A whipping process of high air permeability gelatin-free starch soft candy

Abstract

The present application relates to the field of food processing, and discloses a whipping process of high-breathability gelatin-free starch soft candy. The process comprises the following steps: adding glutamine transaminase to plant protein to perform cross-linking modification, destroying the globular quaternary structure and exposing the hydrophobic group, so as to obtain modified plant protein; mixing the modified plant protein with anionic polysaccharide to perform pre-emulsification, so as to obtain a pre-emulsified liquid; injecting the pre-emulsified liquid into starch syrup after boiling and cooling to perform aeration and whipping, the modified plant protein is adsorbed on the gas-liquid interface, the anionic polysaccharide is hydrated into a network in the continuous phase, and a composite three-dimensional gas-liquid interface film is constructed. The present application solves the problems of bubble combination and escape caused by low interface film strength of the gelatin-free system, and realizes the stability of the bubble of the soft candy matrix.

Description

Technical Field

[0001] This invention relates to the field of food processing and discloses a whipping process for highly breathable gelatin-free starch gummies. Background Technology

[0002] In the preparation of existing high-permeability gelatin-free starch gummies, unmodified plant proteins and hydrophilic colloids are typically added directly to replace gelatin for whipping. Gelatin has amphoteric molecular characteristics, enabling it to rapidly adsorb and spread at the gas-liquid interface to form a tough film. In gelatin-free systems, operators directly add unmodified pea protein isolate and gellan gum to cooked starch syrup and introduce gas through mechanical stirring. Unmodified plant protein molecules have a tightly packed spherical structure with hydrophobic groups encapsulated within the molecules, making it difficult for them to spread and adsorb at the gas-liquid interface; gellan gum is highly susceptible to premature cross-linking in the ion-containing syrup environment, forming localized micelles.

[0003] The aforementioned existing technologies result in low mechanical strength of the gas-liquid interface film in the gelatin-free starch gummy whipping system, making it unable to suppress the coalescence and escape of air bubbles. Unmodified plant protein has weak interfacial adsorption capacity, and premature cross-linking of gellan gum leads to uneven distribution of the continuous phase network. Consequently, the two cannot synergistically form a dense protective layer at the gas-liquid interface, causing the injected air bubbles to coalesce, grow, and rupture during shearing and subsequent pouring and drying processes. Summary of the Invention

[0004] To address the shortcomings of existing gelatin-free starch gummy whipping systems, such as low mechanical strength of the gas-liquid interface film which fails to effectively suppress bubble coalescence and escape, this invention provides a high-permeability gelatin-free starch gummy whipping process.

[0005] To address the aforementioned technical problems, this invention provides a whipping process for highly permeable gelatin-free starch gummies, comprising the following steps: preparing plant protein, adding transglutaminase to the plant protein for cross-linking modification, disrupting the globular quaternary structure of the plant protein and exposing hydrophobic groups to obtain modified plant protein; preparing anionic polysaccharides, mixing the modified plant protein and the anionic polysaccharides for pre-emulsification to obtain a pre-emulsion; preparing a starch syrup matrix, cooking and then cooling the starch syrup matrix; injecting the pre-emulsion into the cooked and cooled starch syrup matrix, and performing aeration and whipping. Under the mechanical shear force of the aeration and whipping, the modified plant protein is adsorbed at the gas-liquid interface, while the anionic polysaccharides hydrate in the continuous phase to form a network, constructing a composite three-dimensional gas-liquid interface membrane containing the modified plant protein and the anionic polysaccharides, locking the aeration and whipping gas to obtain whipped gummies.

[0006] The working principle is as follows: Glutamine transaminase specifically catalyzes the transamide reaction of the γ-carboxamide groups of glutamine residues in plant protein molecules, forming ε-(γ-glutamyl)lysine covalent cross-links between different protein molecules, thereby breaking the originally stable spherical quaternary structure of the plant proteins. The cross-linked protein molecular chains are stretched, exposing the hydrophobic regions originally encased within the molecules to the molecular surface, significantly improving the surface hydrophobicity and interfacial adsorption capacity of the proteins. During the aeration and whipping process, the highly surface-active modified plant proteins can rapidly migrate to the gas-liquid interface and align themselves, forming a dense primary protein interfacial film. Simultaneously, the anionic polysaccharides are fully hydrated in the continuous phase through intermolecular hydrogen bonds, forming a continuous three-dimensional network structure. This network not only increases the viscosity of the continuous phase, slowing down the rate of bubble rise and coalescence, but also binds to the modified plant proteins on the interface through electrostatic interactions, forming a polysaccharide reinforcement layer on the outer side of the interfacial film. Together, they construct a composite three-dimensional gas-liquid interfacial film with high mechanical strength and good elasticity, effectively locking in the gas introduced during the aeration process and preventing bubble coalescence, growth, and escape.

[0007] Furthermore, in the above technical solution, the plant protein is pea protein isolate; the cross-linking modification treatment includes: dispersing the pea protein isolate in an aqueous phase, adding the transglutaminase to carry out an enzymatic reaction, so that the pea protein isolate molecules form covalent cross-links; after the enzymatic reaction is completed, performing a step-by-step heating heat treatment, so that the cross-linked pea protein isolate undergoes thermal denaturation and further stretches the molecular chains, fully exposing the hydrophobic groups, to obtain the modified plant protein.

[0008] The working principle is as follows: Pea protein isolate molecules contain abundant glutamine residues, making them an ideal substrate for transglutaminase. The covalent bonds formed by enzymatic cross-linking cause moderate aggregation of pea protein isolate molecules, forming larger protein aggregates and further enhancing their interfacial activity. Stepwise heating has a dual effect: first, it thermally denatures and inactivates transglutaminase, precisely terminating the enzymatic reaction and avoiding excessive cross-linking that would lead to a sharp decrease in protein solubility; second, it thermally denatures the cross-linked pea protein isolate molecules, further unfolding the molecular chains and enriching more hydrophobic groups originally embedded within the molecules at the gas-liquid interface, thereby significantly enhancing the surface hydrophobicity and interfacial adsorption capacity of the protein molecules.

[0009] Furthermore, in the above technical solution, the anionic polysaccharide is a low-acyl gellan gum; before the pre-emulsification treatment, the low-acyl gellan gum is subjected to a chelation and decation treatment, specifically by dispersing the low-acyl gellan gum in an aqueous solution containing a chelating agent to remove the inherent divalent cations in the low-acyl gellan gum, thereby obtaining a decationized low-acyl gellan gum dispersion to prevent the low-acyl gellan gum from prematurely crosslinking and gelling in the subsequent pre-emulsification and mixing stages.

[0010] The working principle is as follows: Low-acyl gellan gum is an anionic linear polysaccharide whose carboxyl groups on its molecular chain can react with divalent cations (such as Ca). 2+ Mg 2+ Specific ionic crosslinking occurs, forming a "double helix" gel network. Natural low-acyl gellan gum typically contains a certain amount of divalent cations. During pre-emulsification and mixing with the starch syrup matrix, these inherent cations cause premature crosslinking of the low-acyl gellan gum, forming localized micelles and disrupting its uniform distribution in the continuous phase. Chelation and decation treatment, utilizing chelating agents to form stable water-soluble chelates with divalent cations, effectively removes these cations, keeping the low-acyl gellan gum in a dissolved state during pre-emulsification and mixing stages. This lays the foundation for controlled in-situ crosslinking in the later stages of aeration and whipping.

[0011] Furthermore, in the above technical solution, the pre-emulsification treatment of mixing the modified plant protein with the anionic polysaccharide includes: mixing the modified plant protein with 10%-20% of the starch syrup matrix, performing a first high-speed shearing to form a protein-embedded bubble dispersion phase with the modified plant protein as the primary interface film; subsequently adding the decationized low-acyl gellan gum dispersion, performing a second low-speed homogenization to uniformly distribute the decationized low-acyl gellan gum in the continuous phase, thereby obtaining the pre-emulsified solution.

[0012] The working principle is as follows: a two-step pre-emulsification process enables functional partitioning of proteins and polysaccharides. The first step involves high-speed shearing to fully disperse the modified plant protein and introducing a small amount of air under mechanical force, forming microbubble nuclei with the modified plant protein as the interfacial membrane. These pre-formed bubble nuclei serve as nucleation sites during subsequent aeration and whipping, promoting uniform bubble formation and preventing the formation of large bubbles. The second step involves low-speed homogenization to add decationized low-acyl gellan gum. This avoids the high-speed shearing process from destroying the already formed protein-embedded bubble structure, while simultaneously ensuring the low-acyl gellan gum is uniformly dispersed in the continuous phase, guaranteeing the formation of a uniform and continuous polysaccharide network in the subsequent process.

[0013] Furthermore, in the above technical solution, the starch syrup matrix comprises modified starch and maltitol syrup; the cooling treatment after cooking includes: cooking the starch syrup matrix to the target solids content, then cooling it in stages, first cooling it to a first temperature range of 70℃-80℃ to reduce the viscosity of the starch syrup matrix to meet the rheological requirements for the injection and dispersion of the pre-emulsion, and then continuing to cool it to a second temperature range of 55℃-65℃ for the aeration and whipping.

[0014] The working principle is as follows: modified starch provides excellent gelling properties and textural support for the gummies, while maltitol syrup provides sweetness and moisturizing properties, and is also low in calories and non-cariogenic. After the starch syrup matrix is ​​cooked to the target solids content, its viscosity becomes extremely high, which is detrimental to the injection and uniform dispersion of the pre-emulsion. Staged cooling treatment allows for precise control of the system's rheological properties: the first temperature range significantly reduces the viscosity of the starch syrup matrix, ensuring smooth injection and uniform dispersion of the pre-emulsion; the second temperature range restores the system viscosity to a moderate level, providing sufficient support for bubbles to prevent rapid upward movement, while also ensuring that the modified plant protein and anionic polysaccharides function effectively at the gas-liquid interface and in the continuous phase.

[0015] Furthermore, in the above technical solution, during the aeration and whipping stage, a divalent cation solution is introduced in stages; in the initial stage of aeration and whipping, without adding additional divalent cations, the mechanical shear force is used to refine the bubbles; in the later stage of aeration and whipping, the divalent cation solution is injected into the system to trigger the decationized low-acyl gellan gum to undergo ionic crosslinking, thereby solidifying the anionic polysaccharide network in the continuous phase in situ.

[0016] The working principle is as follows: the segmented introduction of divalent cations enables precise control of the crosslinking timing of low-acyl gellan gum. In the initial stage of aeration and whipping, the system contains no divalent cations, and the low-acyl gellan gum remains in a dissolved state. The continuous phase has a low viscosity, which facilitates the mechanical shearing force to refine the bubbles into uniform microbubbles. Once the bubble size reaches the required level, a divalent cation solution is injected in the later stage of whipping. The divalent cations rapidly undergo an ionic crosslinking reaction with the carboxyl groups on the low-acyl gellan gum molecular chains, causing the polysaccharide network in the continuous phase to solidify instantaneously. The system viscosity and elasticity increase dramatically, stably locking the refined bubbles within the three-dimensional network structure and preventing bubble merging and escape during subsequent pouring and curing processes.

[0017] Furthermore, in the above technical solution, when the pre-emulsion is injected into the starch syrup matrix after boiling and cooling, the pre-emulsion accounts for 15%-20% of the total mass of the mixing system, and after injection, the pre-emulsion is uniformly dispersed in the starch syrup matrix by low-speed stirring to avoid high-speed shearing damaging the protein-embedded bubble structure already formed in the pre-emulsion.

[0018] The working principle is as follows: controlling the addition ratio of the pre-emulsion ensures that the concentration of modified plant protein and anionic polysaccharides in the system is within the optimal range, forming a sufficiently strong composite interfacial film without causing the gummy texture to become too hard due to excessive concentration. The low-speed tumbling mixing method avoids the strong mechanical force generated by high-speed shearing, which could destroy the pre-formed protein-embedded bubble cores in the pre-emulsion. This ensures that these bubble cores can function properly during the subsequent aeration and whipping process, promoting the uniform generation and stability of bubbles.

[0019] Furthermore, in the above technical solution, the mass ratio of the modified plant protein to the anionic polysaccharide is controlled at 2:1-5:1, and the total solids content of the modified plant protein and the anionic polysaccharide in the pre-emulsion is 12%-18%, so that the modified plant protein occupies the dominant position at the gas-liquid interface and the anionic polysaccharide provides steric hindrance.

[0020] The working principle is as follows: the mass ratio of modified plant protein to anionic polysaccharides directly determines the structure and performance of the composite interfacial membrane. When the proportion of modified plant protein is high, it can preferentially adsorb onto the gas-liquid interface and arrange itself tightly to form a continuous and dense primary protein interfacial membrane. The anionic polysaccharides are mainly distributed on the continuous phase and the outer side of the interfacial membrane, binding to protein molecules through electrostatic interactions, providing steric hindrance to prevent protein molecules on the interfacial membrane from agglomerating, while simultaneously increasing the viscosity of the continuous phase, further enhancing bubble stability. Controlling the total solids content ensures that there are sufficient protein molecules at the gas-liquid interface to form a complete interfacial membrane.

[0021] Furthermore, in the above technical solution, the environmental conditions for the enzymatic reaction include: controlling the amount of glutamine transaminase added to be 0.3%-0.8% of the amount of pea protein isolate, maintaining the reaction system at a constant temperature, and inactivating the enzyme by the stepwise heating heat treatment after the reaction, while promoting the enrichment of hydrophobic groups of the pea protein isolate at the gas-liquid interface.

[0022] The working principle is as follows: The amount of transglutaminase added is a key parameter for controlling the degree of protein cross-linking. If the amount added is too low, the cross-linking degree is insufficient, failing to effectively break down the globular structure of pea protein isolate and resulting in inadequate exposure of hydrophobic groups; if the amount added is too high, it will lead to excessive cross-linking of the protein, forming insoluble aggregates, which will actually reduce its interfacial activity. The isothermal reaction ensures that transglutaminase is at its optimal catalytic temperature, improving reaction efficiency and controllability. Stepwise heating treatment, while inactivating the enzyme, also promotes thermal denaturation of the cross-linked protein molecules, further stretching the molecular chains and fully exposing the hydrophobic groups.

[0023] Furthermore, in the above technical solution, after the whipped sugar paste is poured, it enters the curing stage. In the curing stage, an alternating temperature field is used for treatment. First, the temperature of the whipped sugar paste is rapidly reduced in a low-temperature environment to quickly solidify the ionic cross-linking network formed by the decationized low-acyl gelling gel. Then, the temperature is raised to a room temperature environment to balance the moisture gradient stress inside and outside the whipped sugar paste.

[0024] The working principle is as follows: Alternating temperature field treatment can significantly improve the textural stability and appearance quality of gummies. Low-temperature rapid curing allows the ionic cross-linking network of low-acyl gellan gum to quickly solidify, stably locking air bubbles inside the gummies and preventing them from migrating and merging during curing. Subsequent heating to room temperature for equilibration allows moisture to gradually diffuse evenly throughout the gummies, eliminating internal moisture gradient stress caused by rapid cooling and preventing defects such as cracking and deformation. This also results in a more uniform and delicate texture for the gummies.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] 1. This invention modifies the interfacial adsorption properties of plant proteins by cross-linking with transglutaminase, thereby disrupting their spherical quaternary structure and exposing hydrophobic groups. The modified plant protein is pre-emulsified with anionic polysaccharides before being injected into syrup and aerated. The modified plant protein adsorbs at the gas-liquid interface, while the anionic polysaccharides hydrate in the continuous phase to form a network. Together, they construct a composite three-dimensional gas-liquid interfacial membrane, solving the problem of low mechanical strength of the gas-liquid interfacial membrane in gelatin-free starch-based soft candy whipping systems, which leads to bubble coalescence and escape.

[0027] 2. Chelating and decation treatment of low-acyl gellan gum inhibits premature cross-linking during the pre-emulsification and mixing stages; injecting divalent cations in the later stage of aeration and whipping triggers in-situ solidification of low-acyl gellan gum through ionic cross-linking, stabilizing the bubble morphology; step-by-step heating after cross-linking modification of pea protein isolate allows the molecular chains to stretch and expose hydrophobic groups; low-speed stirring after injection of pre-emulsion maintains the protein-embedded bubble structure; alternating temperature field treatment allows the low-acyl gellan gum network to quickly solidify and balance internal moisture stress. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to embodiments. Those skilled in the art can reproduce the technical solution of the present invention and achieve its claimed technical effects based on the content disclosed in this specification. It should be noted that the following embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention. Any non-substantial improvements and adjustments made based on the core concept of the present invention should fall within the scope of protection of the present invention.

[0029] Example 1: This example provides a whipping process for highly breathable gelatin-free starch-free gummies. The specific steps are as follows:

[0030] Preparation of modified plant protein: Weigh 10g of pea protein isolate and disperse it in 90g of deionized water. Stir until completely dissolved. Adjust the pH of the system to 7.5 with 0.1mol / L sodium hydroxide solution. Add 0.05g of transglutaminase (enzyme activity 100U / g) and place in a 37℃ constant temperature water bath for 2h of enzymatic reaction. After the reaction, perform stepwise heating treatment: heat to 50℃ at a rate of 2℃ / min and hold for 10min, continue to heat to 70℃ and hold for 10min, and finally heat to 90℃ and hold for 5min to completely inactivate the enzyme. At the same time, promote the protein molecular chain to unfold and expose hydrophobic groups. Cool to room temperature to obtain modified pea protein isolate solution.

[0031] Anionic polysaccharide pretreatment: Weigh 2g of low-acyl gellan gum and disperse it in 98g of deionized water containing 0.1g of sodium citrate. Heat to 80℃ and stir for 30min to completely dissolve the low-acyl gellan gum and complete the chelation and decation treatment to obtain a decationized low-acyl gellan gum dispersion. Cool to room temperature for later use.

[0032] Preparation of pre-emulsion: Take the above modified pea protein isolate and mix with 20g maltitol syrup, place in a high-speed shear machine and shear at 12000rpm for 2min to form a protein-embedded bubble dispersion phase with modified pea protein isolate as the primary interface film; then add the above decationized low-acyl gellan gum dispersion and homogenize at 3000rpm for 1min to make the gellan gum evenly distributed in the continuous phase to obtain the pre-emulsion.

[0033] Starch syrup matrix preparation and treatment: Weigh 30g of hydroxypropyl modified starch and mix with 150g of maltitol syrup, add 20g of deionized water, stir evenly and place in a sugar boiling pot to cook until the solid content is 75%; after stopping heating, perform staged cooling: first, cool naturally to 75℃ (first temperature range) to reduce the viscosity of the system to 1500mPa・s, which meets the requirements for pre-emulsion injection and dispersion; continue cooling to 60℃ (second temperature range) for later use.

[0034] Aeration and whipping: The pre-emulsion was slowly injected into the starch syrup matrix that had been boiled and cooled to 60°C. The pre-emulsion accounted for 20% of the total mass of the mixture. After injection, the mixture was stirred at a low speed of 50 rpm for 3 minutes to ensure uniform dispersion. Then, it was transferred to an aeration whipping machine for aeration and whipping: initially, the mixture was stirred at 600 rpm for 5 minutes to refine the bubbles using mechanical shearing force without additional divalent cations. In the later stage of whipping, 5g of 0.1mol / L calcium chloride solution was slowly injected into the system, and whipping was continued at 400 rpm for 3 minutes to trigger the ionic cross-linking of the decationized low-acyl gellan gum, which solidified the polysaccharide network in the continuous phase in situ to obtain whipped sugar paste.

[0035] Pouring and curing: The whipped sugar paste is poured into the gummy candy mold and sent to the curing chamber for alternating temperature field treatment: First, it is placed in a low temperature environment of 4℃ for 30 minutes to allow the ionic cross-linking network to quickly solidify; then it is transferred to a room temperature environment of 25℃ for 2 hours to eliminate the internal moisture gradient stress and obtain highly permeable gelatin-free starch gummy candy.

[0036] Example 2: The only difference between this example and Example 1 is that the mass ratio of modified pea protein isolate to low-acyl gellan gum is 2:1, that is, the amount of pea protein isolate is 10g and the amount of low-acyl gellan gum is 5g. All other conditions are the same as in Example 1.

[0037] Example 3: The only difference between this example and Example 1 is that the amount of transglutaminase added is 0.3% of the pea protein isolate, i.e., the amount of transglutaminase used is 0.03g. All other conditions are the same as in Example 1.

[0038] Example 4: The only difference between this example and Example 1 is that the modified starch used in the starch syrup matrix is ​​acetylated distarch phosphate. All other conditions are the same as in Example 1.

[0039] Example 5: The only difference between this example and Example 1 is that the sweetener used in the starch syrup base is sorbitol syrup, instead of maltitol syrup. All other conditions are the same as in Example 1.

[0040] Example 6: The only difference between this example and Example 1 is that the pre-emulsion accounts for 15% of the total mass of the mixed system. All other conditions are the same as in Example 1.

[0041] Example 7: The only difference between this example and Example 1 is that the first cooling temperature after the starch syrup matrix is ​​boiled is 70°C, corresponding to a system viscosity of 2000 mPa·s. All other conditions are the same as in Example 1.

[0042] Example 8: The only difference between this example and Example 1 is that the concentration of the calcium chloride solution injected during the later stage of aeration and whipping is 0.06 mol / L. All other conditions are the same as in Example 1.

[0043] Example 9: The only difference between this example and Example 1 is that the starch syrup matrix is ​​boiled until the target solids content is 72%. All other conditions are the same as in Example 1.

[0044] Example 10: The only difference between this example and Example 1 is that the stepwise heating rate after the enzymatic reaction is 5°C / min. All other conditions are the same as in Example 1.

[0045] Example 11: The only difference between this example and Example 1 is that the mixing time in the initial stage of aeration and whipping is 7 minutes, the mixing time in the later stage is 3 minutes, and the total whipping time is 10 minutes. All other conditions are the same as in Example 1.

[0046] Example 12: The only difference between this example and Example 1 is that the low-temperature treatment time during the curing stage is 45 minutes. All other conditions are the same as in Example 1.

[0047] Comparative Example 1: The only difference between this comparative example and Example 1 is that no transglutaminase was added, and the pea protein isolate was not cross-linked and was directly dispersed in water for use. All other conditions were the same as in Example 1.

[0048] Comparative Example 2: This comparative example uses the conventional preparation process described in the background art: 10g of unmodified pea protein isolate and 2g of low-acyl gellan gum that has not undergone chelation and decation treatment are weighed and directly added to a starch syrup matrix that has been boiled to a solid content of 75% and cooled to 60°C (formula same as Example 1); the mixture is whipped at 600 rpm for 8 minutes to obtain whipped sugar paste; after pouring, it is cured at room temperature of 25°C for 4 hours. Other conditions are the same as in Example 1.

[0049] Comparative Example 3: The only difference between this comparative example and Example 1 is that the amount of transglutaminase added is 2% of the pea protein isolate, i.e., the amount of transglutaminase used is 0.2g. All other conditions are the same as in Example 1.

[0050] Comparative Example 4: The only difference between this comparative example and Example 1 is that the chelation and decation treatment step of the low-acyl gellan gum is omitted, and the low-acyl gellan gum is directly dispersed in deionized water for use. All other conditions are the same as in Example 1.

[0051] Test method:

[0052] Average bubble diameter: The particle size distribution of bubbles in whipped sugar paste was measured using a laser particle size analyzer, and the volume average diameter was calculated.

[0053] Bubble retention rate: The volume of bubbles in the gummies was measured immediately after whipping and 24 hours after pouring and curing. Bubble retention rate = (bubble volume after curing / bubble volume immediately after whipping) × 100%.

[0054] Interfacial film strength: The expansion modulus of the gas-liquid interfacial film was measured using an interfacial rheometer to characterize the mechanical strength of the interfacial film.

[0055] Air permeability: The amount of water vapor that passes through the gummies at 25°C and 90% relative humidity was measured using a water vapor transmission rate tester to characterize the air permeability.

[0056] Texture properties: TPA test was performed using a texture analyzer to determine the hardness and elasticity of the gummies. Test conditions: probe P / 5, pre-compression speed 1 mm / s, test speed 1 mm / s, compression ratio 50%.

[0057] Test results:

[0058] Table 1 Performance test results of each embodiment and comparative example

[0059] Example 1 5:1 0.5 yes 48 95.2 36.2 1245 248 0.86 Example 2 2:1 0.5 yes 55 92.7 33.5 1180 275 0.82 Example 3 5:1 0.3 yes 52 93.1 34.1 1210 256 0.83 Example 4 5:1 0.5 yes 50 94.5 35.7 1230 262 0.85 Example 5 5:1 0.5 yes 51 93.8 35.2 1225 245 0.84 Example 6 5:1 0.5 yes 54 92.3 33.8 1170 260 0.82 Example 7 5:1 0.5 yes 53 92.8 34.0 1195 258 0.83 Example 8 5:1 0.5 yes 50 94.2 35.5 1220 252 0.85 Example 9 5:1 0.5 yes 52 93.5 34.6 1205 238 0.84 Example 10 5:1 0.5 yes 51 93.9 35.0 1215 250 0.84 Example 11 5:1 0.5 yes 46 94.8 35.8 1235 242 0.85 Example 12 5:1 0.5 yes 49 95.0 36.0 1240 246 0.86 Comparative Example 1 5:1 0 yes 215 38.7 14.3 485 142 0.48 Comparative Example 2 5:1 0 no 198 42.5 16.8 560 175 0.53 Comparative Example 3 5:1 2.0 yes 162 49.3 19.7 675 312 0.59 Comparative Example 4 5:1 0.5 no 176 45.8 17.5 620 285 0.56

[0060] Results analysis:

[0061] The high-permeability gelatin-free starch gummies prepared in Examples 1-12 all exhibited excellent bubble stability and permeability. Example 1 showed the best overall performance, with an average bubble diameter of only 48 μm, a bubble retention rate as high as 95.2%, an interfacial film strength of 36.2 mN / m, and a permeability of 1245 g / (m³). 2 • 24h), while possessing moderate hardness and good elasticity. This indicates that the technical solution of the present invention, which combines glutamine transaminase cross-linking modification of plant protein, anionic polysaccharide pre-emulsification treatment, segmented aeration whipping, and controllable ionic cross-linking, can effectively construct a high-strength composite three-dimensional gas-liquid interface film, significantly improving the whipping effect and product performance of gelatin-free starch gummies.

[0062] Comparing Example 1 and Comparative Example 1, it is evident that the pea protein isolate without cross-linking modification using transglutaminase did not exhibit a disrupted spherical quaternary structure, resulting in insufficient exposure of hydrophobic groups and extremely poor interfacial adsorption capacity. In Comparative Example 1, the average bubble diameter reached 215 μm, with a bubble retention rate of only 38.7%, and the interfacial film strength was less than half that of Example 1. This clearly demonstrates that transglutaminase cross-linking modification is a crucial step in enhancing the interfacial activity of plant proteins.

[0063] Comparing Example 1 and Comparative Example 2, it is evident that the traditional process of directly adding unmodified protein and undecationized gellan gum, as described in the background art, cannot form a uniform and stable composite interfacial film. Unmodified protein exhibits weak interfacial adsorption, and the undecationized gellan gum prematurely crosslinks in the syrup environment, forming localized micelles, leading to a large number of bubble coalescence and escape. The bubble retention rate of Comparative Example 2 is only 42.5%, and its permeability is less than half that of Example 1, strongly demonstrating the significant advancement of the present invention compared to existing technologies.

[0064] Comparing Example 1 and Comparative Example 3, it can be seen that when the amount of transglutaminase added is too high (2%), the pea protein isolate undergoes excessive cross-linking, forming a large number of insoluble protein aggregates. This not only reduces the interfacial activity of the protein but also leads to an excessively hard texture and decreased elasticity in the gummy candy. The bubble retention rate of Comparative Example 3 is only 49.3%, and the hardness is as high as 312g, indicating that the range of transglutaminase added as defined in this invention is reasonable and necessary.

[0065] Comparing Example 1 and Comparative Example 4, it is evident that omitting the chelation and decation treatment step of the low-acyl gellan gum leads to premature crosslinking of the gellan gum during the pre-emulsification and mixing stages, preventing the formation of a uniform three-dimensional network in the continuous phase. Comparative Example 4 showed an average bubble diameter of 176 μm and a bubble retention rate of 45.8%, demonstrating that the chelation and decation treatment, combined with the subsequent segmented introduction of divalent cations into in-situ curing technology, is the core method for achieving controllable construction of the gellan gum network and a stable bubble structure.

[0066] Examples 2-12 involved adjusting the formulation ratios and process parameters within the scope defined by this invention. All samples exhibited a bubble retention rate exceeding 92%, an interfacial film strength higher than 33 mN / m, and an air permeability exceeding 1170 g / (m³). 2 •24h) indicates that the technical solution of the present invention has good robustness and repeatability, and can adapt to parameter fluctuations in industrial production.

[0067] In summary, this invention achieves the synergistic effect of modified plant protein and anionic polysaccharide at the gas-liquid interface and in the continuous phase by specifically cross-linking the plant protein, controlling the cross-linking of the anionic polysaccharide, and optimizing the pre-emulsification and aeration whipping processes. This successfully solves the technical problems of low gas-liquid interface film strength and easy bubble merging and escape in the existing gelatin-free starch gummy whipping system, and achieves unexpected technical results.

Claims

1. A whipping process for highly breathable gelatin-free starch gummies, characterized in that, Includes the following steps: Prepare plant protein, add transglutaminase to the plant protein for cross-linking modification treatment, destroy the globular quaternary structure of the plant protein and expose hydrophobic groups to obtain modified plant protein; Prepare anionic polysaccharides by mixing the modified plant protein with the anionic polysaccharides and performing a pre-emulsification treatment to obtain a pre-emulsion. Prepare a starch syrup base, and then boil and cool the starch syrup base. The pre-emulsion is injected into the starch syrup matrix after boiling and cooling, and then aerated and whipped. Under the mechanical shear force of the aeration and whipping, the modified plant protein is adsorbed at the gas-liquid interface, while the anionic polysaccharide is hydrated in the continuous phase to form a network, thus constructing a composite three-dimensional gas-liquid interface membrane containing the modified plant protein and the anionic polysaccharide, locking in the aerated and whipped gas to obtain whipped sugar paste.

2. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 1, characterized in that, The plant protein is pea protein isolate; The crosslinking modification treatment includes: The pea protein isolate was dispersed in an aqueous phase, and the transglutaminase was added to carry out an enzymatic reaction, causing covalent cross-linking between the pea protein isolate molecules; After the enzymatic reaction is completed, a step-by-step heating heat treatment is performed to cause the cross-linked pea protein isolate to undergo thermal denaturation and further stretch the molecular chains, fully exposing the hydrophobic groups, thereby obtaining the modified plant protein.

3. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 1, characterized in that, The anionic polysaccharide is a low-acyl gellan gum; Before the pre-emulsification treatment, the low-acyl gellan gum is subjected to a chelation and decation treatment. Specifically, the low-acyl gellan gum is dispersed in an aqueous solution containing a chelating agent to remove the inherent divalent cations in the low-acyl gellan gum, thereby obtaining a decationized low-acyl gellan gum dispersion to prevent the low-acyl gellan gum from prematurely crosslinking and gelling in the subsequent pre-emulsification and mixing stages.

4. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 3, characterized in that, The pre-emulsification treatment of mixing the modified plant protein with the anionic polysaccharide includes: The modified plant protein is mixed with 10%-20% of the starch syrup matrix and subjected to a first high-speed shearing to form a protein-embedded bubble dispersion phase with the modified plant protein as the primary interface film. Subsequently, the decationized low-acyl gellan gum dispersion is added, and a second low-speed homogenization is performed to ensure that the decationized low-acyl gellan gum is uniformly distributed in the continuous phase, thereby obtaining the pre-emulsion.

5. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 1, characterized in that, The starch syrup matrix comprises modified starch and maltitol syrup; The cooling process after boiling includes: After the starch syrup matrix is ​​boiled to the target solids content, it is cooled in stages. First, it is cooled to a first temperature range of 70℃-80℃ to reduce the viscosity of the starch syrup matrix to meet the rheological requirements for the injection and dispersion of the pre-emulsion. Then, it is cooled to a second temperature range of 55℃-65℃ for the aeration and whipping.

6. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 4, characterized in that, During the aeration and foaming stage, a divalent cation solution is introduced in stages; In the initial stage of the aeration and foaming process, the air bubbles are refined using the mechanical shearing force without the addition of additional divalent cations. In the later stage of the aeration and foaming process, the divalent cation solution is injected into the system to trigger the ionic crosslinking of the decationized low-acyl gellan gum, thereby solidifying the anionic polysaccharide network in the continuous phase in situ.

7. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 1, characterized in that, When the pre-emulsion is injected into the starch syrup matrix after boiling and cooling, the pre-emulsion accounts for 15%-20% of the total mass of the mixing system. After injection, the pre-emulsion is evenly dispersed in the starch syrup matrix by low-speed stirring to avoid high-speed shearing that would damage the protein-embedded bubble structure already formed in the pre-emulsion.

8. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 1, characterized in that, The mass ratio of the modified plant protein to the anionic polysaccharide is controlled at 2:1-5:1, and the total solids content of the modified plant protein and the anionic polysaccharide in the pre-emulsion is 12%-18%, so that the modified plant protein occupies the dominant position at the gas-liquid interface and the anionic polysaccharide provides steric hindrance.

9. The whipping process for a highly breathable gelatin-free starch-free gummy candy according to claim 2, characterized in that, The environmental conditions for the enzyme-catalyzed reaction include: The amount of glutamine transaminase added is controlled to be 0.3%-0.8% of the amount of pea protein isolate. The reaction system is kept at a constant temperature. After the reaction is completed, the enzyme is inactivated by the stepwise heating heat treatment, which at the same time promotes the enrichment of hydrophobic groups of pea protein isolate at the gas-liquid interface.

10. The whipping process for a high-permeability gelatin-free starch-based soft candy according to claim 6, characterized in that, After being poured, the whipped sugar paste enters the curing stage. In the curing stage, an alternating temperature field is used to treat the whipped sugar paste. First, the temperature of the whipped sugar paste is rapidly reduced in a low-temperature environment to quickly solidify the ionic cross-linking network formed by the decationized low-acyl gelling gel. Then, the temperature is raised to a room temperature environment to balance the moisture gradient stress inside and outside the whipped sugar paste.