Method for preparing 3D printing ink based on double-protein nanoparticles

Abstract

The invention discloses a method for preparing 3D printing ink based on double-protein nanoparticles, and belongs to the technical field of food processing. The method comprises the following steps: preparing soybean protein isolate-A type gelatin composite nanoparticles, stabilizing a high internal phase Pickering emulsion (75% oil phase) by using the nanoparticles, then mixing with chitosan quaternary ammonium salts with different solubilities, homogenizing to obtain emulsion gel, researching the rheological property and macroscopic stability of the emulsion gel, and investigating the appearance and contour of a 3D printed sea turtle model. Along with improvement of global health consciousness and transformation of dietary structure, development of a novel food system with excellent nutritional characteristics, ideal sensory quality and sustainability becomes an important direction in the field of food science. The 3D printing ink with excellent rheological property, macroscopic stability and 3D printing performance is prepared on the basis of the combination of the double-protein nanoparticle structure and the chitosan quaternary ammonium salt, and a theoretical and technical foundation is laid for creating customizable 3D printing ink and advanced food manufacturing materials; the method has important theoretical significance and practical value for promoting high-value utilization of vegetable protein and promoting development of the healthy food industry.

Description

Technical Field

[0001] This invention belongs to the field of food processing technology, and specifically relates to a method for preparing 3D printing ink based on dual protein nanoparticles. Background Technology

[0002] Soy protein, due to its rich nutritional value, low cost, and excellent functional properties, has been widely used in many fields. Type A gelatin (GE) is typically made from pig skin, fish skin, etc., through soaking, extraction, purification, and drying under acidic conditions. Its isoelectric point (pI) is usually between 7.0 and 9.0, higher than type B gelatin (pI approximately 4.8-5.2). GE's amino acid composition exhibits typical collagen characteristics: glycine (Gly) accounts for about one-third, proline (Pro) and hydroxyproline (Hyp) are high, while sulfur-containing amino acids (such as cysteine ​​and methionine) and aromatic amino acids (such as tryptophan) are extremely low. GE's unique amino acid composition can be used to enhance the hydrophilicity of composite nanoparticles, preparing dual-protein nanoparticles with excellent amphiphilicity. Dual-protein composite nanoparticles show broad application prospects in the food, pharmaceutical, and materials fields. In the food industry, they are mainly used as highly efficient natural emulsifiers, stabilizers, texture modifiers, and fat mimics in the production of products such as salad dressings, yogurt, and plant-based cheeses, to simulate the full-bodied taste and smooth texture of full-fat products. Despite their huge application potential, some issues remain regarding batch stability, cost control, and the preparation of certain complex food matrices in large-scale production.

[0003] Polysaccharides can interact with proteins through non-covalent, covalent, and steric interactions to form complexes with specific spatial structures. Multiple studies have confirmed that the introduction of polysaccharides can be an effective means of improving protein properties. Chitosan (CS) is a natural cationic polysaccharide obtained by deacetylation of chitin, composed of β-(1,4)-linked D-glucosamine and N-acetyl-D-glucosamine units. Based on the different modification sites and groups, quaternized chitosan (QCS) is mainly divided into two categories: N-chitosan quaternary ammonium salts (introducing quaternary ammonium groups onto the amino group) and O-chitosan quaternary ammonium salts (introducing quaternary ammonium groups onto the hydroxyl group). Among them, HACC (Chitosan quaternary ammonium salt) is a relatively typical N-chitosan quaternary ammonium salt. Quaternization modification endows chitosan with a series of significantly enhanced or newly formed physicochemical properties. First and foremost, it enhances its water solubility. HACC exhibits excellent water solubility in acidic, neutral, and even alkaline pH ranges, overcoming the limitation of chitosan's solubility only in acidic media and greatly expanding its application scenarios. Secondly, it possesses strong and stable cationic properties. Its permanent positive charge enables HACC to undergo strong electrostatic interactions with negatively charged substances (such as proteins, DNA, and anionic polysaccharides), forming the basis for its excellent coagulation ability.

[0004] Food 3D printing, as an emerging digital manufacturing technology, places strict requirements on the rheological properties of the "ink" material: it needs to possess good extrudability and the ability to rapidly recover its structure after extrusion to maintain shape fidelity (i.e., shear thinning and self-support). High internal phase Pickering emulsion gels (HIPPE-Gels) perfectly meet these requirements. Their typical shear thinning behavior causes their viscosity to decrease under the shearing action of the printhead, making them easy to extrude; once extruded, the shear force disappears, and the internal three-dimensional particle / droplet network is rapidly reconstructed, restoring high viscosity or modulus, thus enabling precise stacking and shaping without collapse. This makes HIPPE-Gels an ideal 3D food printing ink. It can be applied to customized nutritional food manufacturing, plant-based fat simulation and structuring, and the construction of complex multiphase food structures. In the future, developing intelligent responsive HIPPE-Gels inks based on various biopolymers will be a cutting-edge direction in this field. Summary of the Invention

[0005] This invention mainly utilizes dual-protein nanoparticles-polysaccharides to prepare an edible 3D printing ink with excellent rheological properties, stability, and 3D printing performance, opening up new avenues for the future manufacturing of customized nutritional foods.

[0006] A method for preparing emulsion gel based on dual-protein composite nanoparticles, characterized by the following steps: (1) preparing composite nanoparticles (SGCPs) and composite aggregates (SGCs) using soy protein isolate (SPI) and type A gelatin (GE) as raw materials; (2) adding SGCPs and SGCs to a certain volume of soybean oil and homogenizing to prepare high internal phase Pickering emulsions (HIPPEs); (3) compounding SGCPs and SGCs-stabilized HIPPEs with chitosan quaternary ammonium salts (HACC) at different mass ratios and then homogenizing to prepare emulsion gels (3D printing inks); (4) investigating the rheological properties, stability, and 3D printing performance of the emulsion gels.

[0007] Further specifying the method for preparing SGCPs and SGCs, the following steps are taken: SPI is suspended at 3 wt% in deionized water until completely dissolved, and then left overnight. A 3 wt% GE solution is heated in a water bath at 45°C for 30 min, and then cooled to room temperature for later use. Then, the SPI and GE suspensions are mixed at a ratio of 5:5 (v / v) to prepare two portions. One portion is adjusted to pH 7 and stirred for 3 h to prepare SGCs; the other portion has its pH adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h, then its pH is adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs.

[0008] Further specifying, the method for preparing HIPPEs is as follows: the prepared aqueous dispersion of SGCPs and SGCs (3wt%) is mixed with soybean oil (W / O=1∶3), and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs.

[0009] Further specifying, the method for preparing the emulsion gel is as follows: HIPPEs stabilized by SGCPs and SGCs are compounded with HACCs at different mass ratios (0, 0.25%, 0.50%, 0.75%, 1 wt%), and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare the emulsion gel.

[0010] Further, the rheological properties, stability, and 3D printing performance of the emulsion gel were investigated.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0012] This invention uses SGCPs (high HACC concentration) to prepare emulsion gels, and compares them with emulsion gels prepared by SGCs at the same HACC concentration. The final prepared dual-protein-based emulsion gel is superior in terms of stability and 3D printing performance. Attached Figure Description

[0013] Figure 1 The apparent viscosity of the sample;

[0014] Figure 2 For sample frequency scanning;

[0015] Figure 3 To assess the centrifugal stability of the sample;

[0016] Figure 4 To assess the freeze-thaw stability of the samples;

[0017] Figure 5 3D printing of samples;

[0018] Figure 6 Flowchart Example 1

[0019] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a ratio of 5:5 (v / v), and the pH of the suspension was adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h. Then, the pH of the dispersion was adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs. The prepared SGCPs dispersion (3 wt%) was mixed with soybean oil (w / o = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. Then, it was compounded with 0 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Example 2

[0020] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a ratio of 5:5 (v / v), and the pH of the suspension was adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h. Then, the pH of the dispersion was adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs. The prepared SGCPs dispersion (3 wt%) was mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. Then, it was compounded with 0.25 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Example 3

[0021] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a ratio of 5:5 (v / v), and the pH of the suspension was adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h. Then, the pH of the dispersion was adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs. The prepared SGCPs dispersion (3 wt%) was mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. Then, it was compounded with 0.5 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Example 4

[0022] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a ratio of 5:5 (v / v), and the pH of the suspension was adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h. Then, the pH of the dispersion was adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs. The prepared SGCPs dispersion (3 wt%) was mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. Then, it was compounded with 0.75 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Example 5

[0023] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a ratio of 5:5 (v / v), and the pH of the suspension was adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h. Then, the pH of the dispersion was adjusted to 7.0 with 2 M HCl and stirred for 3 h to prepare SGCPs. The prepared SGCPs dispersion (3 wt%) was mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. Then, it was compounded with 1 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Comparative Example 1

[0024] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a 5:5 (v / v) ratio, the pH was adjusted to 7, and the mixture was stirred for 3 h to prepare SGCs. The prepared SGCs (3 wt%) were mixed with soybean oil (w / o = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. These were then compounded with 0 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Comparative Example 2

[0025] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a 5:5 (v / v) ratio, the pH was adjusted to 7, and the mixture was stirred for 3 h to prepare SGCs. The prepared SGCs (3 wt%) were mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. These were then compounded with 0.25 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Comparative Example 3

[0026] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a 5:5 (v / v) ratio, the pH was adjusted to 7, and the mixture was stirred for 3 h to prepare SGCs. The prepared SGCs (3 wt%) were mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. These were then compounded with 0.5 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Comparative Example 4

[0027] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a 5:5 (v / v) ratio, the pH was adjusted to 7, and the mixture was stirred for 3 h to prepare SGCs. The prepared SGCs (3 wt%) were mixed with soybean oil (w / O = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. These were then compounded with 0.75 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel. Comparative Example 5

[0028] Spirulina (SPI) was suspended at 3 wt% in deionized water until completely dissolved, and then left to stand overnight. A 3 wt% GE solution was heated in a water bath at 45°C for 30 min, then cooled to room temperature. The SPI and GE suspensions were mixed at a 5:5 (v / v) ratio, the pH was adjusted to 7, and the mixture was stirred for 3 h to prepare SGCs. The prepared SGCs (3 wt%) were mixed with soybean oil (w / o = 1:3) and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs. These were then compounded with 1 wt% HACC and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare an emulsion gel.

Claims

1. A method for preparing 3D printing ink based on dual-protein nanoparticles, characterized in that, Includes the following steps: (1) Composite nanoparticles (SGCPs) and composite aggregates (SGCs) were prepared using soy protein isolate (SPI) and type A gelatin (GE) as raw materials; (2) SGCPs and SGCs were added to a certain volume of soybean oil and homogenized to prepare high internal phase Pickering emulsions (HIPPEs); (3) HIPPEs stabilized by SGCPs and SGCs were compounded with chitosan quaternary ammonium salts (HACC) at different mass ratios and then homogenized to prepare emulsion gels (3D printing inks); (4) The rheological properties, stability and 3D printing performance of the emulsion gels were investigated.

2. The method according to claim 1, characterized in that, The method for preparing SGCPs and SGCs is as follows: SPI is suspended at 3 wt% in deionized water until completely dissolved, and then left overnight. A 3 wt% GE solution is heated in a water bath at 45°C for 30 min, and then cooled to room temperature for later use. Then, the SPI and GE suspension is mixed at a ratio of 5:5 (v / v) to prepare two portions. One portion is adjusted to pH 7 and stirred for 3 h to prepare SGCs; the other portion has its pH adjusted to 12.0 with 2 M NaOH and stirred at 1000 rpm for 2 h, then the pH of the dispersion is adjusted to 2 M HCl. 7.0, stir for 3 h to prepare SGCPs.

3. The method according to claim 1, characterized in that, The method for preparing HIPPEs is as follows: the prepared aqueous dispersion of SGCPs and SGCs (3wt%) is mixed with soybean oil (W / O=1∶3), and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare HIPPEs.

4. The method according to claim 1, characterized in that, The method for preparing the emulsion gel is as follows: HIPPEs stabilized by SGCPs and SGCs are compounded with HACCs at different mass ratios (0, 0.25%, 0.50%, 0.75%, 1 wt%), and homogenized at 12000 rpm for 3 min using an IKA homogenizer to prepare the emulsion gel.

5. The method according to claim 1, characterized in that, The rheological properties, stability, and 3D printing performance of the emulsion gel were investigated.

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