A baking product anti-aging quality management system with complex enzyme synergistic effect

Abstract

This invention belongs to the technical field of food processing and preservation technology, and relates to a quality management system for anti-aging of baked goods based on the synergistic effect of compound enzymes. The system includes the following modules: a core unit microcarrier preparation module to generate core unit microcarriers; a satellite unit microcarrier synthesis module to generate satellite unit microcarriers; a topology assembly module to generate a core-satellite topology composite micro / nano carrier system; a matrix interface construction module to generate an initial matrix for baked goods containing a physical monitoring interface; a first enzyme group release module to catalyze the generation of maltose-specific molecular groups; a second enzyme group release module to unblock and release the second enzyme group aqueous solution to the starch retrogradation core region; and a barrier generation module to generate a three-dimensional network polymer of starch lipids. This invention solves the problem of lack of spatiotemporal control in the release of compound enzymes in food matrices.

Description

Technical Field

[0001] This invention belongs to the technical field of food processing and preservation technology, and relates to an anti-aging quality management system for baked goods with the synergistic effect of compound enzymes. Background Technology

[0002] The aging phenomenon in baked goods during storage is mainly manifested as a decline in quality caused by starch retrogradation, which is essentially a rearrangement of the microcrystalline structure of gelatinized amylopectin. Using enzymes to intervene in starch recrystallization is a common anti-aging method, but in practical applications, the timing and spatial location of enzyme action are difficult to precisely control. Adding enzymes directly during dough preparation can easily lead to premature overconsumption or damage to the initial food structure, while conventional addition methods can easily cause temporal conflicts in the multi-enzyme synergistic process, resulting in a decrease in subsequent anti-aging efficacy.

[0003] In response to the above situation, the industry has proposed some improvement solutions. For example, patent application number CN103651662B discloses a bread preservative enzyme preparation and its application, which involves physically mixing multiple enzymes with excipients and applying them directly to the dough, aiming to ensure that some enzymes survive and function after baking. However, certain limitations still exist in practical applications. The physical mixing and addition method mainly relies on the residual activity of the enzymes, making it difficult to maintain a stable anti-aging effect over a long shelf life. Traditional encapsulation technologies are mostly passive release systems, where the enzyme release rate is mainly driven by macroscopic environmental gradients such as external temperature and humidity, lacking a direct triggering mechanism between the enzyme release rate and the actual process of starch micro-crystallization and aging within the food matrix. This passive release method makes it difficult to form high concentrations of active enzymes at the microscopic key sites where starch rearrangement begins in a timely manner, and it lacks sequential and directional release control for multi-enzyme complex systems.

[0004] Therefore, the technical problem to be solved by this invention is how to construct a triggering mechanism that can respond to the microscopic process of starch retrogradation and solve the problem of lack of spatiotemporal control in the release of compound enzymes in food matrix. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a quality management system for anti-aging of baked goods based on the synergistic effect of compound enzymes.

[0006] A quality management system for anti-aging of baked goods based on the synergistic effect of compound enzymes includes: The core unit microcarrier preparation module obtains an aqueous solution of the second enzyme group, crosslinks a preset polymer network with a preset phenylboronic acid fragment and encapsulates the aqueous solution of the second enzyme group to generate a core unit microcarrier. The satellite unit microcarrier synthesis module obtains the first enzyme group mixture, prepares a brittle silica shell with preset weak bonds to encapsulate the first enzyme group mixture, grafts a preset amylose fragment to construct a molecular anchoring chain, and generates a satellite unit microcarrier. The topology assembly module drives the preset short peptide crosslinking arms to connect the core unit microcarrier and the satellite unit microcarrier, generating a core satellite topology composite micro-nano carrier system. The matrix interface construction module integrates the core satellite topology composite micro-nano carrier system into a preset matrix raw material for baking and cooling, generating an initial matrix for baked goods containing a physical monitoring interface; The first enzyme release module extracts the contraction force released from the initial matrix of baked goods, and conducts the contraction force to cause the satellite unit microcarrier to disintegrate and release the first enzyme mixture, which catalyzes the generation of maltose-specific molecular groups. The second enzyme release module drives the maltose-specific molecular group to undergo a substitution reaction with the cross-linking sites in the core unit microcarrier, thereby releasing the second enzyme aqueous solution into the starch retrogradation core region. The barrier generation module mobilizes the second enzyme group's aqueous solution to degrade lipid molecules to generate a monoglyceride molecular layer, and guides the monoglyceride molecular layer to interact with the preset starch residue to generate a three-dimensional network polymer of starch lipids.

[0007] A further aspect of the present invention involves generating a core unit microcarrier, comprising the following steps: Maltose α-amylase was mixed and dissolved with a specific lipase to generate an aqueous solution of the second enzyme group; A polymeric gel network system was formed by using a pre-defined phenylboronic acid fragment to perform targeted cross-linking on an alginate solution, thus creating a pre-defined polymeric network. The aqueous solution of the second enzyme group was injected into the polymer gel network system and solidified by ion gelation to generate the core unit microcarrier.

[0008] A further aspect of the present invention involves generating satellite unit microcarriers, comprising the following steps: Mix debranching enzyme and β-amylase to generate the first enzyme group mixture; An interfacial condensation reaction is carried out between tetraethyl orthosilicate and an acetal-bridged bissilane precursor to generate a brittle silica shell with a pre-set weak bond, which then encapsulates the first enzyme group mixture. Low-polymerization-degree amorphous amylose fragments are grafted at high density onto the exterior of a brittle silica shell as pre-defined amylose fragments to construct molecular anchoring chains and generate satellite unit microcarriers.

[0009] A further aspect of the present invention involves generating a core satellite topology composite micro / nano carrier system, comprising the following steps: The core unit microcarriers and satellite unit microcarriers are co-dispersed and injected into a mild hypertonic buffer system to form a mixed suspension system; Short peptide molecules are introduced into a mixed suspension system as pre-set short peptide crosslinking arms, and chemical coupling agents are used to activate the surface of the core unit microcarrier and the ends of the short peptide molecules. A core unit microcarrier system is generated by covalently connecting one end of a pre-defined short peptide crosslinking arm to a core unit microcarrier and binding multiple satellite unit microcarriers to the other end.

[0010] A further aspect of the present invention involves generating an initial matrix for baked goods that includes a physical monitoring interface, comprising the following steps: The core satellite topology composite micro-nano carrier system is uniformly kneaded into the preset matrix raw material in the form of solid powder to form a mixed preform. High-temperature baking of the mixed dough drives starch gelatinization, maintaining the topology of the core satellite topology composite micro-nano carrier system unchanged; The process guides the heated product to cool down, resulting in double-helix shrinkage and crystallization. This causes the matrix's own network to reconstruct and become entangled around the molecular anchoring chains, generating an initial matrix for baked goods that includes a physical monitoring interface.

[0011] A further embodiment of the present invention catalyzes the generation of a maltose-specific molecular group, comprising the following steps: Relying on the constraint effect of the physical monitoring interface, the shrinkage force is reversed to the connection anchor point of the satellite unit microcarrier. The shrinkage force is effectively transmitted through the physical entanglement generated between the non-crystalline amylose fragments and the food matrix network. The conduction of contraction tension causes stress concentration in the brittle silica shell, tearing the pre-set weak bonds and triggering the disintegration of the satellite unit microcarrier, releasing the first enzyme group mixture; The first enzyme group mixture is controlled to shear and recrystallize the amylopectin side layer linkages, catalyze the production of free short chains and their aggregation, and generate maltose-specific molecular groups.

[0012] A further embodiment of the present invention, which unblocks and releases the second enzyme group aqueous solution into the starch retrogradation core region, includes the following steps: The maltose-specific molecular group is driven to cross the spatial distance limited by the preset short peptide crosslinking arm, fully covering and wetting the surface of the core unit microcarrier. The concentration gradient of the maltose-specific molecular group is limited by the nanoscale spatial distance limited by the short peptide crosslinking arm. The specific molecular group of maltose is driven to intervene in the cross-linking site to undergo an irreversible strong complexation and substitution chemical reaction, thereby severing the cross-linking site; Cutting off the cross-linking sites causes the core unit microcarrier to liquefy and unblock, releasing the second enzyme group aqueous solution into the starch regeneration core region.

[0013] A further embodiment of the present invention generates a three-dimensional network polymer of starch lipids, comprising the following steps: The specific lipase contained in the aqueous solution of the second enzyme group is activated, which degrades the surrounding free and latent lipid molecules and generates a monoglyceride molecular layer. The fragments of free amylose molecules accumulated by cutting and peeling off the first enzyme group mixture were used as the preset starch fragments. The monoglyceride molecular layer and the pre-set starch residue are thermodynamically stable entangled and interacted, and solidified and deposited to form a three-dimensional network polymer of starch lipids.

[0014] In summary, the present invention has the following beneficial technical effects: 1. By grafting low-polymerization-degree amorphous amylose fragments onto the surface of satellite unit microcarriers to form molecular anchoring chains, these chains can spontaneously entangle with the food matrix during starch gelatinization and cooling. This structure effectively captures the volumetric shrinkage force generated during the transformation of amylopectin to a microcrystalline state and transmits this micromechanical signal to the microcarrier shell. This mechanism converts the initial molecular-level aging signal into a mechanical trigger force, reducing the system's reliance on manual judgment or external timed release mechanisms, and facilitating precise matching of enzyme release timing with the actual aging process of the food.

[0015] 2. The brittle silica shell of the satellite unit microcarrier contains a bridging structure with weak acetal conformation bonds. When the molecular anchoring chain transmits concentrated stress, the shell can undergo point-to-point fracture in the weak bond region, triggering structural disintegration and thus prompting the in-situ release of the first enzyme mixture encapsulated inside at the stress concentration point. This stress-response-based mechanical release mechanism overcomes the slow release problem caused by passive diffusion relying on concentration gradients in traditional encapsulation systems, and helps to rapidly form an effective enzymatic reaction center in the core region where amylopectin initially crystallizes.

[0016] 3. The core unit microcarrier utilizes a polymeric gel network grafted with phenylboronic acid functionalized fragments, which can generate a specific competitive complexation response to the maltose structure produced by the enzymatic hydrolysis of the first enzyme group. When the local accumulation of the first enzyme group product reaches a certain concentration, maltose molecules can replace the original phenylboronic acid ester cross-linking bonds, causing the gel network to liquefy and release the second enzyme group. This chemical decoding mechanism ensures that the release of the secondary enzyme is strictly dependent on the concentration conditions of the primary reaction products, providing reasonable timing control for multi-enzyme synergy and reducing the risk of efficiency loss due to premature contact between debranched enzyme products and lipases.

[0017] 4. The specific lipase released by the second enzyme group can degrade endogenous lipids in the food system to generate monoglycerides, and guide them to spontaneously assemble with amylose residues accumulated in the primary reaction to form a dense starch-lipid three-dimensional network polymer. This polymer can occupy the microscopic space required for the secondary crystallization of residual starch grains in a physical filling manner, structurally hindering the further ordered rearrangement of starch molecular chains, thereby delaying starch retrogradation and improving quality during long-term storage of baked goods. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. The drawings are used to provide a further understanding of the present invention.

[0019] Figure 1 This discloses a schematic diagram of the framework in the embodiments of this application.

[0020] Figure 2 This discloses a flowchart of an embodiment of this application. Detailed Implementation

[0021] The following is in conjunction with the appendix Figure 1 - Figure 2 A preferred description of the present invention is provided below.

[0022] See attached document Figure 1 - Figure 2 This invention proposes a quality management system for anti-aging of baked goods based on the synergistic effect of compound enzymes, comprising the following modules: The core unit microcarrier preparation module obtains an aqueous solution of the second enzyme group, crosslinks a preset polymer network with a preset phenylboronic acid fragment and encapsulates the aqueous solution of the second enzyme group to generate a core unit microcarrier. The satellite unit microcarrier synthesis module obtains the first enzyme group mixture, prepares a brittle silica shell with preset weak bonds to encapsulate the first enzyme group mixture, grafts a preset amylose fragment to construct a molecular anchoring chain, and generates a satellite unit microcarrier. The topology assembly module drives the preset short peptide crosslinking arms to connect the core unit microcarrier and the satellite unit microcarrier, generating a core satellite topology composite micro-nano carrier system. The matrix interface construction module integrates the core satellite topology composite micro-nano carrier system into a preset matrix raw material for baking and cooling, generating an initial matrix for baked goods containing a physical monitoring interface; The first enzyme release module extracts the contraction force released from the initial matrix of baked goods, and conducts the contraction force to cause the satellite unit microcarrier to disintegrate and release the first enzyme mixture, which catalyzes the generation of maltose-specific molecular groups. The second enzyme release module drives the maltose-specific molecular group to undergo a substitution reaction with the cross-linking sites in the core unit microcarrier, thereby releasing the second enzyme aqueous solution into the starch retrogradation core region. The barrier generation module mobilizes the second enzyme group's aqueous solution to degrade lipid molecules to generate a monoglyceride molecular layer, and guides the monoglyceride molecular layer to interact with the preset starch residue to generate a three-dimensional network polymer of starch lipids.

[0023] In one embodiment of the present invention, the core unit microcarrier fabrication module is used to perform the following operations: Maltose α-amylase and specific lipase were mixed and dissolved to generate an aqueous solution of the second enzyme group; a pre-set phenylboronic acid fragment was used to perform targeted cross-linking on the alginate solution to form a polymeric gel network system as the pre-set polymeric network; the aqueous solution of the second enzyme group was injected into the polymeric gel network system and ionized gelled to generate the core unit microcarrier.

[0024] Specifically, this embodiment discloses a process for preparing a gel core microcarrier carrying a second enzyme product, used to construct a core unit microcarrier with competitive dissociation response to a specific oligosaccharide. The process first obtains high-purity maltose α-amylase and a specific lipase derived from Aspergillus oryzae, both stored in lyophilized powder form.

[0025] On a thermostatic magnetic stirrer, a predetermined mass ratio of... The two enzymes mentioned above were added to a volume of In a phosphate buffer solution. Wherein, the predetermined mass ratio The aim is to balance the synergistic relationship between the initial hydrolysis product formation rate and the subsequent lipid modification; the pH of this phosphate buffer solution is [value missing]. This pH range is an overlapping window that maintains the stable activity of both enzymes and the stable structure of the phenylboronic ester bond.

[0026] temperature Low speed stirring The enzyme powder is dissolved and evenly distributed over a period of time until it is completely dissolved, thus obtaining the second enzyme group aqueous solution. The maltose α-amylase has an activity unit of no less than 1500 U / mg to ensure efficient treatment of amylopectin hydrolysates; the specific lipase has an activity unit of no less than 100 U / mg, which acts on triglycerides in the flour matrix.

[0027] Meanwhile, a separate alginate solution was prepared, with the molecular weight range being [missing information]. Sodium alginate powder was dissolved in deionized water to form a solution with a mass concentration of [missing value]. A homogeneous polymer solution was prepared. Subsequently, an amount of [amount missing] was introduced into the alginate solution. The crosslinking agent and its mass are 3-Aminophenylboronic acid salt is used as a functionalized segment of phenylboronic acid. The crosslinking agent is a composition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, which drives a covalent coupling reaction between the amino group of 3-aminophenylboronic acid salt and the carboxyl group of alginate, grafting the phenylboronic acid functional group onto the alginate molecular chain. The quality is determined by the proportion of carboxyl groups in the alginate to generate an appropriate number of response sites.

[0028] This targeted cross-linking action occurs at a pH value of In an environment of continuous After a certain period of time, anhydrous calcium chloride, a secondary crosslinking agent, is used to perform ionogelation, thereby forming a polymeric gel network system with a specific affinity for cis-diphenol hydroxyl groups. Before the polymeric gel network system is completely solidified, the aqueous solution of the second enzyme group prepared above is injected into the alginate solution at a constant flow rate using a microfluidic device, and the two are thoroughly mixed.

[0029] Finally, this mixture is dripped through a micron-sized nozzle to a final concentration of [missing information]. In an anhydrous calcium chloride curing bath, the mixed droplets solidify instantaneously, thereby sealing the entire aqueous solution of the second enzyme group inside. After time-curing treatment, the material is filtered through a 200-mesh stainless steel screen and washed several times with deionized water to remove residual ions on the surface. Finally, it is vacuum freeze-dried to obtain the core unit microcarrier that maintains a tight closed defense state and has a uniform particle size distribution.

[0030] In the aforementioned preparation process, some key process parameters were set as the enzyme mass ratio. The volume of the phosphate buffer solution was set within the range of 1:2 to 2:1. Typically 10-50 mL, Set to 6.5-7.5; stirring temperature The temperature should be controlled between 4-10℃ to prevent enzyme deactivation due to localized overheating during dissolution. Stirring time should also be controlled. The time is 20-40 minutes. The molecular weight range of alginate is... The preferred viscosity range is 150-250 kDa, as this range is beneficial for the formation and structural stability of the microspheres; its mass concentration The concentration should be 1.5-2.5% w / v; too low a concentration will result in a loose network, while too high a concentration will affect the fluidity of the solution. The mass of 3-aminophenylboronic acid salt... Feeding should be carried out at 5-15% of the molar amount of carboxyl groups in the alginate. Coupling reaction. The value is 4.5-5.5, and the reaction time is... The curing time is 12-24 hours. The final calcium ion concentration in the anhydrous calcium chloride curing bath... The concentration was set at 0.1-0.3 mol / L, which ensures rapid and sufficient ionic cross-linking and curing, and the curing time... For 30-60 minutes.

[0031] In a specific application scenario, to prepare a batch of core unit microcarriers, 100 mg of maltose α-amylase powder with an enzyme activity of 1500 U / mg and 100 mg of specific lipase powder with an enzyme activity of 100 U / mg are weighed and added to a beaker placed in an ice-water bath. The beaker contains 20 mL of 0.1 mol / L phosphate buffer solution with a pH of 7.0.

[0032] A magnetic stirrer was started and stirred at 200 r / min for 30 min to obtain a clear and transparent aqueous solution of the second enzyme group. In another beaker, 2 g of sodium alginate with a molecular weight of 200 kDa was dissolved in 98 mL of deionized water and stirred until completely dissolved to obtain an alginate solution with a mass concentration of 2.0% w / v. 100 mg of N-hydroxysuccinimide and 190 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added to the alginate solution. After they dissolved, 125 mg of 3-aminophenylborate salt powder was added. The pH of the mixed solution was adjusted to 5.0, and the reaction was carried out at room temperature in the dark for 18 h.

[0033] After the reaction, 10 mL of the second enzyme group aqueous solution was slowly injected into the modified alginate solution and gently mixed. Using a syringe pump, the mixed enzyme solution was dripped into 500 mL of 0.2 mol / min anhydrous calcium chloride solution through a 0.5 mm needle for solidification, with continuous slow stirring during the dripping process. Upon contact with the calcium chloride solution, the droplets formed white gel microspheres, which solidified for 45 min. After the reaction, the microspheres were collected by filtration through a Buchner funnel, washed three times with 500 mL of deionized water, and then freeze-dried at -50 °C for 24 h, finally yielding approximately 2.2 g of white powdery core unit microcarriers with a particle size of 1.8 µm, which completely encapsulated the second enzyme group aqueous solution.

[0034] In one embodiment of the present invention, the satellite unit microcarrier synthesis module is used to perform the following operations: Debranching enzyme and β-amylase are mixed to generate the first enzyme group mixture; an interfacial condensation reaction is carried out by tetraethyl orthosilicate and acetal-bridged bissilane precursor to generate a brittle silica shell with a preset weak bond and encapsulate the first enzyme group mixture; low-polymerization degree non-crystalline amylose fragments are grafted at high density onto the outside of the brittle silica shell as preset amylose fragments to construct molecular anchoring chains and generate satellite unit microcarriers.

[0035] Specifically, this embodiment further discloses a method for synthesizing a silicon-shell carrier loaded with the first enzyme product. This method aims to ultimately construct a satellite unit microcarrier capable of responding to micro-stress during crystallization through mechanical weak bonds and spatial recognition and conduction mechanisms. The process first involves preparing a mixture of the first enzyme group, combining a debranched enzyme derived from *Bacillus stearothermophilus* and β-amylase extracted from barley in a specific ratio of enzyme activity units. At pH value The enzymes were dissolved in acetate buffer to obtain the first enzyme mixture. The debranching enzyme in the mixture was used to cleave the α-1,6 glycosidic bonds of amylopectin, and the β-amylase was used to cleave the α-1,4 glycosidic bonds from the non-reducing end to produce maltose.

[0036] Simultaneously, a brittle silica shell material was prepared using a reverse microemulsion method. In a reaction vessel, an oil-phase system consisting of a surfactant and a non-polar solvent was prepared. Then, the first enzyme mixture was used as the aqueous phase and dispersed in the oil phase under high-speed shearing to form stable microemulsion droplets.

[0037] Tetraethyl orthosilicate was used as the main structural precursor and incorporated in a specific molar ratio. An acetal-bridged bissilane precursor was used, and this mixed silane precursor was slowly added dropwise to a microemulsion system. Ammonia was used as a catalyst at a specific temperature. The reaction initiates an interfacial condensation reaction, causing the silane precursor to hydrolyze and condense on the surface of the aqueous droplet, forming a silica network structure. The acetal-bridged bissilane precursor contains pre-defined weak acetal conformations sensitive to mechanical stretching, and its copolymerization and embedding within the silica framework imparts the material's inherent brittleness. The reaction continues... After a period of time, the mixture was centrifuged and washed alternately with ethanol and deionized water to obtain the initial silica-shell carrier containing the first enzyme group mixture.

[0038] The obtained initial silicon-shell carrier was surface functionalized by grafting high-density molecular anchoring chains onto its outer surface. The silanol groups on the silicon-shell surface were activated by hydrolysis or acid treatment, followed by amination modification using aminopropyltriethoxysilane as a coupling agent. Soluble amylose was then enzymatically degraded and purified using size exclusion chromatography to obtain polymers with a degree of polymerization ranging from [insert value here]. The low-polymerization-degree amorphous amylose fragments have a polymerization degree range that ensures effective entanglement of the starch network in the matrix to transmit tension, while also preventing crystallization due to their low polymerization degree, thus avoiding interference with the triggering mechanism.

[0039] Finally, the aminated silica shell was covalently linked to a low-polymerization-degree amorphous amylose fragment in a suitable buffer solution. This process was carried out at a temperature... Next After a certain period of time, the microcarriers were washed and dried, resulting in satellite unit microcarriers with densely distributed molecular anchoring chains on their surface. These microcarriers exhibited anisotropic and fragile properties due to the implantation of weak bonds in the pre-defined acetal conformation and the stress concentration effect. The anisotropic and fragile properties here refer to the microcarriers exhibiting an extremely low fracture threshold for directional tensile stress transmitted through the molecular anchoring chains, while demonstrating high tolerance to isotropic hydrostatic pressure.

[0040] In the aforementioned preparation process, the optimal setting for each process parameter is the ratio of enzyme activity units between the two components. The ratio is typically controlled between 1:5 and 1:10 to ensure effective cleavage of crystalline side chains while rapidly generating signal molecules; acetate buffer... Value is 5.0-6.0. The molar ratio of acetal-bridged bissilane precursors, such as bis(trimethoxysilylpropyl)methylacetal, to tetraethyl orthosilicate. Set to 0.1-0.3, this ratio determines the density of weak bonds in the shell and the final mechanical response threshold. The temperature of the interfacial condensation reaction. Maintain at 25-40 ℃, reaction time The time is 6-12 h. The degree of polymerization range of low-polymerization-degree amorphous amylose fragments. The temperature was set between 15 and 30. The surface grafting density of the molecular anchoring chains was controlled by adjusting the concentration of aminopropyltriethoxysilane, with a target density of no less than 100 molecular chains per square 100 nanometers of surface area. The temperature of the covalent grafting reaction was also set. 20-30℃, time It lasts 12-24 hours.

[0041] In a specific application scenario, to prepare satellite unit microcarriers, 1000 U of debranching enzyme and 8000 U of β-amylase were first dissolved in 10 mL of 0.2 mol acetate buffer at pH 5.5 to prepare the first enzyme group mixture. In a 250 mL beaker, 2 g of Span 80 surfactant was dissolved in 100 mL of cyclohexane, and then the above 10 mL of the first enzyme group mixture was added. The mixture was then emulsified using a homogenizer at 10000 r / min for 5 min to form a homogeneous W / O oil-in-water reverse microemulsion.

[0042] Under magnetic stirring, a mixed silane solution consisting of 5 mL of tetraethyl orthosilicate and 1.3 mL of bis(trimethoxysilylpropyl)methyl acetal was slowly added dropwise to the emulsion. After the addition was complete, 2 mL of concentrated ammonia was added, and the system was sealed and reacted in a water bath at 30 °C for 8 h. After the reaction was completed, the emulsion was centrifuged... The precipitate is collected by relative centrifugal force, wherein, The acceleration due to gravity is represented by the number of particles, and the particles are washed five times with ethanol and water in sequence. The resulting silicon spheres are suspended in 50 mL of toluene, and 1 mL of aminopropyltriethoxysilane is added. The mixture is then refluxed at 80 °C for 6 h to carry out surface amination.

[0043] On the other hand, a 1% amylose solution was hydrolyzed with α-amylase at 50 °C for 2 h, and low-polymerization degree amorphous amylose fragments with a degree of polymerization (DP) of approximately 25 were collected by column chromatography and freeze-dried to obtain a white powder. Finally, 1 g of aminated silica spheres were dispersed in phosphate buffer containing 2 g of amylose fragments, and a reductive amination reaction was carried out by adding sodium cyanoborohydride at 25 °C for 24 h. The product was centrifuged, washed, and freeze-dried to obtain approximately 1.05 g of uniform white powdery satellite unit microcarriers with an average particle size of approximately 5 µm and a shell wall thickness of 500 nm.

[0044] In one embodiment of the present invention, the topology assembly module is configured to perform the following steps: The core unit microcarrier and satellite unit microcarriers are co-dispersed and injected into a mild hypertonic buffer system to form a mixed suspension system. Short peptide molecules are introduced into the mixed suspension system as pre-set short peptide cross-linking arms. The surface of the core unit microcarrier and the ends of the short peptide molecules are activated by a chemical coupling agent. One end of the pre-set short peptide cross-linking arm is covalently connected to the core unit microcarrier, and the other end is bound to multiple satellite unit microcarriers to generate a core-satellite topology composite micro-nano carrier system.

[0045] Specifically, this embodiment assembles the aforementioned two sets of functional microcarriers with causal interlocking relationships. By introducing short peptide chains as spatial connection media, a composite micro / nanocarrier system with core satellite topological structure characteristics is generated. This process selects the core unit microcarrier and satellite unit microcarriers prefabricated in previous steps, and stores them in dry powder form at a predetermined mass ratio. Weighing was performed. Then, the two microcarrier powders were added together to a reaction vessel containing a hypertonic buffer solution. An additional solution of a concentration of [missing information] was added to this buffer solution. Nonionic osmotic pressure regulators, such as sucrose or glycerol, are designed to inhibit excessive swelling of the core unit microcarrier during aqueous phase reactions.

[0046] Dispersion by low-power ultrasound The reaction proceeds for several seconds, allowing the two microcarriers to suspend uniformly, thus forming a stable mixed suspension system. Based on this, short peptide molecules are added to the mixed suspension system as flexible cross-linking arms, followed by the sequential addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide as chemical coupling agents. This reaction system is maintained at a pH of [value missing]. and temperature The process is carried out under specific conditions. The chemical coupling agent first activates the residual carboxyl groups on the outer surface of the core unit microcarrier and the carboxyl ends of the short peptide flexible crosslinking arms themselves. The activated carboxyl ends of the short peptide molecules react with the modified amino groups on the outer wall of the satellite unit microcarrier to form stable amide bonds, thereby achieving the connection between the short peptide and the satellite unit.

[0047] Simultaneously, the amino terminus of the short peptide molecule reacts with the activated carboxyl groups on the surface of the core unit microcarrier, forming amide bonds and completing the connection between the core unit and the short peptide. By controlling the feed ratio, one end of each short peptide's flexible crosslinking arm is covalently attached to the outer polymer network of a core unit microcarrier, while the other end forms multi-site branches to bind to the silica outer walls of multiple satellite unit microcarriers, thus constructing a microscopic topology with a core at the center and satellites surrounding it. The reaction continues. After a period of time, the product was purified by centrifugation and filtration. The reaction mixture was transferred to ultrafiltration centrifuge tubes with specific molecular weight cutoff values. Through multiple centrifugation and buffer replacement operations, unreacted short peptide flexible cross-linking arms, residual coupling agents, and other free molecular entities were effectively eluted from the system. The washed product was then freeze-dried to dehydrate, and finally purified to obtain a core satellite topology composite micro / nano carrier system that combines spatial attachment and chemical function.

[0048] In the aforementioned assembly process, the various proportions and environmental parameters are set as follows: the mass ratio of the core unit microcarrier to the satellite unit microcarrier. Set within the range of 1:0.3 to 1:0.8, this ratio aims to ensure that each core unit can covalently link 5-15 satellite units, forming an effective local functional cluster. The hypertonic buffer system is preferably a 0.05-0.1M 2-(N-morpholino)ethanesulfonic acid buffer solution. The pH value was set between 5.5 and 6.5, an environment that maintained the enzyme's biological activity while providing suitable acid-base conditions for the coupling reaction. The dispersion time using low-power ultrasound... The reaction time should be controlled within 30-90 s. The short peptide flexible crosslinking arm is preferably a polypeptide chain containing 10-20 amino acid residues, such as a poly(glycine-serine) sequence, with amino and carboxyl groups at both ends suitable for coupling reactions. Its flexible structure allows the satellite unit to have peripheral space. The temperature of the coupling reaction... Control the temperature between 4-25 °C, and the reaction time The time is 12-24 hours. The molecular weight cutoff of the ultrafiltration centrifuge tube is 100-300 kDa. This size can retain composite micro / nano carriers with huge molecular weights, while allowing small molecular weight impurities to pass through the filter membrane.

[0049] In a specific application scenario, to assemble a composite micro / nano carrier system for the core satellite topology structure, 220 mg of the prepared core unit microcarrier powder and 105 mg of the prepared satellite unit microcarrier powder were weighed. Both were placed in a 50 mL Erlenmeyer flask, and 20 mL of 0.1 M 2-(N-morpholino)ethanesulfonic acid buffer (pH 6.0) containing 0.2 mol of sucrose was added. The Erlenmeyer flask was then treated with an ultrasonic cleaner for 60 s to form a uniformly dispersed suspension. Subsequently, 8 mg of a short peptide flexible cross-linked arm consisting of the sequence (Gly-Ser)5 was added to the system in an ice bath. After dissolution, 40 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 22 mg of N-hydroxysuccinimide were added. The entire reaction system was placed on a shaker at 4 °C and reacted at 100 r / min in the dark for 24 h.

[0050] After the reaction was complete, the mixture was aliquoted into several ultrafiltration centrifuge tubes with a molecular weight cutoff of 200 kDa. Centrifuge for 15 min under relative centrifugal force. Discard the filtrate, resuspend the precipitate in fresh buffer, and repeat the centrifugation and washing process three times. Finally, wash once with deionized water, pre-freeze the collected product at -80 °C, and then freeze-dry for 48 h to obtain 312 mg of a pale yellow, loose powder core satellite topology composite micro / nano carrier system.

[0051] In one embodiment of the present invention, the matrix interface construction module is used to perform the following steps: The core satellite topology composite micro-nano carrier system is uniformly kneaded into the preset matrix raw material in the form of solid powder to form a mixed dough. The mixed dough is then subjected to high-temperature baking to drive starch gelatinization, while maintaining the topology of the core satellite topology composite micro-nano carrier system. The heated product is then guided to cool down to produce double-helix shrinkage crystallization, which causes the matrix itself to reconstruct its network and become entangled around the molecular anchoring chain, generating an initial matrix for baked goods containing a physical monitoring interface.

[0052] Specifically, this embodiment integrates the core satellite topology composite micro / nano carrier system into the dough processing flow to create an initial matrix for baked goods containing monitoring feature interfaces. This process first utilizes the matrix raw materials required for the baking process, such as flour, drinking water, yeast, and sugar. The composite micro / nano carrier system, purified into a solid powder form in the previous stage, is then added in a specific proportion based on the weight of the flour. The yeast is premixed with flour and other dry matrix ingredients in a mixing container, and stirring is used to ensure uniform dispersion in the flour matrix. Then, a measured amount of water and activated yeast are added, and a dough mixer is started to perform a kneading program until the gluten network in the flour expands, forming a homogeneous dough embryo encapsulating the composite micro-nano carrier system. After proofing, the shaped dough embryo is subjected to high-temperature baking within a specific temperature range.

[0053] The temperature and time parameters of this process are designed to drive the starch granules in the flour matrix to absorb water and swell, ultimately achieving a starch gelatinization state in the matrix network. During this high-temperature stage, the core and satellite units constituting the composite micro / nano carrier system maintain their intact topology and morphology due to their inherent high thermal stability.

[0054] Specifically, the silica shell of the satellite unit microcarrier and the cross-linked alginate gel network of the core unit microcarrier maintain stable chemical bonds at the above baking temperature, without melting, decomposition or significant changes; and the maintenance of its internal enzyme activity depends on the effective protection of the low-hydration gel and silica shell, which isolates the direct action of water vapor at high temperature, thereby ensuring that the internally encapsulated enzyme products do not undergo thermal inactivation or premature leakage.

[0055] After baking, the heated product is removed from the oven and placed in room temperature storage, where its internal temperature gradually decreases. As the temperature drops, the gelatinized starch molecules, especially amylopectin, begin to rearrange their molecular chains, undergoing a double-helix contraction and crystallization process of the primary complex. During this process, the reconstructing matrix's own starch network tightly entangles and attaches to the densely distributed molecular anchoring chains on the surface of the satellite unit microcarriers. This molecular-level physical entanglement establishes a mechanical conduction path between the composite micro / nanocarrier system and the baked food matrix, thereby generating a mutually restraining molecular-level physical monitoring interface. The formation of this interface allows the spontaneously generated micro-stress within the food matrix to be effectively captured and conducted.

[0056] During the aforementioned integration process, the protein content of the flour in the matrix raw material should be no less than 13.0% to ensure that the dough has good extensibility and gas encapsulation ability. The addition ratio of the core satellite topology composite micro / nano carrier system... The concentration is typically set between 0.05% and 0.5% of the flour weight. This range represents a balance between anti-aging efficacy and dough rheological properties. If it is below 0.05%, the density of the 'monitoring nodes' deployed by the microcarriers within the dough is insufficient, making it impossible to effectively capture the microscopic stresses in the early stages of starch retrogradation. If it is above 0.5%, excessive micro- and nano-particles will interfere with the cross-linking network of gluten protein macromolecules through steric hindrance, resulting in a decrease in the specific volume of the baked food and a rough texture.

[0057] High-temperature baking within a specific temperature range typically refers to baking the dough in an oven with a bottom temperature of 210-230 ℃ and a top temperature of 190-210 ℃ for 20-30 minutes, ensuring that the center temperature of the dough reaches and exceeds the critical temperature for complete starch gelatinization, i.e., 95-98 ℃. Room temperature storage refers to storing the product at an ambient temperature of 20-25 ℃ and a relative humidity of 50-65%. These environmental parameters not only simulate the actual shelf-life storage scenario of commercially available baked goods to the greatest extent possible, but more importantly, the 20-25 ℃ range is precisely the high-thermal-mechanical window for the nucleation and crystallization of the amylopectin double helix structure, effectively triggering the mechanical tensile force sensing mechanism designed in this system.

[0058] In a specific application scenario, to prepare the initial matrix for baked goods, 500g of flour was used as a baseline. The obtained 312mg core satellite topology composite micro-nano carrier system powder was dry-mixed with 500g of flour, 6g of salt, 10g of yeast, and 25g of sugar in the mixing bowl of a dough mixer for 3 minutes. Subsequently, 300g of 30℃ warm water was added, and the dough was kneaded at low speed for 5 minutes, then at medium-high speed for 10 minutes, until the dough could be stretched into a strong thin film. The dough was then fermented for the first time at 35℃ and 80% relative humidity for 60 minutes.

[0059] After fermentation, divide the dough, round it, and let it rest for 15 minutes. Then shape it into the size of the mold. Place it in a loaf pan and let it rise a second time for about 50 minutes under the same temperature and humidity. Preheat the oven to 200°C top temperature and 220°C bottom temperature. Bake the risen dough for 25 minutes. Use a temperature probe to measure the center temperature of the bread; if it reaches 97°C, it indicates that the starch has been completely gelatinized.

[0060] The baked bread is removed from the mold and placed on a cooling rack to cool naturally to room temperature (24°C). During cooling and subsequent storage, the branched starch molecules inside the bread spontaneously recrystallize. Simultaneously, the composite micro / nano carrier is evenly distributed throughout the bread core, and its surface molecular anchoring chains form tight physical entanglements with the recrystallizing starch molecules. Thus, a molecular-level physical monitoring interface capable of sensing starch aging stress at the microscopic level is constructed inside the finished bread, creating the initial matrix for baked goods and laying the structural foundation for subsequent autonomous anti-aging processes.

[0061] In one embodiment of the present invention, the first enzyme release module is configured to perform the following steps: Relying on the constraint effect of the physical monitoring interface, the shrinkage force is reversed to the connection anchor point of the satellite unit microcarrier. The shrinkage force is effectively transmitted through the physical entanglement generated by the non-crystalline amylose fragments and the food matrix network. The transmitted shrinkage force causes the brittle siliceous shell to encounter stress concentration, tearing the preset weak bonds and causing the satellite unit microcarrier to disintegrate, releasing the first enzyme mixture. The first enzyme mixture is controlled to shear and recrystallize the amylopectin side layer connecting chains, catalyzing the production of free short chains and their aggregation, generating maltose-specific molecular groups.

[0062] Specifically, this embodiment describes the cascade reaction process in which the aforementioned system passively triggers and executes primary anti-aging functions within the food matrix. When starch retrogradation occurs within the initial matrix of baked goods during storage, the branched starch molecules within it begin to aggregate and transform into a microcrystalline structure. During this ordering process, due to the elimination of water molecules and the reconstruction of the hydrogen bond network, the intermolecular distance shortens, releasing extremely small volumetric shrinkage forces, i.e., endogenous forces. Through the constructed molecular-level physical monitoring interface, this force is effectively collected and amplified by the constraint effect of the molecular anchoring chains, and then transformed into piezoelectric tension transmitted along the molecular chain direction, which is then channeled back to the connection anchor points of the various satellite unit microcarriers connected to it.

[0063] When tension is continuously conducted and concentrated on the brittle silica shell of the satellite unit microcarrier, stress becomes highly concentrated in the regions of pre-embedded, pre-defined acetal conformation weak bonds due to the discontinuity of the material geometry and the differences in weak bond regions of the chemical composition. The fracture threshold energy of the pre-defined acetal conformation weak bonds is designed to be lower than the bond energy of the Si-O-Si bonds in the silica framework, ensuring the precision and controllability of the fracture process.

[0064] Once the accumulated stress exceeds the chemical bond breaking threshold of the weak bonds in the preset acetal conformation, these weak bonds will undergo irreversible tearing, triggering a chain reaction of mechanical collapse and disintegration of the entire microcarrier shell. This releases the entire first enzyme mixture, which was completely sealed inside, into the surrounding matrix voids. Upon release, the debranching enzymes and β-amylases in the mixture diffused into the external environment rapidly come into contact with the side-layer linkages of the amylopectin undergoing recrystallization and undergo synergistic hydrolytic shearing.

[0065] In this process, debranching enzymes first cleave the α-1,6-glycosidic bonds of amylopectin, exposing more non-reducing ends. Subsequently, β-amylase efficiently hydrolyzes the α-1,4-glycosidic bonds from these ends, effectively increasing the reaction rate. Within a narrow space of tens of micrometers around the disintegration point of the satellite unit microcarrier, a large number of free short chains are instantaneously catalyzed and produced, mainly maltobiose and a small amount of low-polymerization maltooligosaccharides. These short chains rapidly aggregate due to limited diffusion, ultimately forming an ultra-high concentration of maltose-specific molecular clusters.

[0066] In this process, the ultra-high concentration of maltose-specific molecular clusters refers to the instantaneous molar concentration of maltose molecules reaching tens to hundreds of millimoles per liter in localized regions at the micrometer scale, far exceeding the background concentration of other soluble sugars in the food matrix, thus providing chemical signals for the next step of chemical decoding. Pebenewton-level tension refers to the tensile force that a single molecular anchoring chain can transmit, typically in the range of 10-100 pN. The synergistic effect of multiple anchoring chains can amplify this force to the nanonewton level.

[0067] In a specific application scenario, the initial matrix of baked goods stored at 24 °C exhibited significant starch retrogradation in a microregion after 36 hours of storage. The double-helix shrinkage and crystallization process of amylopectin within this region stretched the surrounding molecular anchoring chains. Assuming that the five satellite unit microcarriers on a single core satellite topology composite micro / nanocarrier system were involved in this process, approximately 500 molecular anchoring chains on the surface of each satellite unit microcarrier were subjected to traction, with each anchoring chain transmitting an average tension of 60 pN, resulting in a total tensile force of approximately 30 nN received by each microcarrier.

[0068] This tensile force is concentrated on the weak bonds of the pre-defined acetal conformation within the brittle silica shell, exceeding its set fracture threshold of 25 nN. The 25 nN threshold is based on the fact that the fracture force of a single covalent bond, such as a Si-O bond, is typically on the order of several nanonewtons, while the instantaneous cumulative stress generated at the nanoscale by the contraction of the starch double helix can reach tens of nanonewtons. 25 nN is located at the critical energy overlap zone between the irreversible contraction period of starch nucleus growth and the collapse of the silica shell structure, thus achieving a mechanical threshold switching effect, causing the shells of the five satellite unit microcarriers to mechanically collapse almost simultaneously.

[0069] Based on the geometric parameters of the previous embodiment, the particle size is 5 µm, the shell thickness is 500 nm, and the internal volume of each satellite unit microcarrier is approximately 33.5 fL, thereby releasing a first enzyme mixture of approximately 33.5 fL. A total of approximately 167.5 fL of enzyme solution is injected into a matrix microporous network with a radius of approximately 20 µm centered on the disintegration point.

[0070] The debranching enzyme in the enzyme solution worked synergistically with β-amylase to rapidly hydrolyze the branched-chain amylose glycosidic bonds at local contact sites within 60 seconds. Five satellite units released a total of 167.5 fL of enzyme solution, catalyzing the production of approximately [amount missing]. The maltose content allows for an instantaneous local concentration of approximately 143 mmol / L within the release micro-region. This concentration constitutes an ultra-high concentration of maltose-specific molecules, preparing a highly specific and concentrated chemical signal for the subsequent steps that will be triggered.

[0071] In one embodiment of the present invention, the second enzyme release module is configured to perform the following steps: The maltose-specific molecular clusters are driven to cross the spatial distance defined by the pre-defined short peptide cross-linking arms, fully coating and wetting the surface of the core unit microcarrier. The concentration gradient of the maltose-specific molecular clusters is limited by the nanoscale spatial distance defined by the short peptide cross-linking arms. The maltose-specific molecular clusters are driven to intervene in the cross-linking sites to undergo an irreversible strong complexation and substitution chemical reaction, severing the cross-linking sites. Severing the cross-linking sites causes the core unit microcarrier to liquefy and unblock, releasing the second enzyme group aqueous solution into the starch retrogradation core region.

[0072] Specifically, this embodiment describes a secondary chemical decoding and release process triggered by a primary mechanical fracture cascade. The high-concentration maltose-specific molecular clusters generated in the aforementioned steps, due to the extremely short spatial distance between their generation location and the core unit microcarrier, which is part of the overall topological structure, defined by short peptide flexible cross-linking arms, are constrained to preferentially and densely contact the protective outer shell surface of the core unit microcarrier during diffusion, thereby achieving panoramic coverage and submersion of the core carrier.

[0073] This extremely short spatial distance structure design improves signal transduction efficiency and further reduces the escape and dilution of signal molecules; the spatial distance is limited to between 2 and 10 nm. Under this high-concentration gradient field environment, the high-concentration maltose-specific molecular group, through the cis-dihydroxy groups present in its molecular structure—that is, the conformation in which the C2 and C3 or C3 and C4 hydroxyl groups of the glucose unit in the maltose molecule are in the same plane—intervenes in the phenylboronic acid cross-linked stable framework of the polymer gel network system that originally constructed the core unit microcarrier.

[0074] At this point, maltose molecules penetrate deep into the polymeric gel network of the core microcarrier. Subsequently, maltose undergoes a strong complexation substitution reaction with the phenylboronic acid crosslinking sites in the network. The essence of this substitution reaction is that the affinity of maltose is much higher than that of the polyol on which the crosslinking in the gel network depends. This polyol is the hydroxyl group of alginate itself, which causes the phenylboronic acid ester bond to be opened, and phenylboronic acid instead forms a more stable five- or six-membered ring complex with maltose.

[0075] The disintegration of multiple satellite unit microcarriers generates a massive amount of maltose, causing almost all key cross-linking sites within the polymeric gel network system to be severed. This systematic collapse of the cross-linking structure leads to a loss of rigidity and a sharp decline in water-holding capacity within the polymeric gel network system, manifesting as a macroscopic liquefaction phenomenon in terms of physical properties, thus releasing its original three-dimensional morphological constraints. The second enzyme group aqueous solution, which had been sealed within and was poised to be released, is therefore fully released and diffuses outward along the microchannel network with higher osmotic pressure due to maltose generation. It is then dripped to the origin of this series of cascade reactions, namely the starch retrogradation core region at the forefront of the current aging process.

[0076] In this process, the strong complex substitution chemical reaction is dynamically reversible relative to the original equilibrium between alginate and phenylboronic acid esters when there is no high concentration of competing small molecules; however, under the impact of maltose at a level of tens of millimoles per liter, the reaction equilibrium is pushed toward the formation of phenylboronic acid-maltose complex.

[0077] In specific application scenarios, five disintegrating satellite unit microcarriers generate a high concentration of maltose-specific molecules (up to 143 mmol / L) around them. Because these molecules are tethered to the central core unit microcarrier via their respective short peptide flexible cross-linking arms, and the microcarriers have a particle size of 1.8 µm, maltose molecules rapidly penetrate into the polymer gel network system with an average pore size of 10-20 nm. Upon contact with the phenylboronic acid sites of the cross-linked alginate polymer network, the equilibrium constant of the complexation reaction between the cis-dihydroxyl groups on the maltose molecules and phenylboronic acid is much greater than that of the alginate hydroxyl groups. Specifically, the equilibrium constant of the complexation reaction is... Alginate hydroxyl group is .

[0078] At a maltose concentration of 143 mM, this substitution reaction was strongly driven, resulting in the breakage of over 99% of the phenylboronic acid ester crosslinks in the core microcarrier gel network within minutes. The gel framework of the core microcarrier subsequently disintegrated, unable to support its spherical structure, and transformed from a solid gel into a very low-viscosity liquid. Approximately 3.1 fL of the second enzyme group aqueous solution, encapsulated within the core microcarrier, was then released, containing approximately 0.1 mU of maltose α-amylase and 0.007 mU of specific lipase. These enzyme solutions flowed along a path established by the maltose concentration gradient to the starch retrogradation core region with a radius of approximately 20 µm, preparing for the next step of deep molecular recombination engineering.

[0079] In one embodiment of the present invention, the barrier generation module is configured to perform the following steps: The specific lipase contained in the aqueous solution of the second enzyme group is activated to degrade the surrounding free and latent lipid molecules, and generate a monoglyceride molecular layer; the free amylose molecules that have been sheared off and accumulated in the mixture of the first enzyme group are captured as the pre-set starch fragments; the monoglyceride molecular layer and the pre-set starch fragments are promoted to perform thermodynamically stable entanglement and interaction, and solidify and deposit to generate a three-dimensional network polymer of starch lipids.

[0080] Specifically, this embodiment elucidates the profound catalytic effect of the second group of enzyme products released in the aforementioned cascade reaction and its barrier construction process. In the preceding steps, the specific lipase contained in the aqueous solution of the second group of enzymes, just released from the core region of the lesion, is rapidly activated. This lipase can efficiently degrade free lipid molecules, such as triglycerides, in its surrounding microenvironment. These lipid molecules typically originate from fats naturally present in flour or added during processing, and are solid or semi-solid at storage temperatures.

[0081] Through catalytic hydrolysis by specific lipases, the two ester bonds of triglyceride molecules are broken, leading to the large-scale in-situ derivatization of amphiphilic monoglyceride molecular layers. Simultaneously, the system captures and utilizes byproducts accumulated during primary aging, namely, numerous free amylose molecule fragments scattered in the matrix due to debranching enzyme cleavage.

[0082] Within specific micro-regions, specifically the area containing the newly formed monoglyceride molecular layer, these amylose molecular fragments spontaneously undergo a more thermodynamically stable entanglement and encapsulation process with the monoglyceride molecules. In this interaction, the hydrophobic helical core of the amylose molecules encapsulates the long fatty acyl chains of the monoglyceride molecules, while the hydrophilic outer surface of the amylose molecules interacts with the glycerol heads of the monoglyceride molecules. This molecular recognition and self-assembly process is driven by an increase in system entropy, forming a stable network that tends to decrease the total free energy of the system. Finally, the results of this series of interactions are used for solidification and in-situ deposition to generate a dense three-dimensional network polymer of starch lipids that cannot be degraded by the original enzyme system.

[0083] The stability of this polymer stems from the synergistic effect of multiple weak interactions, such as hydrophobicity, hydrogen bonding, and van der Waals forces. Once formed, its dense structure protects the internal glycosidic and ester bonds from subsequent enzymatic attack. This newly formed polymer physically occupies the microscopic space necessary for the secondary crystallization of residual starch through physical filling, i.e., it prevents the starch chains from effectively aligning and forming nuclei, and blocks the possible pathways for structural restructuring, thus constructing a three-dimensional spatial barrier that prevents secondary aging.

[0084] In this process, the broken-tail fragments of free amylose molecules typically have a degree of polymerization between 50 and 150. This degree of polymerization range represents the optimal fragment length for inducing the formation of highly stable inclusion complexes from monoglycerides. If the degree of polymerization is below 50, the starch molecule chain is too short to form a single-helix cavity capable of completely encapsulating the hydrophobic tail of the lipid. If the degree of polymerization is above 150, the rigidity and steric hindrance of the molecular chain increase dramatically, leading to a significant reduction in the self-assembly kinetics efficiency with monoglycerides. These fragments are linear polysaccharide fragments produced by debranching enzymes, which cannot be further hydrolyzed by β-amylase. These fragments are key raw materials for the formation of starch-lipid complexes.

[0085] In a specific application scenario, 0.007 mU of specific lipase in the aqueous solution of the second enzyme group, delivered to the starch retrogradation core region, acts on approximately 12 pg of microcrystalline triglycerides within this microregion within about 1 hour. The preset enzyme activity level here is significantly higher than the theoretical value for substrate consumption, designed to compensate for enzyme activity loss and diffusion inhibition effects in complex food matrices. The lipase efficiently hydrolyzes the substrate, ultimately retaining approximately 4.8 pg of monoglyceride molecules. These monoglyceride molecules form a molecular thin layer covering an area of ​​approximately 400 µm² in situ. Approximately 3 pg of amylose molecule fragments remain in the same region, with an average degree of polymerization of approximately 100.

[0086] Simultaneously with lipase activity, these amylose fragments rapidly entangle with newly formed monoglyceride molecules. The hydrophobic lumen of amylose, with a helical diameter of approximately 0.5 nm, precisely accommodates the saturated fatty acyl chains of the monoglyceride molecules, forming inclusion complexes. These inclusion complexes further aggregate, interconnecting through a network of intermolecular hydrogen bonds, depositing and solidifying into a dense starch-lipid three-dimensional network. This newly formed polymer network occupies all the microscopic gaps that could have been used for starch chain rearrangement. Its dense and robust structure physically blocks the approach and alignment of residual short-branched starch molecules, preventing them from forming new crystal nuclei. Calculations show that the porosity of this three-dimensional barrier is less than 5%, achieving long-term inhibition of the aging process in this localized area.

[0087] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should all be included within the protection scope of the present invention.

Claims

1. A quality management system for anti-aging of baked goods based on the synergistic effect of compound enzymes, characterized in that, include: The core unit microcarrier preparation module obtains an aqueous solution of the second enzyme group, crosslinks a preset polymer network with a preset phenylboronic acid fragment and encapsulates the aqueous solution of the second enzyme group to generate a core unit microcarrier. The satellite unit microcarrier synthesis module obtains the first enzyme group mixture, prepares a brittle silica shell with preset weak bonds to encapsulate the first enzyme group mixture, grafts a preset amylose fragment to construct a molecular anchoring chain, and generates a satellite unit microcarrier. The topology assembly module drives the preset short peptide crosslinking arms to connect the core unit microcarrier and the satellite unit microcarrier, generating a core satellite topology composite micro-nano carrier system. The matrix interface construction module integrates the core satellite topology composite micro-nano carrier system into a preset matrix raw material for baking and cooling, generating an initial matrix for baked goods containing a physical monitoring interface; The first enzyme release module extracts the contraction force released from the initial matrix of baked goods, conducts the contraction force to cause the satellite unit microcarrier to disintegrate and release the first enzyme mixture, catalyzing the generation of maltose-specific molecular groups; The second enzyme release module drives the maltose-specific molecular group to undergo a substitution reaction with the cross-linking sites in the core unit microcarrier, thereby releasing the second enzyme aqueous solution into the starch retrogradation core region. The barrier generation module mobilizes the second enzyme group's aqueous solution to degrade lipid molecules to generate a monoglyceride molecular layer, and guides the monoglyceride molecular layer to interact with the preset starch residue to generate a three-dimensional network polymer of starch lipids.

2. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, The generation of the core unit microcarrier includes the following steps: Maltose α-amylase was mixed and dissolved with a specific lipase to generate an aqueous solution of the second enzyme group; A polymeric gel network system was formed by using a pre-defined phenylboronic acid fragment to perform targeted cross-linking on an alginate solution, thus creating a pre-defined polymeric network. The aqueous solution of the second enzyme group was injected into the polymer gel network system and solidified by ion gelation to generate the core unit microcarrier.

3. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 2, characterized in that, The molding of a polymer gel network system, as a pre-designed polymer network, includes the following steps: Sodium alginate powder was obtained and dissolved in deionized water to form an alginate solution; A crosslinking agent and 3-aminophenylboronic acid salt were introduced into an alginate solution as a pre-defined phenylboronic acid fragment; The amino group of 3-aminophenylborate acid salt undergoes a covalent coupling reaction with the carboxyl group of alginate solution to form a polymeric gel network system as a pre-designed polymeric network.

4. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, The process of generating satellite unit microcarriers includes the following steps: Mix debranching enzyme and β-amylase to generate the first enzyme group mixture; An interfacial condensation reaction is carried out between tetraethyl orthosilicate and an acetal-bridged bissilane precursor to generate a brittle silica shell with a pre-set weak bond, which then encapsulates the first enzyme group mixture. Low-polymerization-degree amorphous amylose fragments are grafted at high density onto the exterior of a brittle silica shell as pre-defined amylose fragments to construct molecular anchoring chains and generate satellite unit microcarriers.

5. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 4, characterized in that, The process of generating a brittle silica shell with pre-defined weak bonds and encapsulating the first enzyme group mixture includes the following steps: Configure an oil-phase system consisting of a surfactant and a nonpolar solvent; The first enzyme group mixture was dispersed in the oil phase system to form microemulsion droplets; Tetraethyl orthosilicate and acetal-bridged bissilane precursors are added to microemulsion droplets to initiate an interfacial condensation reaction, generating a brittle silica shell with pre-set weak bonds that encapsulates the first enzyme group mixture.

6. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, The generation of a core satellite topology composite micro / nano carrier system includes the following steps: The core unit microcarriers and satellite unit microcarriers are co-dispersed and injected into a mild hypertonic buffer system to form a mixed suspension system; Short peptide molecules are introduced into a mixed suspension system as pre-set short peptide crosslinking arms, and chemical coupling agents are used to activate the surface of the core unit microcarrier and the ends of the short peptide molecules. A core unit microcarrier system is generated by covalently connecting one end of a pre-defined short peptide crosslinking arm to a core unit microcarrier and binding multiple satellite unit microcarriers to the other end.

7. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, Generating an initial matrix for baked goods that includes a physical monitoring interface includes the following steps: The core satellite topology composite micro-nano carrier system is uniformly kneaded into the preset matrix raw material in the form of solid powder to form a mixed preform. High-temperature baking of the mixed dough drives starch gelatinization, maintaining the topology of the core satellite topology composite micro-nano carrier system unchanged; The process guides the heated product to cool down, resulting in double-helix shrinkage and crystallization. This causes the matrix's own network to reconstruct and become entangled around the molecular anchoring chains, generating an initial matrix for baked goods that includes a physical monitoring interface.

8. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, Catalytic generation of maltose-specific molecular groups includes the following steps: Relying on the constraint effect of the physical monitoring interface, the shrinkage force is reversed to the connection anchor point of the satellite unit microcarrier. The shrinkage force is effectively transmitted through the physical entanglement generated between the non-crystalline amylose fragments and the food matrix network. The conduction of contraction tension causes stress concentration in the brittle silica shell, tearing the pre-set weak bonds and triggering the disintegration of the satellite unit microcarrier, releasing the first enzyme group mixture; The first enzyme group mixture is controlled to shear and recrystallize the amylopectin side layer linkages, catalyze the production of free short chains and their aggregation, and generate maltose-specific molecular groups.

9. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, Unblocking and releasing the second enzyme group aqueous solution into the starch retrogradation core region includes the following steps: The maltose-specific molecular group is driven to cross the spatial distance limited by the preset short peptide crosslinking arm, fully covering and wetting the surface of the core unit microcarrier. The concentration gradient of the maltose-specific molecular group is limited by the nanoscale spatial distance limited by the short peptide crosslinking arm. The specific molecular group of maltose is driven to intervene in the cross-linking site to undergo an irreversible strong complexation and substitution chemical reaction, thereby severing the cross-linking site; Cutting off the cross-linking sites causes the core unit microcarrier to liquefy and unblock, releasing the second enzyme group aqueous solution into the starch regeneration core region.

10. The anti-aging quality management system for baked goods with synergistic effects of compound enzymes according to claim 1, characterized in that, The process of generating a three-dimensional network polymer of starch lipids includes the following steps: The specific lipase contained in the aqueous solution of the second enzyme group is activated, which degrades the surrounding free and latent lipid molecules and generates a monoglyceride molecular layer. The fragments of free amylose molecules accumulated by cutting and peeling off the first enzyme group mixture were used as the preset starch fragments. The monoglyceride molecular layer and the pre-set starch residue are thermodynamically stable entangled and interacted, and solidified and deposited to form a three-dimensional network polymer of starch lipids.

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