Performance self-feedback regulation of concentrated ratio of super-high industrial circulating water biochemical reagent and method

Abstract

This invention belongs to the field of microencapsulation formulation technology, specifically relating to a biochemical agent and method for regulating the concentration ratio of ultra-high industrial circulating water using self-feedback regulation. It solves the technical problems of existing biochemical agents' inability to sense changes in the localized fouling microenvironment, the spatiotemporal disconnect between efficacy release and fouling, and the susceptibility to structural inactivation and damage. The self-feedback regulated biochemical agent is a core-shell microcapsule with a three-layer structure. From the inside out, it comprises an ultra-high concentration biochemical core in a dehydrated, vitrified dormant state; a flexible stress buffer layer composed of a modified polysiloxane elastomer; and a stimulus-responsive dynamic polymer shell assembled from a polysaccharide backbone grafted with calcium ion shielding groups, a dynamic covalent crosslinking agent, and fouling signal molecule receptors. The stimulus-responsive dynamic polymer shell triggers reversible dissociation and recombination of dynamic covalent bonds based on changes in the concentration of quorum sensing signal molecules, achieving self-feedback release and termination of biochemically active substances, thus completing the autonomous degradation of fouling.

Description

Technical Field

[0001] This invention belongs to the field of microcapsule formulation technology, specifically relating to biochemical agents and methods for ultra-high concentration ratio of industrial circulating water with self-feedback regulation of efficacy. Background Technology

[0002] Industrial circulating cooling water systems are major water-consuming units in industrial production. Increasing the concentration ratio of circulating water to ultra-high concentration ratios of 10 to 30 times has become a recognized direction for water-saving technology evolution in the industry. Under ultra-high concentration ratio conditions, the circulating water system is in a state of extreme thermodynamic imbalance, accompanied by extremely high osmotic pressure gradients, high concentrations of hardness ions, and strong mechanical shear forces generated by high-frequency pumping circulation. Biochemical agents, due to their environmental friendliness and ability to degrade complex organic pollutants, have attracted attention for application under such extreme water quality conditions.

[0003] For the treatment of circulating water with high concentration ratios, existing technical solutions mostly employ a combination of compound microbial agents and exogenous nutrient regulation, and use online monitoring systems to sense macroscopic water quality parameters such as conductivity, pH value, and redox potential, and add agents according to preset ratios. For example, CN116332370A discloses a method for operating and controlling circulating cooling water at high concentration ratios, which automatically adjusts the dosage of biochemical agents based on online monitoring of macroscopic water quality parameters such as pH and conductivity.

[0004] The risk of fouling in circulating water systems first emerges in localized microenvironments such as heat exchanger surfaces or dead zones in pipe walls. Macroscopic water quality parameters often only show significant fluctuations after localized fouling has formed a dense biofilm or scale layer. At this point, because biochemical agents lack the ability to autonomously sense changes in the microenvironment, they cannot provide targeted responses in the early stages of fouling. This results in low agent utilization rates, and the fouling control effect lags behind the actual development of fouling. This forces the system to increase the total agent dosage to compensate for insufficient localized effectiveness, further exacerbating operating costs and environmental burden.

[0005] High osmotic pressure environment causes irreversible hypertonic dehydration and inactivation of microbial cells in conventional biochemical agents; extremely high concentrations of calcium ions (usually above 2000 mg / L, and even exceeding 4000 mg / L under extreme conditions) crosslink and chelate with functional polymers in the agent, causing the functional polymers to lose their activity; the mechanical shear force generated by high-frequency pumping can easily cause physical rupture of the agent's encapsulation structure, causing the active material to leak prematurely and rapidly inactivate before reaching the contamination site. Summary of the Invention

[0006] The purpose of this invention is to provide a biochemical agent and method for high-efficiency self-feedback regulation of ultra-high concentration ratio of industrial circulating water, which solves the technical problems of existing biochemical agents being unable to sense changes in the local fouling microenvironment, the spatiotemporal disconnect between agent activity release and fouling degree, and the deactivation or destruction of agent structure under the conditions of high osmotic pressure, high calcium ion concentration and strong mechanical shear force in ultra-high concentration ratio operation.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: A biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback efficiency regulation, wherein the agent is a core-shell microcapsule with a three-layer structure, comprising, from the inside out: The ultra-high concentration biochemical core contains extreme halophilic engineered bacteria, complex biological enzymes, and osmotically compatible solutes, and the ultra-high concentration biochemical core is in a dehydrated vitrified dormant state with a water content of less than 5%. A flexible stress buffer layer, covering the outer surface of the ultra-high concentration biochemical core, is composed of a modified polysiloxane elastomer with a crosslinking degree of 15% to 25%. The stimulus-responsive dynamic polymer shell is assembled from a polysaccharide backbone, a dynamic covalent crosslinking agent, and a fouling signaling molecule receptor through a dual crosslinking network. The polysaccharide backbone is covalently grafted with a calcium ion shielding group, which is an ethylenediaminetetraacetic acid derivative. The chelation constant Log K of the calcium ion shielding group for calcium ions is greater than 10.5, and the grafting amount is 5% to 12% of the mass of the polysaccharide backbone. The crosslinking bonds constructed by the dynamic covalent crosslinking agent are dynamic covalent bonds with thermodynamically reversible dissociation properties; The fouling signaling molecule receptor is a protein receptor or molecularly imprinted polymer with high affinity for quorum sensing signaling molecules. The quorum sensing signaling molecules comprise at least one of N-acylhomoserine lactone and self-inducer-2. The density of the fouling signaling molecule receptor in the stimulus-responsive dynamic polymer shell is 10. -6 mol / g to 10 -4 mol / g; The contamination signaling molecule receptor, upon binding to the quorum sensing signaling molecule, triggers the dissociation of the dynamic covalent bond.

[0008] Furthermore, the dynamic covalent bond is selected from one of the following: borate ester bond, acylhydrazone bond, and disulfide bond.

[0009] Furthermore, the extreme halophilic engineered bacteria is a mixed bacterial community of genetically engineered Halomonas sp. and Marinococcus sp. with a mixing mass ratio of 1:1. Both Halomonas sp. and Marinococcus sp. have undergone site-directed mutagenesis to enhance the expression of osmolarity regulatory proteins ProU and ProP. The composite bioenzyme is composed of salt-tolerant cellulase, protease and lipase, and the enzyme activity of each enzyme is not less than 50,000 U / g. The anti-hyperosmolarity compatibility solute is a mixture of tetrahydropyrimidine, betaine, and trehalose, wherein the mass ratio of tetrahydropyrimidine, betaine, and trehalose is 5:3:2.

[0010] Furthermore, the microcapsules have a particle size distribution ranging from 50 micrometers to 150 micrometers and a density ranging from 1.05 g / cm³ to 1.15 g / cm³; the flexible stress buffer layer has a thickness of 10 micrometers to 20 micrometers and a Shore hardness of A10 to A20.

[0011] Furthermore, the outer surface of the flexible stress buffer layer is covalently anchored with a halophilic quorum sensing quenching enzyme; When the stimulus-responsive dynamic polymer shell is in a closed state, the stimulus-responsive dynamic polymer shell forms a steric barrier shield for the halophilic quorum sensing quenching enzyme. After the stimulus-responsive dynamic polymer shell swells, the halophilic quorum sensing quenching enzyme is exposed to circulating water to catalytically degrade the residual quorum sensing signal molecules.

[0012] Furthermore, the halophilic quorum sensing quencher enzyme is a halophilic N-acylhomoserine lactonease, which is anchored to the outer surface of the flexible stress buffer layer through multi-point covalent cross-linking, with a fixed density range of 1.0 × 10⁻⁶. -11 mol / cm² to 5.0×10 -10 mol / cm².

[0013] In addition, this invention also discloses a method for self-feedback regulation of the efficacy of biochemical agents with ultra-high concentration ratio in industrial circulating water based on the above-mentioned self-feedback regulation, comprising the following steps: Step 1: The agent is added to the industrial circulating water system at an initial concentration of 150-250 mg / L; during normal system operation, the stimulus-responsive dynamic polymer shell remains closed, isolating the ultra-high concentration biochemical core from the external circulating water environment. Step 2: When the concentration of quorum sensing signal molecules in a local area exceeds the response threshold of the fouling signal molecule receptor, the fouling signal molecule receptor captures the quorum sensing signal molecules, triggering the dissociation of the dynamic covalent bonds, and causing the stimulus-responsive dynamic polymer shell to swell with a swelling rate of not less than 300%, thereby releasing the biochemically active substances encapsulated in the ultra-high concentration biochemical core to the local area in situ. Step 3: The released biochemically active substances biodegrade the contaminants in the localized area; Step four: When the concentration of quorum sensing signal molecules in the local area decreases below the response threshold, the dynamic covalent bonds spontaneously recombine, and the stimulus-responsive dynamic polymer shell returns to its closed state.

[0014] Furthermore, in step three, the release flux of the agent and the quorum sensing signal molecular load follow the following mapping relationship:

[0015] in, The flux released is expressed in mg / (m²·h); To release the kinetic constant, its unit is... The value of is determined by; The concentration of quorum sensing signal molecules measured in a local microenvironment is expressed in nmol / L. The response threshold concentration of the contamination signaling molecule receptor is given in nmol / L. The response sensitivity coefficient is dimensionless and ranges from 1.5 to 3.0.

[0016] Furthermore, during normal system operation, the closed stimulus-responsive dynamic polymer shell forms a steric barrier shielding against the halophilic quorum sensing quenching enzyme. In step two, after the stimulus-responsive dynamic polymer shell swells, moisture and the quorum sensing signal molecules permeate to the surface of the flexible stress buffer layer, and the halophilic quorum sensing quenching enzyme catalytically degrades the quorum sensing signal molecules. In step four, the halophilic quorum sensing quenching enzyme catalyzes the degradation of residual quorum sensing signal molecules, accelerating the process of reducing their concentration to below the response threshold, thereby driving the spontaneous recombination of the dynamic covalent bonds.

[0017] Furthermore, the degradation of the quorum sensing signal molecule by the halophilic quorum sensing quencher enzyme follows the Michaelis-Menten equation:

[0018] in, For degradation rate, For the maximum reaction rate, It is the Michaelis constant. This represents the measured concentration of molecules in the quorum sensing signal.

[0019] Furthermore, the ultra-high concentration biochemical core also incorporates D-type amino acid biofilm dispersant; The D-type amino acid biofilm dispersant is composed of a mixture of D-tyrosine, D-methionine and D-tryptophan; The D-type amino acid biofilm dispersant and the anti-hyperosmotic compatibility solute form a homogeneous co-amorphous solid solution embedded in the dehydrated glassy dormant state through intermolecular hydrogen bonding. When the stimulus-responsive dynamic polymer shell swells and allows water to penetrate, the release rate of the D-type amino acid biofilm dispersant is greater than that of the composite bioenzyme due to the molecular hydrodynamic volume difference. This creates a spatiotemporal cascade release pathway in the local microenvironment, where small molecules lead the dispersion and then macromolecules undergo subsequent degradation.

[0020] Furthermore, the mass fraction of the D-type amino acid biofilm dispersant in the ultra-high concentration biochemical core is 3% to 8%; Due to the leading depolymerization effect of the D-type amino acid biofilm dispersant, the apparent biodegradation rate of the fouling material by the composite bioenzyme follows the following kinetic correction model:

[0021] in, The apparent biodegradation rate after introducing the D-type amino acid biofilm dispersant is expressed in mg / (L·h). The initial biodegradation rate under the action of the aforementioned composite enzyme alone is expressed in mg / (L·h). The dispersion synergy coefficient is dimensionless and ranges from 1.5 to 3.5. The real-time concentration of the D-type amino acid biofilm dispersant released in the local microenvironment, in units of mol / L; The half-maximum effective concentration constant of the D-type amino acid biofilm dispersant is given, in units of... mol / L.

[0022] Compared with the prior art, the present invention has the following beneficial effects: This invention integrates microscopic sensing, dynamic response, targeted release, and spontaneous closure functions into a single particle scale by constructing a three-layer core-shell microcapsule consisting of an ultra-high concentration biochemical core, a flexible stress buffer layer, and a stimulus-responsive dynamic polymer shell. The specific capture of quorum sensing signal molecules by the fouling signal receptors in the stimulus-responsive dynamic polymer shell drives reversible dissociation and recombination of dynamic covalent bonds, enabling the on-demand release of bioactive substances only at the fouling site. This avoids the spatiotemporal lag defects caused by relying on macroscopic water quality parameter feedback in traditional methods, significantly improving reagent utilization efficiency and fouling response speed. The ultra-high concentration biochemical core is in a dehydrated, vitrified dormant state, maintaining biological activity for a long time under extreme high osmotic pressure environments. The flexible stress buffer layer dissipates shear energy through viscoelastic polymer chain conformational relaxation, protecting the structural integrity of the core. Calcium ion shielding groups grafted onto the polysaccharide backbone maintain low free calcium levels locally in the shell, inhibiting shell cross-linking and locking caused by high concentrations of calcium ions, ensuring the long-term stability of the dynamic reversible switching function.

[0023] This invention further anchors a halophilic quorum sensing quenching enzyme on the outer surface of a flexible stress buffer layer. This accelerates the degradation of residual signaling molecules after fouling is removed, shortens the shell closure response time, inhibits the ineffective loss of active ingredients, and improves the recycling rate of the agent. By combining a D-type amino acid biofilm dispersant within the ultra-high concentration biochemical core, and utilizing a spatiotemporal cascade pathway of small molecule lead release and subsequent enzyme degradation, it can effectively penetrate dense biofilms, achieving efficient removal and degradation of fouling substances. The overall solution relies entirely on the physicochemical properties of the agent itself for autonomous regulation, requiring no external control system or energy input, reducing system complexity and operating costs. It achieves long-term stable operation and maximized efficiency in ultra-high concentration industrial circulating water systems. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained from these drawings without creative effort.

[0025] Figure 1 This is a flowchart of the efficiency self-feedback control method of the present invention.

[0026] Figure 2 This is a flowchart of the efficacy regulation method of the present invention with a halophilic quorum sensing quenching enzyme.

[0027] Figure 3 This is a flowchart of the release and degradation method of the biofilm dispersant containing D-type amino acids according to the present invention. Detailed Implementation

[0028] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of the embodiments of the invention. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0029] The following is in conjunction with the appendix Figures 1-3 The embodiments of the present invention will be described in detail below.

[0030] Example 1: This example provides a biochemical agent for regulating the concentration ratio of ultra-high industrial circulating water using self-feedback, and a method for regulating the efficacy of the self-feedback biochemical agent.

[0031] In this embodiment, the self-feedback biochemical agent is a core-shell microcapsule with a three-layer structure, comprising, from the inside out, an ultra-high concentration biochemical core, a flexible stress buffer layer, and a stimulus-responsive dynamic polymer shell. The microcapsule has a particle size distribution ranging from 50 μm to 150 μm and a density ranging from 1.05 g / cm³ to 1.15 g / cm³.

[0032] The ultra-concentrated biochemical core consists of extreme halophilic engineered bacteria, complex bioenzymes, and osmotically compatible solutes. The extreme halophilic engineered bacteria are a mixed bacterial community of genetically engineered Halomonas sp. and Marinococcus sp., with a mass ratio of 1:1. Both Halomonas and Marinococcus have undergone site-directed mutagenesis to enhance the expression of osmotic pressure regulating proteins ProU and ProP.

[0033] The complex bioenzyme is composed of salt-tolerant cellulase, protease, and lipase, with each enzyme having an activity unit of not less than 50,000 U / g.

[0034] The hypertonic compatibility solute is a mixture of tetrahydropyrimidine, betaine, and trehalose in a mass ratio of 5:3:2. The ultra-concentrated biochemical core is in a dehydrated, glassy dormant state with a water content of 4.2%. Differential scanning calorimetry (DSC) determined that the glass transition temperature (Tg) of this dehydrated, glassy dormant state is 68℃, significantly higher than the maximum operating temperature of the circulating water system (45℃), ensuring that the core remains in a glassy state throughout operation, effectively restricting molecular motion.

[0035] A flexible stress buffer layer is coated on the outer surface of the ultra-high concentration biochemical core. It is composed of a modified polysiloxane elastomer with a crosslinking degree of 20%, specifically an elastomer formed by crosslinking hydroxyl-terminated polydimethylsiloxane and vinyltriethoxysilane under the action of an organotin catalyst. The Shore hardness is A15 and the thickness of the buffer layer is 15μm.

[0036] The stimulus-responsive dynamic polymer shell is assembled from a polysaccharide backbone, a dynamic covalent crosslinking agent, and a fouling signaling molecule receptor through a double crosslinking network.

[0037] The polysaccharide backbone is modified sodium alginate. Calcium ion-shielding groups, derived from ethylenediaminetetraacetic acid (EDA), are covalently grafted onto the backbone via an NHS / EDC coupling system. The grafting amount is 10% of the polysaccharide backbone mass, and the chelation constant Log K for calcium ions by these groups is 10.8. The dynamic covalent crosslinking agent is phenylboronic acid-modified polyvinyl alcohol, which forms borate ester bonds with the ortho-diol groups on the polysaccharide backbone.

[0038] The contamination signaling molecule receptor is a TraR protein receptor with high affinity for N-acylhomoserine lactones (AHL), and its density in the stimulus-responsive dynamic polymer shell is 5 × 10⁻⁶. -5 mol / g. The TraR protein receptor is rich in serine and threonine residues on its surface, and its side chains contain vicinal diol groups. When not bound to AHL, these residues are buried inside the protein. When AHL is captured, the TraR protein receptor undergoes a conformational change, exposing the residues containing vicinal diol groups. These groups act as competitive ligands and bind to phenylboronic acid groups, replacing the vicinal diols on the polysaccharide backbone, leading to competitive displacement dissociation of the borate ester crosslinks.

[0039] The preparation method of the self-feedback biochemical agent in this embodiment includes the following steps.

[0040] The first step is the preparation of an ultra-high concentration biochemical core.

[0041] *Haloxylon ammodendron* and *Cordyceps sinensis* were inoculated into LB medium containing 10% sodium chloride at a 1:1 mass ratio and cultured at 30°C until the late logarithmic growth stage. The bacterial sludge was collected by centrifugation at 6000 rpm, and the moisture content of the sludge was approximately 80%. The wet bacterial sludge (dry weight) was mixed with a compound biological enzyme lyophilized powder and a tetrahydropyrimidine / betaine / trehalose mixture at a dry weight ratio of 1:0.3:0.5 to form a biochemical slurry. The biochemical slurry was pre-frozen at -50°C for 12 hours and then sublimated in a freeze dryer under a vacuum of 8 Pa for 48 hours until the moisture content dropped to 4.2%, yielding vitrified lumps. The vitrified lumps were then subjected to ultrafine grinding and airflow sieving to obtain vitrified core particles with a particle size range of 30 μm to 80 μm.

[0042] The second step is to coat the area with a flexible stress buffer layer.

[0043] A fluidized bed spray coating process was employed, in which hydroxyl-terminated polydimethylsiloxane and vinyltriethoxysilane were mixed at a mass ratio of 100:8, and 0.5% organotin catalyst was added. A 20% (w / w) prepolymer solution was prepared using ethyl acetate as the solvent. Within the fluidized bed, the vitrified core particles were suspended under a 45°C hot gas flow. The prepolymer solution was atomized through a two-fluid nozzle and uniformly sprayed onto the surface of the vitrified core particles. Thermal curing at 45°C for 2 hours resulted in a uniform, flexible stress-relief layer with a thickness of 15 μm.

[0044] The third step is the assembly of the stimulus-responsive dynamic polymer shell.

[0045] Modified sodium alginate grafted with ethylenediaminetetraacetic acid derivatives was dissolved in a borate buffer solution with a pH of 8.5 to prepare a 3% (w / w) polysaccharide solution. A phenylboronic acid-modified polyvinyl alcohol crosslinking agent (15% (w / w) relative to the polysaccharide backbone) and a TraR protein receptor were added to the polysaccharide solution and mixed thoroughly to form the aqueous phase. The aqueous phase was slowly added dropwise to a liquid paraffin oil phase containing Span-80 dispersant, and a water-in-oil emulsion was formed under stirring at 800 rpm. The system temperature was adjusted to 40°C, and the reaction was maintained for 4 hours. After dehydration and washing with isopropanol and drying under reduced pressure at 30°C, the finished microcapsules were obtained.

[0046] In this embodiment, the aforementioned self-feedback biochemical agent is applied to the industrial circulating cooling water system of a coastal power plant with a concentration ratio of 25 times. The system's makeup water hardness is 350 mg / L (calculated as CaCO3), the measured total dissolved solids in the circulating water is 128,500 mg / L, and the calcium ion concentration is 4,200 mg / L.

[0047] The efficiency self-feedback control method is implemented according to the following steps.

[0048] Step 1: The self-feedback biochemical agent is added to the circulating water tank in a single dose at an initial concentration of 150 mg / L. During normal system operation, the pH of the circulating water is maintained between 8.5 and 9.2. The borate ester bonds in the stimulus-responsive dynamic polymer shell are in a stable associated state, resulting in a dense shell structure and a water permeability coefficient below 1 × 10⁻⁶. -8 m / s, the ultra-high concentration of the biochemical core maintains a dehydrated, glassy dormant state.

[0049] Step two: When microorganisms proliferate and form an initial biofilm in a localized area of ​​the heat exchanger tube wall, the N-acylhomoserine lactone secreted by the microorganisms accumulates in the localized area, and the measured concentration in the localized microenvironment is... The concentration reached 80 nmol / L, exceeding the response threshold concentration of the TraR protein receptor. = 50 nmol / L (This threshold corresponds to the apparent dissociation characteristics of AHL by the TraR protein receptor, calibrated by in vitro fluorescence polarization experiments). The TraR protein receptor captures AHL and undergoes a conformational change, exposing residues containing vicinal diol groups. Through a competitive substitution mechanism, it induces the dissociation of borate ester bonds, stimulating the swelling of the responsive dynamic polymer shell, with a swelling rate reaching 420%.

[0050] Step three: Water enters the ultra-concentrated biochemical core, triggering a glass transition and dissolution of the matrix. The extreme halophilic engineered bacteria regain metabolic activity within 45 minutes, synergistically working with complex bioenzymes to hydrolyze and degrade extracellular polymers in the biomembrane. Flux release... The mapping relationship between molecular load and quorum sensing signal follows the formula:

[0051] in The flux released is expressed in mg / (m²·h); To determine the kinetic constant, it was calibrated through pilot-scale pellet experiments, and in this embodiment, the value was taken as [value missing]. mg / (m²·h·(nmol / L) ); The measured AHL concentration in a local microenvironment was 80 nmol / L. The response threshold concentration is 50 nmol / L; The response sensitivity coefficient is set to 2.1. Substituting this into the equation yields... (nmol / L), Therefore mg / (m²·h). This release flux, accumulated over the local microcapsule surface area, is sufficient to provide an effective mass of bioactive substances in the early stages of fouling.

[0052] Step four: After degradation by biochemically active substances, the local biofilm is peeled off, and the AHL concentration drops back to 12 nmol / L (below...). After the free AHL decreases, the TraR protein receptor releases AHL and restores its original conformation. The vicinal diol group is re-buried, and phenylboronic acid and the vicinal diol on the polysaccharide backbone reform borate ester bonds. The stimulus-responsive dynamic polymer shell returns to its dense closure, and the release of the active substance terminates.

[0053] After 90 days of operation, the microcapsules in the system were removed for testing. The viable / dead bacteria suspension after the microcapsules were broken was analyzed by propidium azide bromide-quantitative PCR (PMA-qPCR), and the recovery rate of the core bacteria was 92.5%. The activity retention rate of the complex enzyme was 88.2% as detected by the corresponding enzyme substrate method, indicating that the dehydrated vitrified dormant state can maintain its activity for a long time under ultra-high TDS environment. The shell calcification deadlock rate was only 0.5%, and the flexible stress buffer layer controlled the pumping shear damage rate to 0.8%.

[0054] Example 2: Based on Example 1, Example 2 further replaced the type of dynamic covalent bond in the stimulus-responsive dynamic polymer shell.

[0055] In this embodiment, the dynamic covalent bond is an acylhydrazone bond. The polysaccharide backbone is oxidized sodium alginate with an oxidation degree of 15%, and aldehyde groups are introduced onto the sodium alginate sugar ring by sodium periodate oxidation.

[0056] The dynamic covalent crosslinking agent is adipic acid dihydrazide, where the aldehyde group and the hydrazide group undergo a Schiff base condensation reaction to form an acylhydrazone crosslinking bond. The contamination signaling molecule receptor still uses the TraR protein receptor, which exposes residues carrying vicinal diol groups through conformational changes. However, in this embodiment, the exposed groups accelerate acylhydrazone bond hydrolysis by promoting the formation of a local acid-catalyzed microenvironment. The specific mechanism is as follows: After the TraR protein receptor binds to AHL, it undergoes a conformational change, exposing the surface carboxyl-rich region to the vicinity of the acylhydrazone bond, reducing the local effective pH, thereby accelerating acid-catalyzed hydrolysis.

[0057] In this embodiment, a self-feedback biochemical reagent was applied to the circulating water system of a coal chemical enterprise with a concentration ratio of 30 times. The system's makeup water hardness was 500 mg / L (calculated as CaCO3), the measured total dissolved solids in the circulating water was 155,200 mg / L, and the calcium ion concentration was 8,500 mg / L. The initial reagent dosage was 250 mg / L, increasing the grafting rate of calcium ion shielding groups on the polysaccharide backbone to 12%, with a Log K of 11.2. The response threshold concentration... Set to 30 nmol / L, response sensitivity coefficient The value is 2.5.

[0058] During the efficiency regulation process, when organic acids are produced in a local area of ​​the circulating water system due to anaerobic metabolism, causing the local microenvironment pH value to drop from 9.0 to 6.5, the acylhydrazone bond enters the acid catalysis sensitive area, and its dissociation rate constant increases by 35 times. The stimulus-responsive dynamic polymer shell completes the swelling response within 15 minutes, and the swelling rate reaches 480%.

[0059] The extreme halophilic engineered bacteria regained their metabolic activity within 40 minutes.

[0060] The remaining steps are the same as in Example 1, and the flux release formula is as follows: It is 80 nmol / L. nmol / L, the difference is 50 nmol / L. , Certified as mg / (m²·h·(nmol / L) ), calculate mg / (m²·h) meets the requirements for fouling control. After 90 days of operation, the biofilm stripping rate reached 92.8%, and the heat transfer coefficient decreased by 5.1%.

[0061] Example 3: This example is basically the same as Example 1, except that the sensing range of the clogging signal molecule receptor is expanded in this example.

[0062] In this embodiment, the dynamic covalent bond is a disulfide bond, the polysaccharide backbone is thiol-modified chitosan, and thiol groups are introduced by forming amide bonds between the carboxyl group of cysteine ​​and the amino group of chitosan, and a disulfide cross-linking network is formed in the shell layer by air oxidation.

[0063] The fouling signaling receptor further includes the PqsR protein, which binds to the Pseudomonas aeruginosa quinolone signal (PQS). The PqsR protein receptor is covalently fixed to the polysaccharide backbone via a click chemistry reaction, with an immobilization density of 8 × 10⁻⁶. -5 mol / g. The PqsR protein receptor undergoes a conformational change upon binding to PQS, exposing thiol-containing residues. These residues act as nucleophiles in the thiol-disulfide exchange reaction, leading to the breakage of disulfide crosslinks.

[0064] In this embodiment, the self-feedback biochemical agent is applied to an industrial circulating water system with a concentration ratio of 20 times and biofouling dominated by Pseudomonas aeruginosa.

[0065] When the concentration of PQS signaling molecules in the anaerobic layer of the biofilm exceeds the response threshold of 60 nmol / L, the PqsR receptor captures PQS and triggers a conformational change. The exposed thiol groups attack disulfide bonds, stimulating the swelling of the responsive dynamic polymer shell and releasing biochemically active substances. After the local redox potential recovers, the disulfide bonds reform, and the shell closes.

[0066] Example 4: Building upon Example 1, Example 4 constructs an active signal molecule removal mechanism based on a halophilic quorum sensing quenching enzyme on the outer surface of a flexible stress buffer layer. This mechanism is used to rapidly reduce the concentration of residual signal molecules in the microenvironment after localized biofouling is degraded by internal biochemically active substances, thereby forcing the stimulus-responsive dynamic polymer shell to accelerate its recombination and closure, thus kinetically preventing excessive depletion of the ultra-concentrated biochemical core.

[0067] The composition of the ultra-high concentration biochemical core and the preparation process of the dehydrated vitrified dormant state are completely consistent with those in Example 1.

[0068] After coating the modified polysiloxane elastomer with a crosslinking degree of 20%, the core particles with a flexible stress buffer layer were immersed in an anhydrous ethanol solution containing 2% by mass of 3-aminopropyltriethoxysilane in a glove box under strict anhydrous and inert atmosphere protection (water content <1 ppm, oxygen content <1 ppm). The reaction was carried out at 35°C for 4 hours to introduce abundant free amino groups on the surface of the elastomer, so as to avoid water penetration and glassy swelling of the core.

[0069] After washing the surface of the particles with phosphate buffer, the particles were resuspended in a 1.5% glutaraldehyde solution and continuously activated for 2 hours to construct a cross-linked substrate with dual covalent reactivity.

[0070] The activated particles were then transferred to a buffer solution containing a halophilic N-acylhomoserine lactonease and coupled at 4°C with shaking for 16 hours. This halophilic N-acylhomoserine lactonease was extracted from Vibrio vulnificus, and its polypeptide chain surface is rich in acidic amino acid residues, enabling it to adapt to extremely high osmotic pressure environments.

[0071] The two aldehyde groups at both ends of glutaraldehyde undergo Schiff base condensation reactions with the amino groups on the surface of the flexible stress buffer layer and multiple lysine residues on the surface of the enzyme molecule, forming a multi-site covalent cross-linked network. The final immobilization density of the enzyme is controlled at 2.8 × 10⁻⁶. -10 mol / cm². The multi-point anchoring structure significantly increases the three-dimensional conformational rigidity of the enzyme molecule, preventing polypeptide chain unfolding and inactivation in the hypertonic environment of circulating water with a total dissolved solids of up to 150,000 mg / L. After centrifugation and washing to remove free enzyme molecules, a stimulus-responsive dynamic polymer shell is assembled on the outermost layer of the particles according to the standard process of Example 1.

[0072] The self-feedback biochemical agent prepared in this embodiment was put into the industrial circulating cooling water system of a coastal power plant, which is the same as that in Example 1.

[0073] During the normal operation phase of the system's regulatory cycle, the dense stimulus-responsive dynamic polymer shell forms a strong steric barrier shield for the internal quenching enzyme array, preventing it from consuming the normal background signal molecules in the water.

[0074] When the measured concentration of quorum sensing signal molecules in the local microenvironment exceeds the response threshold, triggering a swelling response in the shell, external circulating water carrying AHL penetrates the porous polymer shell and reaches the surface of the flexible stress buffer layer. The halophilic quorum sensing quenching enzyme then performs high-frequency catalytic hydrolysis on the infiltrated signal molecules. This enzymatic degradation process follows the kinetic equation below:

[0075] in, The real-time enzymatic degradation rate of the quorum sensing signal molecule is expressed in nmol / (L·min). The maximum catalytic reaction rate of this immobilized enzyme system is expressed in nmol / (L·min); is the Michaelis constant, with units of nmol / L; The measured quorum induction signal molecule concentration is expressed in nmol / L.

[0076] Biochemical assays showed that the Michaelis constant of the halophilic N-acylhomoserine lactoneases anchored at multiple points in this embodiment was determined. The concentration was 18 nmol / L. This value is lower than the system's set response threshold concentration. (50 nmol / L) allows the quenching enzyme to rapidly operate at near-zero concentrations upon initial shell expansion and the influx of high-concentration substrate. The high-efficiency catalytic range.

[0077] After the released complex bioenzymes and extreme halophilic engineered bacteria irreversibly disintegrate the biofilm matrix and cut off the continuous secretion source of AHL, the high-frequency hydrolytic bond-breaking effect of the immobilized quenching enzymes causes a rapid decrease in the concentration of residual signal molecules in the local microenvironment. The above-mentioned dual scavenging mechanism (physical stripping of the source plus biochemical degradation residues) forces the dynamic covalent bonds to rapidly recombine under the drive of local thermodynamic equilibrium, and the stimulus-responsive dynamic polymer shell quickly recovers its dense closure.

[0078] The core operational performance monitoring data obtained in Example 4 and Example 1 within the same 90-day experimental period are detailed in Table 1.

[0079] Table 1. Comparison of operating performance parameters between Example 4 and Example 1;

[0080] The halophilic quorum sensing quenching enzyme introduced through multi-point covalent cross-linking technology exhibits excellent structural stability under ultra-high concentration ratio conditions, with an enzyme activity retention rate as high as 92.4% after 90 days of operation.

[0081] Unlike Example 1, which relies solely on natural diffusion mechanisms leading to a slow decline of signal molecules, the enzymatic quenching mechanism in this example significantly reduces the spontaneous recombination and closure response time of the shell from 45 minutes to 11 minutes.

[0082] The precise narrowing of the reaction window fundamentally curbs the ineffective trailing effect of dormant bacteria and bioenzymes in the macroscopic water body after the removal of fouling, increases the recycling rate of the active ingredients of the agent to 96.3%, and reduces the concentration of useless residual active substances in the water body to 2.1 mg / L, achieving the dual technical effects of reducing system operating costs and controlling secondary water pollution.

[0083] Example 5: This example provides a self-feedback biochemical agent that uses a molecularly imprinted polymer as a molecular acceptor for fouling signals.

[0084] The difference from Example 1 is that the clogging signaling molecule receptor in the stimulus-responsive dynamic polymer shell is replaced with a molecularly imprinted polymer targeting N-acyl homoserine lactone.

[0085] The specific preparation method is as follows: Using N-acylhomoserine lactone as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a crosslinking agent, and azobisisobutyronitrile (AIB) as an initiator, molecularly imprinted polymer particles were obtained by thermal polymerization in acetonitrile at 60 °C for 24 hours. After removing the template by Soxhlet extraction with methanol / acetic acid (9:1, v / v), the particles were vacuum dried and ground to a particle size of less than 200 nm. The molecularly imprinted polymer exhibited a binding capacity of 85 μmol / g for AHL and an imprinting factor of 3.8.

[0086] The molecularly imprinted polymer was used as a contamination signaling molecular acceptor at a concentration of 5 × 10⁻⁶. -5 It is incorporated into a network composed of a polysaccharide backbone and a dynamic covalent crosslinking agent at a density of mol / g.

[0087] When AHL molecules enter the imprinted cavity, the cavity swells, applying mechanical stress to the surrounding cross-linked network and assisting in triggering the dissociation of the borate ester bonds. The remaining structure and method are the same as in Example 1. This example demonstrates that molecularly imprinted polymers can also serve as signal sensing elements for autonomous regulation, expanding the range of acceptors.

[0088] Comparative Example 1: Comparative Example 1 used a conventional unencapsulated biochemical bactericide, specifically a compound formulation of isothiazolinone and quaternary ammonium salt (mass ratio 1:1), operating in an industrial circulating water system with a concentration ratio of 25 times. The dosing method was based on online conductivity monitoring data, with daily timed shock dosing according to a preset program, at a concentration of 80 mg / L each time. The system makeup water hardness was 350 mg / L (calculated as CaCO3), and the total dissolved solids in the circulating water were 128,100 mg / L.

[0089] The results showed that, within the 90-day experimental period, the biofilm stripping rate of Comparative Example 1 was 32.4%, the heat transfer coefficient decreased by 28.7%, and the utilization rate of the active ingredient was only 21.5%. The reason for this is that conventional unencapsulated biochemical bactericides are rapidly passivated by their active ingredients in high-salinity environments and lack the ability to target and release them at fouling sites.

[0090] Comparative Example 2: Comparative Example 2 adopted the scheme in Example 1, but the flexible stress buffer layer was removed. Only the stimulus-responsive dynamic polymer shell was directly coated on the surface of the ultra-high concentration biochemical core. The remaining structure, components and preparation process were the same as in Example 1, and it was operated under the same conditions with a concentration ratio of 25 times.

[0091] The results showed that, under the shearing action of the circulating pump, the microcapsules of Comparative Example 2 had a drug breakage rate of 38.5%, which caused the active substances in the ultra-high concentration biochemical core to be released prematurely before reaching the fouling area and to be rapidly deactivated due to the high osmotic pressure environment. The biofilm inhibition rate dropped to 58.6%, and the heat transfer coefficient reduction rate increased to 15.4%.

[0092] Comparative Example 3: Comparative Example 3 adopted the scheme in Example 1, except that the polysaccharide backbone was not grafted with ethylenediaminetetraacetic acid derivative as a calcium ion shielding group. The rest of the structure, components and preparation process were the same as in Example 1, and it was operated under the same conditions of a concentration ratio of 25 times and a calcium ion concentration of 4200 mg / L.

[0093] The results showed that the shell calcification deadlock rate of Comparative Example 3 was as high as 45.3%. A large number of stimulus-responsive dynamic polymer shells lost their dynamic response ability due to the formation of static ionic cross-linking networks between high concentrations of calcium ions and polysaccharide carboxyl groups. When the concentration of fouling signal molecules exceeded the response threshold, they could not swell and release active substances normally. The biofilm peeling rate was only 41.2%, and the utilization rate of effective drug components dropped to 36.7%.

[0094] Table 2 summarizes the main operating performance parameters of Example 1, Example 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3 during the 90-day experimental period.

[0095] Table 2. Comparison of operating performance parameters between the embodiment and the comparative example;

[0096] As shown in Table 2, under the conditions of 25 to 30 times ultra-high concentration ratio, the biofilm peeling rate of Examples 1 and 2 both exceeded 92%, the heat transfer coefficient reduction rate was controlled below 5.1%, the utilization rate of effective components of the agent exceeded 85%, the breakage rate after pumping and shearing was less than 1.2%, the shell calcification deadlock rate was less than 0.8%, and the recommended cleaning cycle of the system was more than 16 months.

[0097] Compared with Comparative Example 1, Example 1 improved the utilization rate of the active pharmaceutical ingredient by more than 4 times; compared with Comparative Example 2, Example 1 reduced the pumping shear failure rate from 38.5% to 0.8% by setting a flexible stress buffer layer; compared with Comparative Example 3, Example 1 reduced the shell calcification deadlock rate from 45.3% to 0.5% by grafting calcium ion shielding groups on the polysaccharide backbone.

[0098] The above comparative data fully demonstrates that the biochemical agent and its self-feedback regulation method for ultra-high concentration ratio industrial circulating water systems provided by this invention, by organically integrating four technical means—dehydration glass dormancy, flexible stress buffering, calcium ion shielding, and dynamic covalent bond reversible regulation—into a single microcapsule structure, can achieve precise perception and autonomous adaptation of agent efficacy to the fouling microenvironment under extreme operating conditions of ultra-high concentration ratio industrial circulating water, and maintain the integrity and functional activity of the agent structure for a long time, significantly extending the system cleaning cycle and improving overall operating efficiency.

[0099] Example 6: Based on Example 1, this example focuses on the deep optimization of the biochemical composition and release sequence of the ultra-high concentration biochemical core to address the dense biofouling formed under the superposition of extremely high hardness and high organic load.

[0100] In the preparation of the ultra-concentrated biochemical core, D-tyrosine, D-methionine, and D-tryptophan were first premixed in a molar ratio of 2:2:1 to prepare a D-type amino acid biofilm dispersant. In the biochemical slurry preparation stage of step one, this dispersant was added at a mass ratio of 5% to a mixture composed of bacterial sludge, composite enzymes, and osmotically compatible solutes (tetrahydropyrimidine, betaine, and trehalose). Due to the strong hydrogen bond donor-acceptor pairing between the free amino groups in the D-type amino acid molecular structure and the hydroxyl groups of solutes such as trehalose, the mixture did not undergo solute recrystallization during the subsequent -50℃ freeze-drying and vacuum sublimation processes. Instead, it formed a highly stable, homogeneous amorphous solid solution.

[0101] The finished microcapsules were applied to the circulating water system of a chemical plant with a concentration ratio of 28 times. The biofilm in this system exhibited extremely high density and strong resistance to enzymatic cleavage.

[0102] When the concentration of local quorum sensing signal molecules exceeds the threshold, the stimulus-responsive dynamic polymer shell swells, and the micropores change from a dense state to a porous state.

[0103] Because the molecular weight of D-amino acids (approximately 131-204 Da) is much smaller than that of complex bioenzymes (approximately 20-60 kDa), their effective hydrodynamic diffusion coefficient is about two orders of magnitude higher than that of enzyme molecules. Experimental observations show that within the first 15 minutes after swelling occurs, D-amino acids are released first and permeate into the biomembrane matrix. By competitively replacing D-alanine in the peptidoglycan network, they cause the biomembrane skeleton to loosen and detach, "softening" the originally dense biomembrane layer and opening up a large number of enzymatic attack sites.

[0104] The subsequently released complex bioenzymes were able to directly penetrate the deep layers of the biomembrane, exhibiting an apparent degradation rate. It exhibits a significant nonlinear gain.

[0105] In this embodiment, the data obtained by the online micro-monitoring device is fitted as follows:

[0106] in, The apparent biodegradation rate after introducing the D-type amino acid biofilm dispersant is expressed in mg / (L·h). The initial biodegradation rate under the action of the aforementioned composite enzyme alone is, in this embodiment, [missing information]. mg / (L·h); The dispersion synergy coefficient is dimensionless and has a value of 2.8. The real-time concentration of the D-type amino acid biofilm dispersant released in the local microenvironment, in units of mol / L; The half-maximum effective concentration constant of the D-type amino acid biofilm dispersant is [value missing]. mol / L. When locally Release concentration reached At mol / L, the calculated values ​​are: mg / (L·h), the apparent degradation rate increased to the initial rate. It is about 3.1 times that.

[0107] The evaluation results after 90 days of operation are shown in Table 3. Due to the implementation of a step-by-step attack of "dispersion first, degradation later", this embodiment not only increased the biofilm stripping rate to over 98%, but also significantly reduced the system cleaning frequency.

[0108] Table 3. Comparison of operating performance parameters between Example 6 and Example 1;

[0109] Data shows that by introducing D-type amino acids and constructing a spatiotemporal cascade release pathway, the technical challenge of single biochemically active substances being unable to penetrate dense fouling layers under ultra-high concentration conditions has been successfully solved.

[0110] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0111] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A biochemical agent with self-feedback efficiency control for ultra-high concentration ratio of industrial circulating water, characterized in that: The pharmaceutical agent is a core-shell microcapsule with a three-layer structure, comprising, from the inside out: The ultra-high concentration biochemical core contains extreme halophilic engineered bacteria, complex biological enzymes, and osmotically compatible solutes, and the ultra-high concentration biochemical core is in a dehydrated vitrified dormant state with a water content of less than 5%. A flexible stress buffer layer, covering the outer surface of the ultra-high concentration biochemical core, is composed of a modified polysiloxane elastomer with a crosslinking degree of 15% to 25%. The stimulus-responsive dynamic polymer shell is assembled from a polysaccharide backbone, a dynamic covalent crosslinking agent, and a fouling signaling molecule receptor through a dual crosslinking network. The polysaccharide backbone is covalently grafted with a calcium ion shielding group, which is an ethylenediaminetetraacetic acid derivative. The chelation constant Log K of the calcium ion shielding group for calcium ions is greater than 10.5, and the grafting amount is 5% to 12% of the mass of the polysaccharide backbone. The crosslinking bonds constructed by the dynamic covalent crosslinking agent are dynamic covalent bonds with thermodynamically reversible dissociation properties; The fouling signal molecule receptor is a protein receptor or a molecularly imprinted polymer having a high affinity for a quorum sensing signal molecule comprising at least one of N-acylhomoserine lactone and autoinducer-2, the density of the fouling signal molecule receptor in the stimulus-responsive dynamic polymer shell is 10 -6 mol / g to 10 -4 mol / g; The contamination signaling molecule receptor, upon binding to the quorum sensing signaling molecule, triggers the dissociation of the dynamic covalent bond.

2. The biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback regulation according to claim 1, characterized in that, The dynamic covalent bond is selected from one of the following: borate ester bond, acylhydrazone bond, and disulfide bond.

3. The biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback regulation according to claim 1, characterized in that, The extreme halophilic engineered bacteria is a mixed bacterial community of genetically engineered Halomonas and Coccidia fuciformis, with a mixing mass ratio of 1:

1. Both Halomonas and Coccidia fuciformis have undergone site-directed mutagenesis to enhance the expression of osmolarity regulatory proteins ProU and ProP. The composite bioenzyme is composed of salt-tolerant cellulase, protease and lipase, and the enzyme activity of each enzyme is not less than 50,000 U / g. The anti-hyperosmolarity compatibility solute is a mixture of tetrahydropyrimidine, betaine, and trehalose, wherein the mass ratio of tetrahydropyrimidine, betaine, and trehalose is 5:3:

2.

4. The biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback regulation according to claim 1, characterized in that, The microcapsules have a particle size distribution ranging from 50 micrometers to 150 micrometers and a density ranging from 1.05 g / cm³ to 1.15 g / cm³; the flexible stress buffer layer has a thickness of 10 micrometers to 20 micrometers and a Shore hardness of A10 to A20.

5. The biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback regulation according to claim 1, characterized in that, The outer surface of the flexible stress buffer layer is covalently anchored with a halophilic quorum sensing quenching enzyme. When the stimulus-responsive dynamic polymer shell is in a closed state, the stimulus-responsive dynamic polymer shell forms a steric barrier shield for the halophilic quorum sensing quenching enzyme. After the stimulus-responsive dynamic polymer shell swells, the halophilic quorum sensing quenching enzyme is exposed to circulating water to catalytically degrade the residual quorum sensing signal molecules.

6. The biochemical agent for ultra-high concentration ratio of industrial circulating water with self-feedback regulation according to claim 5, characterized in that, The halophilic quorum quenching enzyme is a halophilic N-acyl homoserine lactonase that is anchored to the outer surface of the flexible stress buffer layer by multipoint covalent cross-linking with a fixed density in the range of 1.0 x 10 -11 mol / cm2to 5.0 x 10 -10 mol / cm2.

7. A method for self-feedback regulation of the efficacy of a biochemical agent with an ultra-high concentration ratio in industrial circulating water, based on the efficacy self-feedback regulation method described in claim 6, characterized in that, Includes the following steps: Step 1: Add the reagent to the industrial circulating water system at the initial concentration; During normal system operation, the stimulus-responsive dynamic polymer shell remains closed, isolating the ultra-concentrated biochemical core from the external circulating water environment. Step 2: When the concentration of quorum sensing signal molecules in a local area exceeds the response threshold of the fouling signal molecule receptor, the fouling signal molecule receptor captures the quorum sensing signal molecules, triggering the dissociation of the dynamic covalent bonds, and causing the stimulus-responsive dynamic polymer shell to swell with a swelling rate of not less than 300%, thereby releasing the biochemically active substances encapsulated in the ultra-high concentration biochemical core to the local area in situ. Step 3: The released biochemically active substances biodegrade the contaminants in the localized area; Step four: When the concentration of quorum sensing signal molecules in the local area decreases below the response threshold, the dynamic covalent bonds spontaneously recombine, and the stimulus-responsive dynamic polymer shell returns to its closed state.

8. The method for self-feedback regulation of drug efficacy according to claim 7, characterized in that, In step three, the release flux of the agent and the quorum sensing signal molecular load follow the following mapping relationship: in, The flux released is expressed in mg / (m²·h); To release the kinetic constant, its unit is... The value of is determined by; The concentration of quorum sensing signal molecules measured in a local microenvironment is expressed in nmol / L. The response threshold concentration of the contamination signaling molecule receptor is given in nmol / L. The response sensitivity coefficient is dimensionless and ranges from 1.5 to 3.

0.

9. The method for self-feedback regulation of drug efficacy according to claim 7, characterized in that, During normal system operation, the closed stimulus-responsive dynamic polymer shell of the biochemical agent with high efficiency self-feedback regulation of ultra-high industrial circulating water concentration ratio forms a spatial steric barrier shield against the halophilic quorum sensing quenching enzyme. In step two, after the stimulus-responsive dynamic polymer shell swells, moisture and the quorum sensing signal molecules permeate to the surface of the flexible stress buffer layer, and the halophilic quorum sensing quenching enzyme catalytically degrades the quorum sensing signal molecules. In step four, the halophilic quorum sensing quenching enzyme catalyzes the degradation of residual quorum sensing signal molecules, accelerating the process of reducing their concentration to below the response threshold, thereby driving the spontaneous recombination of the dynamic covalent bonds.

10. The method for self-feedback regulation of drug efficacy according to claim 9, characterized in that, The degradation of the quorum sensing signal molecule by the halophilic quorum sensing quencher enzyme follows the Michaelis-Menten equation: in, For degradation rate, For the maximum reaction rate, It is the Michaelis constant. This represents the measured concentration of molecules in the quorum sensing signal.

Images