figure 9 Picture of the 3D structure directly printed with antifreeze peptide-based surimi ink after 4 freeze-thaw cycles.

[0049] Figure 10 Mechanism analysis results of surimi ink and antifreeze peptide-based surimi ink (SI in the figure represents surimi ink, ASI represents antifreeze peptide-based surimi ink, A is the circular dichroism spectrum analysis result of surimi ink and antifreeze peptide-based surimi ink; B is the secondary structure content of surimi and antifreeze peptide-based surimi ink after four F-T calculated from the CD spectrum; C is the intermolecular force test result of surimi ink and antifreeze peptide-based surimi ink after 4 F-T; D is the Low-NMR signal result of surimi ink).

[0050] Figure 11 3D structures directly printed with the composite surimi 3D printing inks prepared in Examples 1-7 respectively (ASI in the figure represents antifreeze peptide-based surimi ink, X represents xanthan gum, C represents carrageenan, L represents locust bean gum, K represents konjac gum, C+X represents carrageenan + xanthan gum, L+X represents locust bean gum + xanthan gum, K+X represents konjac gum + xanthan gum).

[0051] Figure 12 Texture test and water holding rate test results of the 3D structures directly printed with the composite surimi 3D printing inks prepared in Examples 1-7 respectively (ASI in the figure represents antifreeze peptide-based surimi ink, X represents xanthan gum, C represents carrageenan, L represents locust bean gum, K represents konjac gum, C+X represents carrageenan + xanthan gum, L+X represents locust bean gum + xanthan gum, K+X represents konjac gum + xanthan gum). Detailed implementation manners

[0052] The present invention will be further described below in conjunction with the accompanying drawings of the specification and specific embodiments, but the embodiments do not impose any form of limitation on the present invention. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.

[0053] Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0054] Comparative Example 1 3D printing of surimi ink

[0055] This comparative example explored the printing performance of surimi ink. The preparation method of the surimi ink was as follows: the fresh silver carp was gutted, skinned, and deboned, then washed with pre-cooled water, and ground with a colloid mill at -4 °C for 30 min; the water content was 80 wt%.

[0056] Use 3D Max to construct the isolation column for printing. The shape of the isolation column is as Figure 1 shown, with a side length of 20 mm, a height of 40 mm, and an inner diameter of 10 mm. After slicing (layer thickness 1.2 mm) with Repetier-Host software, the G code was output. The parameters of the 3D printer: the rated extrusion pressure, nozzle length, diameter, filling density, and printing speed parameters were 71 N, 3.0 cm, 1.2 mm, 100%, and 30.0 mm / s respectively. After the ground surimi ink was degassed in a vacuum drying oven (25 °C, -0.08 MPa), it was loaded into the material tube for printing.

[0057] The rheological properties of the surimi ink are as Figure 2 shown. From the amplitude sweep ( Figure 2 A in it), it can be seen that the yield stress of the surimi ink is 387.26 Pa. According to the formula P rated = (F rated / S) = (4L / D) τ yield calculation shows that it is less than the rated extrusion force of the printer, 451.27 Pa (P rated , F rated , S, L, D, τ yield represent the rated pressure, rated thrust, thrust surface area, nozzle length, nozzle diameter, and ink yield stress of the ink respectively), indicating that the surimi ink can be smoothly extruded. At the same time, through the shear thinning test ( Figure 2 B and C in it), it can be seen that as the shear force increases, the viscosity of the surimi ink decreases, and the shear force increases, indicating that the surimi ink is a shear-thinning pseudoplastic fluid, which is very important for 3D printing. Through the frequency sweep ( Figure 2As can be seen from Figure D), the yield stress G' of surimi ink is greater than G", indicating that surimi ink is similar to a solid and can meet the support requirements.

[0058] The 3D structure directly printed with surimi ink is as Figure 3 shown. It can be seen from Figure 3 that the 3D structure directly printed with surimi ink has poor shape retention, indicating that the mechanical strength provided by the surimi ink itself is insufficient to support a higher structure. The texture test results of the 3D structure directly printed with surimi ink are as Figure 4 shown. Through texture testing, it was found that the fracture strength of the 3D printed structure is 56.3 g. Figure 5 This is a picture of the 3D structure directly printed with surimi ink after 4 freeze-thaw cycles. There is an obvious phenomenon of juice loss on the surface of the 3D structure (marked with a circle in the figure, and its water holding rate is 77.21%), and at the same time, the 3D structure shows significant collapse (marked with a line in the figure). The above results indicate that surimi ink is not suitable for 3D printing, and the printed structure cannot be applied to frozen storage.

[0059] Comparative Example 2 3D Printing of Antifreeze Peptide-Based Surimi Ink

[0060] This comparative example explored the printing performance of antifreeze peptide-based surimi ink. The preparation method of the antifreeze peptide-based surimi ink is as follows:

[0061] (1) Preparation of surimi: Fresh silver carp fish is gutted, skinned, and deboned, then washed with pre-cooled water and ground in a colloid mill at -4 °C for 30 min; the water content is 80 wt%.

[0062] (2) Preparation of antifreeze peptide: 15 g of silver carp fish scales are added to 300 g of deionized water and extracted by ultrasonic wave for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged at low temperature for 10 min, and the supernatant is freeze-dried to obtain antifreeze peptide;

[0063] (3) In a cold water bath, antifreeze peptide with a weight fraction of 3 is added to surimi with a weight fraction of 97 and dispersed at a stirring speed of 3000 r / min to prepare antifreeze peptide-based surimi ink.

[0064] Similarly, the printing performance was evaluated using the isolation column constructed in Comparative Example 1.

[0065] The rheological properties of the antifreeze peptide-based surimi ink are as Figure 6 shown. As can be seen from the amplitude sweep ( Figure 6 in Figure A), the yield stress of the surimi ink is 278.72 Pa, indicating that the surimi ink can be smoothly extruded. Comparing Figure 2As can be seen from A in the figure, after adding antifreeze peptides, the yield stress of surimi ink decreases. The yield stress can also reflect the mechanical strength of the material, indicating that adding antifreeze peptides reduces the mechanical strength of surimi ink. Through the shear thinning test ( Figure 6 in B and C in the figure), it can be seen that the antifreeze peptide-based surimi ink is a shear-thinning pseudoplastic fluid. Through frequency scanning ( Figure 6 in D in the figure), it can be known that the yield stress G' of surimi ink > G", indicating that surimi ink is similar to a solid and can meet the support. The 3D structure directly printed by the antifreeze peptide-based surimi ink is as shown in Figure 7 . Combining the results shown in Figure 7 , it can be seen that the 3D structure printed by the antifreeze peptide-based surimi ink has worse conformability than the 3D structure of surimi ink ( Figure 3 ), indicating that adding antifreeze peptides reduces the mechanical strength of surimi ink. The texture test results of the 3D structure directly printed by the antifreeze peptide-based surimi ink are as shown in Figure 8 . Through the texture test, it is found that the fracture strength of the 3D printed structure is 37.2 g, directly indicating that adding antifreeze peptides reduces the mechanical strength of surimi ink. The picture of the 3D structure directly printed by the antifreeze peptide-based surimi ink after 4 freeze-thaw cycles is as shown in Figure 9 . Even after 4 freeze-thaw cycles, the antifreeze peptide-based surimi ink can better maintain its original structure, indicating that antifreeze peptides have a good cryoprotective effect on surimi ink during the freeze-thaw cycle.

[0066] Furthermore, through circular dichroism (CD, Figure 10 in A in the figure), it is found that both surimi and the antifreeze peptide-based surimi ink are observed to have two negative bands at 222 and 208 nm respectively, which are typical CD spectra of myofibrillar proteins. Moreover, the CD spectrum of surimi is significantly stronger than that of the antifreeze peptide-based surimi ink, while the intensities of the two negative bands (222 and 208 nm) of surimi are significantly weaker than those of the antifreeze peptide-based surimi ink, indicating that after 4 freeze-thaw cycles, the secondary structure of myofibrillar proteins in surimi has changed significantly compared with that of the antifreeze peptide-based surimi ink. The secondary structure contents of surimi and the antifreeze peptide-based surimi ink after four F-T obtained by calculating the CD spectrum are as shown in Figure 10 in B in the figure; the α-helix and β-turn of surimi ink are significantly lower than those of the antifreeze peptide-based surimi ink ( p < 0.05), and the β-sheet is significantly higher than that of the antifreeze peptide-based surimi ink ( p < 0.05); hydrogen bonds are the stabilizing force of α-helices, and disulfide bonds are the main force of β-sheets; it is speculated that the α-helices of myofibrillar proteins in SI unfold after four F-T, exposing many hydrophobic groups and forming β-sheet structures. In order to confirm the above conjecture, the intermolecular force test of surimi and the antifreeze peptide-based surimi ink after 4 F-T was carried out ( Figure 10 in C in the figure), and the results show that the hydrogen bond content of surimi ink is lower than that of the antifreeze peptide-based surimi ink ( p<0.05), the hydrophobic interaction and disulfide bond content of surimi ink were higher than those of antifreeze peptide-based surimi ink ( p <0.05), and the results supported Figure 10 Conjecture B in. The above results confirmed that AFPs could prevent the secondary structure changes of surimi during the freeze-thaw process. Hydrogen bonds and hydrophobic groups are the groups that attract and repel water in proteins, respectively. Therefore, the presence of a small number of hydrogen bonds and a large number of hydrophobic groups would reduce the ability of surimi to bind free water. The Low-NMR signal ( Figure 10 in D) results could reflect the relaxation time (T2) of the water state and distribution in surimi ink. Obviously, after four freeze-thaw cycles, the relaxation time (T2) of surimi ink shifted significantly to the right compared with that of antifreeze peptide-based surimi ink, indicating that the mobility of free water in surimi ink was stronger than that of antifreeze peptide-based surimi ink, which was consistent with Figure 10 the results in C. Further analysis found that the water holding rate of antifreeze peptide-based surimi ink was 86.68%.

[0067] In summary, antifreeze peptides are a potential solution to prevent frostbite in 3D printed meat products. Generally speaking, after four freeze-thaw cycles, the secondary structure of surimi ink changed. Due to the destruction of hydrogen bonds and the exposure of hydrophobic groups, its α-helix became β-sheet; the reduction of hydrogen bonds and the exposure of hydrophobic groups weakened the binding ability of proteins to water, causing the relaxation time T2 in the NMR signal to shift to the right, forming a large amount of free water, enhancing the fluidity of water, resulting in juice loss in the 3D structure and reducing the shape retention of the 3D structure. Antifreeze peptides can prevent juice loss in the 3D structure, but adding antifreeze peptides will reduce the mechanical strength of surimi ink, making it impossible for antifreeze peptide-based surimi ink to print 3D structures with high mechanical strength, which needs further improvement.

[0068] Example 1 Preparation of Composite Surimi 3D Printing Ink Suitable for 3D Printing

[0069] The present invention provides a composite surimi 3D printing ink suitable for 3D printing, which is composed of 95.0 parts by weight of silver carp surimi, 3.0 parts by weight of silver carp scale antifreeze peptide, and 2.0 parts by weight of xanthan gum.

[0070] Specifically, the preparation of the surimi ink includes the following steps:

[0071] S1. Preparation of silver carp surimi: After the fresh fish is eviscerated, skinned, and deboned, it is washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 100 min, with a water content of 80 wt%;

[0072] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and ultrasonically extracted for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymatic hydrolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged at low temperature for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide;

[0073] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, the antifreeze peptide AFPs are added to the surimi at a stirring speed of 3000 r / min for dispersion, then xanthan gum is added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0074] Example 2 Preparation of composite surimi 3D printing ink suitable for 3D printing

[0075] The present invention provides a surimi ink suitable for 3D printing, which is composed of 94.0 parts by weight of silver carp surimi, 3.0 parts by weight of antifreeze peptide from silver carp scales, and 3.0 parts by weight of carrageenan.

[0076] Specifically, the preparation of the surimi ink includes the following steps:

[0077] S1. Preparation of silver carp surimi: Fresh fish are gutted, skinned, boned, and then washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 150 min, with a water content of 80 wt%;

[0078] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and ultrasonically extracted for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymatic hydrolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged at low temperature for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide;

[0079] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, the antifreeze peptide AFPs are added to the surimi at a stirring speed of 3000 r / min for dispersion, then carrageenan is added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0080] Example 3 Preparation of composite surimi 3D printing ink suitable for 3D printing

[0081] The present invention provides a surimi ink suitable for 3D printing, which is composed of 96.0 parts by weight of silver carp surimi, 3.5 parts by weight of silver carp scale antifreeze peptide, and 0.5 parts by weight of locust bean gum.

[0082] Specifically, the preparation of the surimi ink includes the following steps:

[0083] S1. Preparation of silver carp surimi: After the fresh fish is eviscerated, skinned, and boned, it is washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 25 min, with a water content of 80 wt%.

[0084] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and extracted by ultrasonic for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged at low temperature for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide.

[0085] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, the antifreeze peptide AFPs are added to the surimi and dispersed at a stirring speed of 3000 r / min, then locust bean gum is added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0086] Example 4 Preparation of composite surimi 3D printing ink suitable for 3D printing

[0087] The present invention provides a surimi ink suitable for 3D printing, which is composed of 96.0 parts by weight of silver carp surimi, 3.0 parts by weight of silver carp scale antifreeze peptide, and 1.0 parts by weight of konjac gum.

[0088] Specifically, the preparation of the surimi ink includes the following steps:

[0089] S1. Preparation of silver carp surimi: After the fresh fish is eviscerated, skinned, and boned, it is washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 20 min, with a water content of 80 wt%.

[0090] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and extracted by ultrasonic for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged at low temperature for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide.

[0091] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, antifreeze peptide AFPs were added to surimi at a stirring speed of 3000 r / min for dispersion, then konjac gum was added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0092] Example 5 Preparation of Composite Surimi 3D Printing Ink Suitable for 3D Printing

[0093] The present invention provides a surimi ink suitable for 3D printing, which is composed of silver carp surimi with a weight fraction of 95.0, antifreeze peptide from silver carp scales with a weight fraction of 3.0, and carrageenan + xanthan gum with a weight fraction of 2.0; the weight ratio of carrageenan to xanthan gum is 1:1.

[0094] Specifically, the preparation of the surimi ink includes the following steps:

[0095] S1. Preparation of silver carp surimi: Fresh fish was eviscerated, skinned, and boned, then washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 30 min, with a water content of 80 wt%.

[0096] S2. Preparation of antifreeze peptide: 15 g of silver carp scales were added with 300 g of deionized water and extracted by ultrasonic for 90 min, then treated at high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH was adjusted to 8.0, 0.57 g of trypsin was added, and enzymolysis was carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it was centrifuged at low temperature for 10 min, and the supernatant was freeze-dried to obtain the antifreeze peptide.

[0097] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, antifreeze peptide AFPs were added to surimi at a stirring speed of 3000 r / min for dispersion, then carrageenan + xanthan gum was added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0098] Example 6 Preparation of Composite Surimi 3D Printing Ink Suitable for 3D Printing

[0099] The present invention provides a surimi ink suitable for 3D printing, which is composed of silver carp surimi with a weight fraction of 95.5, antifreeze peptide from silver carp scales with a weight fraction of 3.5, and locust bean gum + xanthan gum with a weight fraction of 1.0; the weight ratio of locust bean gum to xanthan gum is 1:1.

[0100] Specifically, the preparation of the surimi ink includes the following steps:

[0101] S1. Preparation of silver carp surimi: Fresh fish is eviscerated, skinned, and boned, then washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 18 min, with a water content of 80 wt%.

[0102] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and extracted by ultrasonic wave for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymatic hydrolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged by freezing for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide.

[0103] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, the antifreeze peptide AFPs are added to the surimi and dispersed at a stirring speed of 3000 r / min, then locust bean gum + xanthan gum is added and stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0104] Example 7 Preparation of composite surimi 3D printing ink suitable for 3D printing

[0105] The present invention provides a surimi ink suitable for 3D printing, which is composed of 94.5 parts by weight of silver carp surimi, 3.5 parts by weight of antifreeze peptide from silver carp scales, and 2.0 parts by weight of konjac gum + xanthan gum; the weight ratio of konjac gum + xanthan gum is 1:1.3.

[0106] Specifically, the preparation of the surimi ink includes the following steps:

[0107] S1. Preparation of silver carp surimi: Fresh fish is eviscerated, skinned, and boned, then washed with pre-cooled water, and then ground with a colloid mill (equipped with a -4 °C cooling circulation device) for 26 min, with a water content of 80 wt%.

[0108] S2. Preparation of antifreeze peptide: 15 g of silver carp scales are added with 300 g of deionized water and extracted by ultrasonic wave for 90 min, then treated under high temperature and high pressure (121 °C, 0.12 MPa) for 30 min. After cooling, the pH is adjusted to 8.0, 0.57 g of trypsin is added, and enzymatic hydrolysis is carried out at 37 °C for 3.5 h. After inactivating the enzyme for 10 min, it is centrifuged by freezing for 10 min, and the supernatant is freeze-dried to obtain the antifreeze peptide.

[0109] S3. Preparation of composite surimi 3D printing ink: In a cold water bath, antifreeze peptide AFPs were added to surimi and dispersed at a stirring speed of 3000 r / min, then konjac gum + xanthan gum were stirred for 3 min, and then incubated in a vacuum drying oven (25 °C, -0.08 MPa) for 30 min to remove the bubbles generated by stirring.

[0110] Example 8 Application of composite surimi 3D printing ink in the preparation of frozen storage products requiring 3D printing

[0111] In this example, referring to the method described in Comparative Example 1, 3D printing was carried out using the composite surimi 3D printing inks prepared in Examples 1 to 7 respectively. The 3D structures directly printed using the composite surimi 3D printing inks prepared in Examples 1 to 7 are as Figure 11 shown. From Figure 11 it can be seen that the shape retention of the 3D structures printed using the composite surimi 3D printing inks prepared in Examples 1 to 7 is better than that of Comparative Examples 1 and 2, indicating that the mechanical strength of the composite surimi 3D printing inks prepared in Examples 1 to 7 is good and suitable for 3D printing. In this example, the texture and water holding rate of the 3D structures directly printed using the composite surimi 3D printing inks prepared in Examples 1 to 7 after 4 freeze-thaw cycles were also tested, and the results are as Figure 12 shown. The breaking strengths of ASI+C, ASI+X, ASI+L, ASI+K, ASI+C+X, ASI+L+X, ASI+K+X are 89.3 g, 55.2 g, 188.6 g, 52.3 g, 54.4 g, 89.4 g, 45.3 g respectively ( Figure 12 in A). The water holding rates of ASI+C, ASI+X, ASI+L, ASI+K, ASI+C+X, ASI+L+X, ASI+K+X are 91.99%, 97.78%, 98.89%, 90.23%, 98.01%, 99.37%, 95.5% respectively ( Figure 12 in B). From Figure 12 it can be seen that the texture and water holding rate of the 3D structures printed using the composite surimi 3D printing inks prepared in Examples 1 to 7 after 4 freeze-thaw cycles are better than those of the antifreeze peptide-based surimi ink described in Comparative Example 2.

[0112] The above results show that the composite surimi 3D printing ink described in the present invention is suitable for 3D printing, not only overcoming the deficiencies of the surimi ink containing antifreeze peptide with poor rheological properties and difficult 3D printing forming; at the same time, the frozen storage products formed by 3D printing using the composite surimi 3D printing ink are not easy to collapse after repeated freeze-thaw cycles and have good stability, and also overcome the deficiency of poor freeze-thaw stability of the existing 3D printed surimi structures, and can be used to prepare frozen storage products requiring 3D printing forming.

[0113] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. Application of a composite surimi 3D printing ink in the preparation of frozen storage products to be 3D printed, characterized in that, The composite surimi 3D printing ink is composed of surimi with a weight fraction of 92.0 - 99.5, antifreeze peptide with a weight fraction of 0.1 - 5.0, and food gum with a weight fraction of 0.5 - 3.0; The surimi is silver carp surimi, the antifreeze peptide is an antifreeze peptide extracted from silver carp scales, and the food gum is a combination of carrageenan and xanthan gum, locust bean gum and xanthan gum, or konjac gum and xanthan gum, and the mass ratio of the two colloids in the compound is 3:1 - 1:3; The preparation method of the composite surimi 3D printing ink includes the following steps: S1. Preparation of silver carp surimi: Fresh silver carp is gutted, skinned, and boned, then washed with pre-cooled water and ground at -4 °C for 10 - 30 min; S2. Preparation of antifreeze peptide: Add deionized water to silver carp scales and ultrasonicate for 80 - 100 min, then treat at 120 - 122 °C and 0.11 - 0.13 MPa for 20 - 40 min. After cooling, adjust the pH to 7.8 - 8.2, add trypsin and enzymolyze for 3 - 4 h. After inactivating the enzyme, centrifuge and take the supernatant and freeze-dry to obtain the antifreeze peptide; S3. Preparation of the composite surimi 3D printing ink: Add the antifreeze peptide prepared in step S2 to the surimi obtained in step S1 and disperse it at a stirring speed of 2500 - 3500 r / min in a cold water bath. Add food gum and stir for 3 min, then place it in a vacuum drying oven and incubate at 25 °C and -0.08 MPa for 30 min to remove the bubbles generated by stirring.

2. The application according to claim 1, characterized in that In step S2, add 260 - 300 g of deionized water to every 15 g of silver carp scales for ultrasonic extraction. The enzymolysis temperature is 36 - 38 °C. After inactivating the enzyme for 10 - 15 min, centrifuge and take the supernatant, and freeze-dry the supernatant to obtain the antifreeze peptide.

3. The application according to claim 1, wherein The storage temperature of the frozen storage product is -25 - -15 °C.

4. The application according to claim 1, wherein The storage time of the frozen storage product is 1 - 180 days, and the number of freeze-thaw cycles does not exceed 6 times.

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