Fermented Chinese herbal non-antibiotic feed additive for beef cattle and preparation method thereof

Abstract

The application discloses a fermented Chinese herbal medicine antibiotic-free feed additive for beef cattle and a preparation method thereof, and relates to the technical field of feed processing.The fermented Chinese herbal medicine antibiotic-free feed additive for beef cattle is composed of polyacrylic resin II modified composite hydrogel balls and Chinese herbal medicine residue fermentation base material; the Chinese herbal medicine residue fermentation base material is structurally compounded with the polyacrylic resin II modified composite hydrogel to form composite particles with a'skeleton-function body' structure and adhesion, a functional complex for nutrition supply and intestinal targeting is constructed, the targeted delivery function of the hydrogel balls enables the composite particles to maintain the structural integrity in the process of passing through the rumen, and the active components are responsively released after entering the intestinal tract, so that the effective release of nutrients and active components is realized, the growth performance of beef cattle is significantly improved, the antibacterial and anti-inflammatory effects are accurately applied to the intestinal target, and the diarrhea risk caused by harmful substances such as mycotoxins in the feed is effectively relieved.

Description

Technical Field

[0001] This invention belongs to the field of feed processing technology, specifically referring to a fermented herbal antibiotic-free feed additive for beef cattle and its preparation method. Background Technology

[0002] With the rapid development of my country's traditional Chinese medicine industry, the demand for Chinese herbal medicines continues to rise. The resulting large amount of Chinese herbal medicine residue has not only brought environmental burden but also caused a great waste of biomass resources. However, Chinese herbal medicine residue not only retains certain medicinal components but is also rich in nutrients such as crude fiber, protein, polysaccharides, amino acids, and trace elements, and has high potential for resource recycling. Therefore, promoting the biomass conversion and utilization of Chinese herbal medicine residue has important practical significance.

[0003] Meanwhile, advancements in modern agriculture and animal husbandry technology have exacerbated animal health issues. The overuse of antibiotics can lead to drug resistance and drug residues, seriously threatening public health and safety, prompting the industry to seek safe alternatives. The natural antibacterial active substances in traditional Chinese medicine residue offer a new approach to this problem. By treating traditional Chinese medicine residue through microbial fermentation technology, its toxic side effects can be reduced, its nutritional level improved, and new beneficial metabolites can be generated, improving palatability. Based on these characteristics, the application value of traditional Chinese medicine residue in animal health and disease prevention is becoming increasingly prominent.

[0004] The existing technology currently has the following main problems:

[0005] Fermented feed has a low degradation rate in the rumen of beef cattle, resulting in low nutrient utilization and difficulty in effectively optimizing growth performance. At the same time, excessive amounts of harmful microorganisms such as mold or E. coli can easily grow during fermentation or storage, thereby damaging the animal's intestinal health and increasing the risk of diarrhea. Summary of the Invention

[0006] In view of the above situation and to overcome the defects of the prior art, the present invention proposes a fermented Chinese herbal medicine antibiotic-free feed additive for beef cattle, comprising the following components in parts by weight: 10-20 parts of polyacrylic acid resin II modified composite hydrogel balls and 50-60 parts of fermented Chinese herbal medicine residue substrate.

[0007] The polyacrylic acid resin II modified composite hydrogel spheres are supported by a three-dimensional framework formed by the cross-linking of sodium alginate and calcium ions. The reinforcing network composed of sodium alginate and gelatin enhances mechanical strength. The introduced polyacrylic acid resin II serves as a pH-responsive modification layer, endowing the system with targeted release characteristics. The three-layer network works synergistically to physically encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, thereby achieving rumen protection and intestinal targeted delivery of active components for ruminants.

[0008] The fermented feed base of traditional Chinese medicine residue is a functional feed base with loose fiber structure and rich in active metabolites, made by using traditional Chinese medicine residue as the main raw material, supplemented with corn flour and soybean meal to provide carbon and nitrogen sources, under the synergistic fermentation of Bacillus subtilis and Lactobacillus plantarum, and with the assistance of enzymatic hydrolysis by neutral protease, alkaline protease and cellulase, and through aerobic fermentation and freeze drying process.

[0009] The Chinese herbal medicine residues include the following components in parts by weight: 5-10 parts Astragalus membranaceus residue, 5-10 parts Acanthopanax senticosus residue, 5-10 parts Codonopsis pilosula residue, 5-10 parts Taraxacum mongolicum residue, 5-10 parts Dioscorea opposita residue, 5-10 parts Plantago asiatica residue, and 5-10 parts Poria cocos residue.

[0010] The preparation method of the polyacrylic acid resin II modified composite hydrogel spheres specifically includes the following steps:

[0011] (1) Montmorillonite K-10 was dispersed in a mixed solvent of 30 mL deionized water and 10 mL anhydrous ethanol and magnetically stirred at room temperature for 24 h to obtain a montmorillonite suspension. Then, 0.3-0.6 g of copper nitrate and 0.2 g of sodium carboxymethyl cellulose were added sequentially, and stirring was continued for 30 min. The suspension was then transferred to a 100 mL hydrothermal reactor and reacted at 180 °C for 12 h. After cooling to room temperature, the mixture was centrifuged at 10000 rpm for 10 min. The precipitate was washed three times each with deionized water and anhydrous ethanol, and vacuum dried at 60 °C for 12 h. The resulting powder was heated to 450 °C at a heating rate of 5 °C / min in air atmosphere, calcined at this temperature for 5 h, and then ground to obtain copper-modified montmorillonite composite. In this composite powder, copper ions enter the interlayer of montmorillonite through ion exchange, loading a carrier with potent antibacterial activity. On the one hand, the surface of the copper-loaded montmorillonite carries a residual positive charge due to the modification of copper ions, which can strongly adsorb negatively charged pathogens, causing their cell membranes to rupture and contents to leak out, thereby directly killing the bacteria. On the other hand, copper ions can effectively inhibit the tricarboxylic acid cycle, a key respiratory metabolic pathway of pathogens, blocking their energy source and causing bacterial death. Through the dual effects of physical adsorption to remove harmful toxins and some pathogens, as well as chemical active killing of pathogenic microorganisms and repair and protection of the intestinal mucosa, this composite powder can systematically improve the health status of beef cattle, reduce the diarrhea rate, and improve production performance.

[0012] (2) Weigh 1.0 g of the copper-modified montmorillonite composite powder described in step (1) and disperse it in 100 mL of deionized water. Stir magnetically for 1 h to form a suspension. Then, add 0.03 mol / L of [N2-(N-glycyl-L-histyl)-L-lysine]copper aqueous solution and 0.3-0.5 g of sodium carboxymethyl cellulose to the suspension in sequence. Continue stirring until the mixture is uniform. Adjust the pH of the system to 7.0-7.5 with sodium hydroxide solution and continue stirring for 30 min. Then, quickly add 5 mL of 0.03-0.05 mol / L ascorbic acid solution and continue stirring magnetically for 10 min. Seal and let stand at room temperature for 3 h. Centrifuge at 10000 rpm for 5 min. Wash the precipitate repeatedly with deionized water 3 times. Finally, dry it in an oven at 60-80℃ to obtain the copper-loaded montmorillonite composite. The sodium carboxymethyl cellulose / copper-modified montmorillonite complex contains [N2-(N-glycyl-L-histyl)-L-lysine]copper loaded on the surface of copper-modified montmorillonite composite powder. Sodium carboxymethyl cellulose acts as a binder and dispersant, encapsulating and fixing the entire system to form a multifunctional complex with physical adsorption, chemical antibacterial properties, and biological activity. Montmorillonite adsorbs mycotoxins and pathogens through its interlayer structure and large specific surface area, exerting a physical defense effect. Copper ions directly kill or inhibit intestinal pathogens, providing a chemical antibacterial barrier. Copper peptides provide a highly efficient bioactive copper source and assist in repairing damaged intestinal mucosa. The combination of these three elements achieves multi-dimensional management of beef cattle's intestinal health through "defense-repair-conditioning," reducing diarrhea caused by harmful substances in feed and ensuring nutrient absorption through a healthy intestinal environment, thereby improving production performance.

[0013] (3) Add polyacrylic acid resin II to 100 mL of sodium alginate aqueous solution with a mass fraction of 1.5%, and stir magnetically at 55 °C until completely dissolved. Then, add 0.75-0.85 g of gelatin and continue stirring at the same temperature until the gelatin is fully swollen. After the composite sol is naturally cooled to room temperature, add 1.0-2.0 g of sodium carboxymethyl cellulose / copper modified montmorillonite composite loaded with copper peptide described in step (2), and stir magnetically for 30 min. Add 0.3-0.5 g of calcium carbonate powder and stir magnetically for 20 min. Then add 5 mL of gluconate-δ-lactone solution with a mass fraction of 0.6%, mix rapidly within 2 min, and use a syringe to draw up the mixed sol and push it into deionized water. Let it stand for 30 min to crosslink and cure. The collected hydrogel spheres yielded polyacrylic acid resin II modified composite hydrogel spheres. In this process, the basic cross-linking network of sodium alginate and calcium ions, the reinforcing network of sodium alginate and gelatin, and the introduced polyacrylic acid resin II modification layer encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, forming a composite hydrogel sphere with a high-strength three-dimensional framework, pH-responsive release characteristics, and the ability to load multiple active components. The protective and targeted delivery function of the hydrogel spheres enables copper peptides and copper-modified montmorillonite to reach the intestines in an active form, reducing gastric loss and improving bioavailability. At the same time, it enhances intestinal targeted adsorption and antibacterial effects. By improving the utilization efficiency of active components and intestinal protection, it improves the growth performance and intestinal health of beef cattle.

[0014] Preferably, in step (1), the amount of montmorillonite used is 0.4-0.8g, and the specific surface area is 240m². 2 Montmorillonite has a huge specific surface area and cation exchange capacity, which can effectively adsorb mycotoxins in feed, reduce their damage to the animal's digestive tract, and also adsorb and inhibit harmful pathogens such as Escherichia coli, protect the gastrointestinal mucosa, and reduce the risk of diarrhea caused by harmful substances in feed from the source.

[0015] Preferably, in step (2), the amount of [N2-(N-glycyl-L-histyl)-L-lysine]copper aqueous solution added is 5-10 mL. [N2-(N-glycyl-L-histyl)-L-lysine]copper, as a stable copper peptide chelate, can be absorbed by the intestine in its intact form, providing bioavailable essential trace elements. At the same time, it has anti-inflammatory and antioxidant effects, can significantly reduce the levels of inflammatory factors such as TNF-α and IL-6, and protect cells from oxidative damage by scavenging free radicals.

[0016] Preferably, in step (3), the amount of polyacrylic acid resin II added is 0.1-0.3g. As an enteric coating material, polyacrylic acid resin II can remain stable in the rumen environment of ruminants and accurately release the active components into the intestines, thereby improving the bioavailability of the active ingredients.

[0017] This invention also provides a method for preparing a fermented herbal antibiotic-free feed additive for beef cattle, specifically including the following steps:

[0018] S1. Mix the residues of Astragalus membranaceus, Acanthopanax senticosus, Codonopsis pilosula, Taraxacum mongolicum, Dioscorea opposita, Plantago asiatica, and Poria cocos to obtain the Chinese herbal medicine residues for later use. Inoculate 1.0-2.0g of Bacillus subtilis and 1.0-2.0g of Lactobacillus plantarum into LB medium for activation. After incubation at 37℃ in a shaker for 1-2 days, the viable count of the bacterial suspension is 3×10⁻⁶. 9 CFU / mL, add Chinese herbal medicine residue, corn flour, and soybean meal powder to 1-2 times the amount of pure water, mix well, sterilize at 100℃ for 30 min, adjust the pH of the material to 7.0-7.5, cool to room temperature, add 3-5% Bacillus subtilis suspension, 1-3% Lactobacillus plantarum suspension, and 4.0-6.0g of compound enzyme, and carry out aerobic fermentation at 37℃ for 72 h. During fermentation, the material thickness is 3-5cm, covered with gauze, and turned 1-2 times a day. Finally, freeze-dry to obtain the fermentation substrate of Chinese herbal medicine residue. Through the synergistic effect of microorganisms and enzymes, the fermentation process of Chinese herbal medicine residue is carried out. The plant cell walls of the medicinal residue are "disassembled" and "recombined" to form a fermented substrate with a looser fibrous structure that provides nutrition, regulates intestinal flora, and has anti-diarrheal functions. This transforms the fibrous medicinal residue, which was originally difficult for animals to directly utilize, into a functional feed substrate rich in active metabolites. By maintaining the balance of the intestinal microecology and leveraging the immunomodulatory function of the active ingredients of traditional Chinese medicine, it systematically reduces the risk of diarrhea and improves production performance. At the same time, the released active ingredients of traditional Chinese medicine have natural antibacterial, anti-inflammatory, and immunomodulatory functions, enhancing the animal's disease resistance and thus reducing the risk of diarrhea caused by harmful bacteria or stress.

[0019] S2. Weigh 50.0-60.0g of the fermented herbal residue substrate mentioned in step S1 and mix it with 10.0-20.0g of polyacrylic acid resin II modified composite hydrogel balls at 20rpm for 10-15min, controlling the moisture content to 30-35%. Transfer the mixture to a granulator for granulation. The screen aperture is 1.5mm, the mixing speed is 20-30rpm, and the shearing speed is 50-60rpm. After granulation, dry the mixture with hot air at 40℃ for 2h to obtain a fermented herbal antibiotic-free feed additive for beef cattle. The fermented herbal residue substrate serves as the main component of the pellets, providing nutrition and active ingredients. Polyacrylic acid resin II... Modified composite hydrogels, as functional enhancement components, are mixed with fermentation substrate in a wet state. After granulation and low-temperature drying, they form "skeleton-functional" composite particles with good adhesion and molding properties. After feeding, the particle structure enables the gradual release of nutrients and active ingredients, which helps maintain a relatively stable nutrient supply environment in the rumen. At the same time, the targeted delivery function of the hydrogel spheres allows the composite particles to maintain structural integrity during the passage of the rumen. After entering the intestine, they release active components in response, precisely targeting the intestinal targets with antibacterial and anti-inflammatory effects, improving bioavailability, and effectively alleviating diarrhea caused by harmful substances such as mycotoxins in feed.

[0020] Preferably, in step S1, the mass ratio of neutral protease, alkaline protease, and cellulase in the compound enzyme is 0.75:0.25:1. Cellulase can directionally degrade fibrous components, making the cell wall structure loose and directly releasing small molecule active ingredients such as flavonoids, polysaccharides, and saponins from the cells. It also reduces the crude fiber content and relatively increases the crude protein ratio, thereby improving the overall nutritional value and digestibility of the medicinal residue. Protease breaks down the large molecule proteins in the medicinal residue that are difficult to utilize into smaller molecule peptides and free amino acids that are easier to absorb.

[0021] The beneficial effects achieved by this invention are as follows:

[0022] This invention structurally combines fermented Chinese herbal medicine residue with polyacrylic acid resin II modified composite hydrogel to form a "skeleton-functional" composite particle with adhesive properties. This creates a functional composite that provides nutrition and targets the intestines. The targeted delivery function of the hydrogel spheres allows the composite particles to maintain their structural integrity during rumen passage and release active components in response after entering the intestines. This achieves effective release of nutrients and active ingredients, significantly improving the growth performance of beef cattle. It also precisely targets the intestinal sites with antibacterial and anti-inflammatory effects, improving bioavailability and effectively alleviating the risk of diarrhea caused by mycotoxins and other harmful substances in feed. In the polyacrylic acid resin II modified composite hydrogel sphere, the basic cross-linking network formed by sodium alginate and calcium ions, the reinforcing network formed by sodium alginate and gelatin, and the introduced polyacrylic acid resin II modification layer together encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, forming a composite hydrogel sphere with a high-strength three-dimensional framework, pH-responsive release characteristics, and the ability to load multiple active components. This structure enables the copper peptide-loaded complex to achieve multi-dimensional management of beef cattle's intestinal health through physical adsorption, chemical antibacterial action, and bioactivity, reducing the risk of infection caused by feed irritation. Diarrhea caused by harmful substances in the feed is mitigated by a healthy intestinal environment that ensures nutrient absorption. The protective and targeted delivery function of the hydrogel spheres ensures that copper peptides and copper-modified montmorillonite reach the intestines in their active form, reducing gastric loss and improving bioavailability. Simultaneously, it enhances intestinal targeted adsorption and antibacterial effects. By improving the utilization efficiency of active components and intestinal protection, this composite hydrogel sphere can systematically improve the growth performance and intestinal health of beef cattle. In the fermented herbal residue substrate, through the synergistic action of microorganisms and enzymes, the plant cell walls of the herbal residue undergo deep degradation and structural transformation, ultimately forming a loosely fibrous, multi-functional... This invention relates to a fermented feed substrate with nutritional supplementation, gut microbiota regulation, and anti-diarrheal functions. This process transforms fibrous medicinal residues, which are difficult for animals to directly utilize, into a functional feed substrate rich in active metabolites. By maintaining the balance of the gut microbiota and leveraging the immunomodulatory function of the active ingredients in traditional Chinese medicine, it enhances animal disease resistance and reduces the risk of diarrhea caused by harmful bacteria or stress, thereby systematically improving the production performance of beef cattle. The invention uses polyacrylic acid resin II modified composite hydrogel balls and fermented medicinal herb residues to create a fermented herbal antibiotic-free feed additive for beef cattle. This additive not only effectively optimizes growth performance but also significantly reduces the diarrhea rate in beef cattle. Attached Figure Description

[0023] Figure 1 The graph shows the diarrhea rate results of Examples 1-3 and Comparative Examples 1-4 of the present invention;

[0024] Figure 2 The figures show the growth performance results of Examples 1-3 and Comparative Examples 1-4 of the present invention. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0027] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; unless otherwise specified, the experimental materials used in the following embodiments are all purchased from commercial channels.

[0028] The reagents used in the examples were sourced from the following sources:

[0029] Bacillus subtilis brand Huankai Microbiology, product number 00711123;

[0030] Lactobacillus plantarum brand Tanmo quality inspection, product number BHCC100926;

[0031] LB culture medium, brand name Yuanye, product number R28105-500ml;

[0032] Neutral protease CAS No: 9068-59-1, Brand: Innochem, Product No. B99905, Specification: 50u / mg;

[0033] Alkaline protease CAS No: 9014-01-1, brand Zunlijia, product number 31094949-500mg, specification 200u / mg;

[0034] Cellulase CASNo:9012-54-8, Brand: Yuanye, Product No.: S10041-5g, Specification: 50u / mg.

[0035] Example 1

[0036] This embodiment proposes a fermented herbal medicine antibiotic-free feed additive for beef cattle, comprising the following components in parts by weight: 20 parts of polyacrylic acid resin II modified composite hydrogel balls and 60 parts of fermented herbal medicine residue substrate.

[0037] The Chinese herbal medicine residues include the following components by weight: 10 parts Astragalus membranaceus residue, 10 parts Acanthopanax senticosus residue, 10 parts Codonopsis pilosula residue, 10 parts Taraxacum mongolicum residue, 10 parts Dioscorea opposita residue, 10 parts Plantago asiatica residue, and 10 parts Poria cocos residue.

[0038] The preparation method of polyacrylic acid resin II modified composite hydrogel spheres specifically includes the following steps:

[0039] (1) Montmorillonite K-10 was dispersed in a mixed solvent of 30 mL deionized water and 10 mL anhydrous ethanol and magnetically stirred at room temperature for 24 h to obtain a montmorillonite suspension. The amount of montmorillonite used was 0.8 g, and the specific surface area was 240 m². 2 Montmorillonite, with its large specific surface area and cation exchange capacity, can effectively adsorb mycotoxins in feed, reducing their damage to the animal's digestive tract. It can also adsorb and inhibit harmful pathogens such as Escherichia coli, protecting the gastrointestinal mucosa and reducing the risk of diarrhea caused by harmful substances in feed from the source. Subsequently, 0.6 g of copper nitrate and 0.2 g of sodium carboxymethyl cellulose were added sequentially, and stirring was continued for 30 min. The suspension was transferred to a 100 mL hydrothermal reactor and reacted at 180 °C for 12 h. After cooling to room temperature, it was centrifuged at 10000 rpm for 10 min. The precipitate was washed three times each with deionized water and anhydrous ethanol, and then vacuum dried at 60 °C for 12 h. The resulting powder was heated to 450 °C in air at a heating rate of 5 °C / min. After calcination for 5 hours and grinding, copper-modified montmorillonite composite powder was obtained. In this composite powder, copper ions enter the interlayer of montmorillonite through ion exchange, loading the carrier with strong antibacterial activity. On the one hand, the surface of copper-loaded montmorillonite carries a residual positive charge due to copper ion modification, which can strongly adsorb negatively charged pathogens, causing their cell membranes to rupture and contents to leak out, thereby directly killing the bacteria. On the other hand, copper ions can effectively inhibit the tricarboxylic acid cycle, a key respiratory metabolic pathway of pathogens, blocking their energy source and causing bacterial death. Through the dual effects of physical adsorption to remove harmful toxins and some pathogens, as well as chemical active killing of pathogenic microorganisms and repair and protection of intestinal mucosa, this composite powder can systematically improve the health status of beef cattle, reduce the diarrhea rate and improve production performance.

[0040] (2) Weigh 1.0 g of the copper-modified montmorillonite composite powder described in step (1) and disperse it in 100 mL of deionized water. Stir magnetically for 1 h to form a suspension. Then, add 0.03 mol / L of a copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] and 0.5 g of sodium carboxymethyl cellulose to the suspension. The amount of copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] added is 10 mL. [N2-(N-glycyl-L-histyl)-L-lysine]copper, as a stable copper peptide chelate, can be absorbed by the intestine in its intact form, providing essential trace elements that are bioavailable. It also possesses anti-inflammatory and antioxidant effects, significantly reducing the levels of inflammatory factors such as TNF-α and IL-6, and protecting cells from oxidative damage by scavenging free radicals. The mixture was stirred continuously until homogeneous, and the pH was adjusted to 7.5 with sodium hydroxide solution. Stirring continued for 30 min, followed by rapid addition of 5 mL of 0.05 mol / L ascorbic acid solution. Magnetic stirring was continued for 10 min, and the mixture was sealed and allowed to age at room temperature for 3 h. After centrifugation at 10000 rpm for 5 min, the precipitate was washed three times with deionized water. Finally, it was dried in an oven at 80℃ to obtain a sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides. In this complex, [N2-(N-glycyl-L-histyl)-L-lysine]copper is loaded on the surface of the copper-modified montmorillonite composite powder. Sodium carboxymethyl cellulose acts as a binder and dispersant, encapsulating and fixing the entire system, forming a complex that combines physical adsorption and... This multifunctional complex combines chemical antibacterial properties with bioactivity. Montmorillonite, through its interlayer structure and large specific surface area, adsorbs mycotoxins and pathogens, exerting a physical defense effect. Copper ions directly kill or inhibit intestinal pathogens, providing a chemical antibacterial barrier. Copper peptides provide a highly efficient bioactive copper source and assist in repairing damaged intestinal mucosa. The combination of these three components achieves multi-dimensional management of beef cattle's intestinal health through "defense-repair-conditioning," reducing diarrhea caused by harmful substances in feed and ensuring nutrient absorption through a healthy intestinal environment, thereby improving production performance.

[0041] (3) Add polyacrylic acid resin II to 100 mL of sodium alginate aqueous solution with a mass fraction of 1.5% and stir magnetically at 55°C until completely dissolved. The amount of polyacrylic acid resin II added is 0.3 g. As an enteric coating material, polyacrylic acid resin II can remain stable in the rumen environment of ruminants and accurately release the active components into the intestine, thereby improving the bioavailability of the active ingredients. Then, add 0.85 g of gelatin and continue stirring at the same temperature until the gelatin is fully swollen. After the composite sol is naturally cooled to room temperature, add 2.0 g of sodium carboxymethyl cellulose / copper modified montmorillonite complex loaded with copper peptides as described in step (2) and stir magnetically for 30 min. Add 0.5 g of calcium carbonate powder and stir magnetically for 20 min. Then add 5 mL of gluconate-δ-lactone solution with a mass fraction of 0.6% and mix rapidly within 2 min. The mixture was homogenized and injected into deionized water using a syringe. After standing for 30 minutes to crosslink and solidify, the resulting hydrogel spheres were collected to obtain polyacrylic acid resin II modified composite hydrogel spheres. In this process, the basic crosslinking network of sodium alginate and calcium ions, the reinforcing network of sodium alginate and gelatin, and the introduced polyacrylic acid resin II modification layer encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, forming a composite hydrogel sphere with a high-strength three-dimensional skeleton, pH-responsive release characteristics, and the ability to load multiple active components. The protective and targeted delivery function of the hydrogel spheres enables copper peptides and copper-modified montmorillonite to reach the intestines in an active form, reducing gastric loss and improving bioavailability. At the same time, it enhances intestinal targeted adsorption and antibacterial effects. By improving the utilization efficiency of active components and protecting the intestines, it improves the growth performance and intestinal health of beef cattle.

[0042] This embodiment provides a method for preparing a fermented herbal antibiotic-free feed additive for beef cattle, specifically including the following steps:

[0043] S1. Mix the residues of Astragalus membranaceus, Acanthopanax senticosus, Codonopsis pilosula, Taraxacum mongolicum, Dioscorea opposita, Plantago asiatica, and Poria cocos to obtain the Chinese herbal medicine residues for later use. Inoculate 2.0g of Bacillus subtilis and 2.0g of Lactobacillus plantarum into LB medium for activation. After culturing in a shaker at 37℃ for 1 day, the viable count of the bacterial suspension is 3×10⁻⁶. 9CFU / mL, add Chinese herbal medicine residue, corn flour, and soybean meal powder to twice the amount of pure water, mix well, sterilize at 100℃ for 30 min, adjust the pH of the material to 7.5, cool to room temperature, and then add 5% Bacillus subtilis suspension, 3% Lactobacillus plantarum suspension, and 6.0g of compound enzyme. In the compound enzyme, the mass ratio of neutral protease, alkaline protease, and cellulase is 0.75:0.25:1. Cellulase can directionally degrade fibrous components, making the cell wall structure loose, and directly releasing small molecule active ingredients such as flavonoids, polysaccharides, and saponins from the cells. It also reduces the crude fiber content and relatively increases the crude protein ratio, thereby improving the overall nutritional value and digestibility of the herbal residue. Protease breaks down the large molecule proteins in the Chinese herbal medicine residue that are difficult to utilize into smaller molecule peptides and free amino acids that are easier to absorb. Aerobic fermentation was carried out at 37℃ for 72 hours. During the fermentation process, the material was 5cm thick, covered with gauze, and turned twice a day. Finally, it was freeze-dried to obtain the fermented base material of Chinese herbal medicine residue. Through the synergistic effect of microorganisms and enzymes, the plant cell walls of the Chinese herbal medicine residue were "disassembled" and "recombined" to form a fermented base material with a looser fiber structure that has the functions of nutritional supplementation, intestinal flora regulation and anti-diarrheal function. This transformed the fibrous medicinal residue, which was originally difficult for animals to directly utilize, into a functional feed base material rich in active metabolites. By maintaining the balance of intestinal microecology and exerting the immune regulation function of active ingredients of Chinese herbal medicine, the risk of diarrhea is systematically reduced and production performance is improved. At the same time, the released active ingredients of Chinese herbal medicine have natural antibacterial, anti-inflammatory and immune regulation functions, which enhance the animal's disease resistance and reduce the risk of diarrhea caused by harmful bacteria or stress.

[0044] S2. Weigh 60.0g of the fermented herbal residue substrate mentioned in step S1 and mix it with 20.0g of polyacrylic acid resin II modified composite hydrogel balls at 20 rpm for 15 minutes, controlling the moisture content to 35%. Transfer the mixture to a granulator for granulation. The screen aperture is 1.5mm, the mixing speed is 30 rpm, and the shearing speed is 60 rpm. After granulation, dry the mixture with hot air at 40℃ for 2 hours to obtain a fermented herbal antibiotic-free feed additive for beef cattle. The fermented herbal residue substrate serves as the main component of the granules, providing nutrition and active ingredients, while the polyacrylic acid resin II modified composite hydrogel serves as the functional component. The fortified components are mixed with the fermentation base in a wet form, and after granulation and low-temperature drying, they form a "skeleton-functional" composite granule with good binding and molding properties. After feeding, the granule structure enables the gradual release of nutrients and active ingredients, which helps maintain a relatively stable nutrient supply environment in the rumen. At the same time, the targeted delivery function of the hydrogel spheres allows the composite granules to maintain structural integrity during the passage of the rumen. After entering the intestine, they release active ingredients in response, precisely targeting the intestinal targets with antibacterial and anti-inflammatory effects, improving bioavailability, and effectively alleviating diarrhea caused by mycotoxins and other harmful substances in the feed.

[0045] Example 2

[0046] This embodiment proposes a fermented herbal medicine antibiotic-free feed additive for beef cattle, comprising the following components in parts by weight: 20 parts of polyacrylic acid resin II modified composite hydrogel balls and 50 parts of fermented herbal medicine residue substrate.

[0047] The Chinese herbal medicine residues include the following components in parts by weight: 7.5 parts Astragalus membranaceus residue, 7.5 parts Acanthopanax senticosus residue, 7.5 parts Codonopsis pilosula residue, 7.5 parts Taraxacum mongolicum residue, 7.5 parts Dioscorea opposita residue, 7.5 parts Plantago asiatica residue, and 7.5 parts Poria cocos residue.

[0048] The preparation method of polyacrylic acid resin II modified composite hydrogel spheres specifically includes the following steps:

[0049] (1) Montmorillonite K-10 was dispersed in a mixed solvent of 30 mL deionized water and 10 mL anhydrous ethanol and magnetically stirred at room temperature for 24 h to obtain a montmorillonite suspension. The amount of montmorillonite used was 0.6 g, and the specific surface area was 240 m². 2 Montmorillonite, with its large specific surface area and cation exchange capacity, can effectively adsorb mycotoxins in feed, reducing their damage to the animal's digestive tract. It can also adsorb and inhibit harmful pathogens such as Escherichia coli, protecting the gastrointestinal mucosa and reducing the risk of diarrhea caused by harmful substances in feed from the source. Subsequently, 0.45g of copper nitrate and 0.2g of sodium carboxymethyl cellulose were added sequentially, and stirring was continued for 30 minutes. The suspension was then transferred to a 100mL hydrothermal reactor and reacted at 180℃ for 12 hours. After cooling to room temperature, it was centrifuged at 10000rpm for 10 minutes. The precipitate was washed three times each with deionized water and anhydrous ethanol, and then vacuum-dried at 60℃ for 12 hours. The resulting powder was heated to 450℃ in air at a heating rate of 5℃ / min. The mixture was calcined for 5 hours and then ground to obtain copper-modified montmorillonite composite powder. In this composite powder, copper ions enter the interlayer of montmorillonite through ion exchange, loading the carrier with strong antibacterial activity. On the one hand, the surface of the copper-loaded montmorillonite carries a residual positive charge due to the modification of copper ions, which can strongly adsorb negatively charged pathogens, causing their cell membranes to rupture and their contents to leak out, thereby directly killing the bacteria. On the other hand, copper ions can effectively inhibit the tricarboxylic acid cycle, a key respiratory metabolic pathway of pathogens, blocking their energy source and causing the bacteria to die. Through the dual effects of physical adsorption to remove harmful toxins and some pathogens, as well as chemical active killing of pathogenic microorganisms and repair and protection of intestinal mucosa, this composite powder can systematically improve the health status of beef cattle, reduce the diarrhea rate, and improve production performance.

[0050] (2) Weigh 1.0 g of the copper-modified montmorillonite composite powder described in step (1) and disperse it in 100 mL of deionized water. Stir magnetically for 1 h to form a suspension. Then, add 0.03 mol / L of a copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] and 0.4 g of sodium carboxymethyl cellulose to the suspension. The amount of copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] added is 7.5 mL. [N2-(N-glycyl-L-histyl)-L-lysine]copper, as a stable copper peptide chelate, can be absorbed by the intestine in its intact form, providing essential trace elements that are bioavailable. It also possesses anti-inflammatory and antioxidant effects, significantly reducing the levels of inflammatory factors such as TNF-α and IL-6, and protecting cells from oxidative damage by scavenging free radicals. The mixture was stirred continuously until homogeneous, and the pH was adjusted to 7.3 with sodium hydroxide solution. Stirring continued for 30 min, followed by rapid addition of 5 mL of 0.04 mol / L ascorbic acid solution. Magnetic stirring was continued for 10 min, and the mixture was sealed and allowed to age at room temperature for 3 h. After centrifugation at 10000 rpm for 5 min, the precipitate was washed three times with deionized water. Finally, it was dried in a 70℃ oven to obtain a sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides. In this complex, [N2-(N-glycyl-L-histyl)-L-lysine]copper is loaded on the surface of the copper-modified montmorillonite composite powder. Sodium carboxymethyl cellulose acts as a binder and dispersant, encapsulating and fixing the entire system, forming a complex that combines physical adsorption and... This multifunctional complex combines chemical antibacterial properties with bioactivity. Montmorillonite, through its interlayer structure and large specific surface area, adsorbs mycotoxins and pathogens, exerting a physical defense effect. Copper ions directly kill or inhibit intestinal pathogens, providing a chemical antibacterial barrier. Copper peptides provide a highly efficient bioactive copper source and assist in repairing damaged intestinal mucosa. The combination of these three components achieves multi-dimensional management of beef cattle's intestinal health through "defense-repair-conditioning," reducing diarrhea caused by harmful substances in feed and ensuring nutrient absorption through a healthy intestinal environment, thereby improving production performance.

[0051] (3) Add polyacrylic acid resin II to 100 mL of sodium alginate aqueous solution with a mass fraction of 1.5% and stir magnetically at 55°C until completely dissolved. The amount of polyacrylic acid resin II added is 0.2 g. As an enteric coating material, polyacrylic acid resin II can remain stable in the rumen environment of ruminants and accurately release the active components into the intestine, thereby improving the bioavailability of the active ingredients. Then, add 0.80 g of gelatin and continue stirring at the same temperature until the gelatin is fully swollen. After the composite sol is naturally cooled to room temperature, add 1.5 g of sodium carboxymethyl cellulose / copper modified montmorillonite complex loaded with copper peptides as described in step (2) and stir magnetically for 30 min. Add 0.4 g of calcium carbonate powder and stir magnetically for 20 min. Then add 5 mL of gluconate-δ-lactone solution with a mass fraction of 0.6% and mix rapidly within 2 min. The mixture was homogenized and injected into deionized water using a syringe. After standing for 30 minutes to crosslink and solidify, the resulting hydrogel spheres were collected to obtain polyacrylic acid resin II modified composite hydrogel spheres. In this process, the basic crosslinking network of sodium alginate and calcium ions, the reinforcing network of sodium alginate and gelatin, and the introduced polyacrylic acid resin II modification layer encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, forming a composite hydrogel sphere with a high-strength three-dimensional skeleton, pH-responsive release characteristics, and the ability to load multiple active components. The protective and targeted delivery function of the hydrogel spheres enables copper peptides and copper-modified montmorillonite to reach the intestines in an active form, reducing gastric loss and improving bioavailability. At the same time, it enhances intestinal targeted adsorption and antibacterial effects. By improving the utilization efficiency of active components and protecting the intestines, it improves the growth performance and intestinal health of beef cattle.

[0052] This embodiment provides a method for preparing a fermented herbal antibiotic-free feed additive for beef cattle, specifically including the following steps:

[0053] S1. Mix the residues of Astragalus membranaceus, Acanthopanax senticosus, Codonopsis pilosula, Taraxacum mongolicum, Dioscorea opposita, Plantago asiatica, and Poria cocos to obtain the Chinese herbal medicine residues for later use. Inoculate 1.5g of Bacillus subtilis and 1.5g of Lactobacillus plantarum into LB medium for activation. After culturing in a shaker at 37℃ for 1.5 days, the viable count of the bacterial suspension is 3×10⁻⁶. 9CFU / mL, add Chinese herbal medicine residue, corn flour, and soybean meal powder to 1.5 times the amount of pure water, mix well, sterilize at 100℃ for 30 min, adjust the pH of the material to 7.3, cool to room temperature, and then add 4% Bacillus subtilis suspension, 2% Lactobacillus plantarum suspension, and 5.0g of compound enzyme. In the compound enzyme, the mass ratio of neutral protease, alkaline protease, and cellulase is 0.75:0.25:1. Cellulase can directionally degrade fiber components, making the cell wall structure loose, and directly releasing small molecule active ingredients such as flavonoids, polysaccharides, and saponins from the cells. It also reduces the crude fiber content and relatively increases the crude protein ratio, thereby improving the overall nutritional value and digestibility of the residue. Protease breaks down the large molecule proteins in the Chinese herbal medicine residue that are difficult to utilize into smaller molecule peptides and free amino acids that are easier to absorb. Aerobic fermentation was carried out at 37℃ for 72 hours. During the fermentation process, the material was 4cm thick, covered with gauze, and turned twice a day. Finally, it was freeze-dried to obtain the fermented base material of Chinese herbal medicine residue. Through the synergistic effect of microorganisms and enzymes, the plant cell walls of the Chinese herbal medicine residue were "disassembled" and "recombined" to form a fermented base material with a looser fiber structure that has the functions of nutritional supplementation, intestinal flora regulation and anti-diarrheal function. This transformed the fibrous medicinal residue that was originally difficult for animals to directly utilize into a functional feed base material rich in active metabolites. By maintaining the balance of intestinal microecology and exerting the immune regulation function of active ingredients of Chinese herbal medicine, the risk of diarrhea is systematically reduced and production performance is improved. At the same time, the released active ingredients of Chinese herbal medicine have natural antibacterial, anti-inflammatory and immune regulation functions, which enhance the animal's disease resistance and reduce the risk of diarrhea caused by harmful bacteria or stress.

[0054] S2. Weigh 50.0g of the fermented herbal residue substrate mentioned in step S1 and mix it with 20.0g of polyacrylic acid resin II modified composite hydrogel balls at 20 rpm for 12.5 min, controlling the moisture content at 32.5%. Transfer the mixture to a granulator for granulation. The screen aperture is 1.5mm, the mixing speed is 25 rpm, and the shearing speed is 55 rpm. After granulation, dry the mixture with hot air at 40℃ for 2 h to obtain a fermented herbal antibiotic-free feed additive for beef cattle. The fermented herbal residue substrate serves as the main component of the granules, providing nutrition and active ingredients. The polyacrylic acid resin II modified composite hydrogel serves as... The functional enhancement components are mixed with the fermentation base in a wet form, and after granulation and low-temperature drying, they form "skeleton-functional" composite particles with good binding and molding properties. After feeding, the particle structure enables the gradual release of nutrients and active ingredients, which helps maintain a relatively stable nutrient supply environment in the rumen. At the same time, the targeted delivery function of the hydrogel balls allows the composite particles to maintain structural integrity during the passage of the rumen. After entering the intestine, they release active components in response, precisely targeting the intestinal targets with antibacterial and anti-inflammatory effects, improving bioavailability, and effectively alleviating diarrhea caused by mycotoxins and other harmful substances in the feed.

[0055] Example 3

[0056] This embodiment proposes a fermented herbal medicine antibiotic-free feed additive for beef cattle, comprising the following components in parts by weight: 10 parts of polyacrylic acid resin II modified composite hydrogel balls and 50 parts of fermented herbal medicine residue substrate.

[0057] The Chinese herbal medicine residues include the following components by weight: 5 parts Astragalus membranaceus residue, 5 parts Acanthopanax senticosus residue, 5 parts Codonopsis pilosula residue, 5 parts Taraxacum mongolicum residue, 5 parts Dioscorea opposita residue, 5 parts Plantago asiatica residue, and 5 parts Poria cocos residue.

[0058] The preparation method of polyacrylic acid resin II modified composite hydrogel spheres specifically includes the following steps:

[0059] (1) Montmorillonite K-10 was dispersed in a mixed solvent of 30 mL deionized water and 10 mL anhydrous ethanol and magnetically stirred at room temperature for 24 h to obtain a montmorillonite suspension. The amount of montmorillonite used was 0.4 g, and the specific surface area was 240 m². 2 Montmorillonite, with its large specific surface area and cation exchange capacity, can effectively adsorb mycotoxins in feed, reducing their damage to the animal's digestive tract. It can also adsorb and inhibit harmful pathogens such as Escherichia coli, protecting the gastrointestinal mucosa and reducing the risk of diarrhea caused by harmful substances in feed from the source. Subsequently, 0.3g of copper nitrate and 0.2g of sodium carboxymethyl cellulose were added sequentially, and stirring was continued for 30 minutes. The suspension was then transferred to a 100mL hydrothermal reactor and reacted at 180℃ for 12 hours. After cooling to room temperature, it was centrifuged at 10000rpm for 10 minutes. The precipitate was washed three times each with deionized water and anhydrous ethanol, and then vacuum-dried at 60℃ for 12 hours. The resulting powder was heated to 450℃ in air at a rate of 5℃ / min. After calcination for 5 hours and grinding, copper-modified montmorillonite composite powder was obtained. In this composite powder, copper ions enter the interlayer of montmorillonite through ion exchange, loading the carrier with strong antibacterial activity. On the one hand, the surface of copper-loaded montmorillonite carries a residual positive charge due to copper ion modification, which can strongly adsorb negatively charged pathogens, causing their cell membranes to rupture and contents to leak out, thereby directly killing the bacteria. On the other hand, copper ions can effectively inhibit the tricarboxylic acid cycle, a key respiratory metabolic pathway of pathogens, blocking their energy source and causing bacterial death. Through the dual effects of physical adsorption to remove harmful toxins and some pathogens, as well as chemical active killing of pathogenic microorganisms and repair and protection of intestinal mucosa, this composite powder can systematically improve the health status of beef cattle, reduce the diarrhea rate and improve production performance.

[0060] (2) Weigh 1.0 g of the copper-modified montmorillonite composite powder described in step (1) and disperse it in 100 mL of deionized water. Stir magnetically for 1 h to form a suspension. Then, add 0.03 mol / L of a copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] and 0.3 g of sodium carboxymethyl cellulose to the suspension. The amount of copper aqueous solution of [N2-(N-glycyl-L-histyl)-L-lysine] added is 5 mL. [Lysine] Copper, as a stable copper peptide chelate, can be absorbed by the intestine in its intact form, providing essential trace elements that are bioavailable. It also possesses anti-inflammatory and antioxidant effects, significantly reducing the levels of inflammatory factors such as TNF-α and IL-6, and protecting cells from oxidative damage by scavenging free radicals. Continue stirring until homogeneous, adjust the pH of the system to 7.0 with sodium hydroxide solution, continue stirring for 30 min, then quickly add 5 mL of 0.03 mol / L ascorbic acid solution, and continue magnetic stirring for 10 min. After sealing and aging at room temperature for 3 hours, the mixture was centrifuged at 10,000 rpm for 5 minutes. The precipitate was washed three times with deionized water and then dried in an oven at 60°C to obtain a sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides. In this complex, [N2-(N-glycyl-L-histyl)-L-lysine]copper is loaded on the surface of the copper-modified montmorillonite composite powder. Sodium carboxymethyl cellulose acts as a binder and dispersant, encapsulating and fixing the entire system to form a multifunctional complex with physical adsorption, chemical antibacterial properties, and biological activity. Montmorillonite adsorbs mycotoxins and pathogens through its interlayer structure and large specific surface area, exerting a physical defense effect. Copper ions directly kill or inhibit intestinal pathogens, providing a chemical antibacterial barrier. Copper peptides provide a highly efficient bioactive copper source and assist in repairing damaged intestinal mucosa. The combination of these three elements achieves multi-dimensional management of beef cattle's intestinal health through "defense-repair-conditioning," reducing diarrhea caused by harmful substances in feed and ensuring nutrient absorption through a healthy intestinal environment, thereby improving production performance.

[0061] (3) Add polyacrylic acid resin II to 100 mL of sodium alginate aqueous solution with a mass fraction of 1.5% and stir magnetically at 55°C until completely dissolved. The amount of polyacrylic acid resin II added is 0.1 g. As an enteric coating material, polyacrylic acid resin II can remain stable in the rumen environment of ruminants and accurately release the active components into the intestine, thereby improving the bioavailability of the active ingredients. Then, add 0.75 g of gelatin and continue stirring at the same temperature until the gelatin is fully swollen. After the composite sol is naturally cooled to room temperature, add 1.0 g of sodium carboxymethyl cellulose / copper modified montmorillonite complex loaded with copper peptides as described in step (2) and stir magnetically for 30 min. Add 0.3 g of calcium carbonate powder and stir magnetically for 20 min. Then add 5 mL of gluconate-δ-lactone solution with a mass fraction of 0.6% and mix rapidly within 2 min. The mixture was homogenized and injected into deionized water using a syringe. After standing for 30 minutes to crosslink and solidify, the resulting hydrogel spheres were collected to obtain polyacrylic acid resin II modified composite hydrogel spheres. In this process, the basic crosslinking network of sodium alginate and calcium ions, the reinforcing network of sodium alginate and gelatin, and the introduced polyacrylic acid resin II modification layer encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, forming a composite hydrogel sphere with a high-strength three-dimensional skeleton, pH-responsive release characteristics, and the ability to load multiple active components. The protective and targeted delivery function of the hydrogel spheres enables copper peptides and copper-modified montmorillonite to reach the intestines in an active form, reducing gastric loss and improving bioavailability. At the same time, it enhances intestinal targeted adsorption and antibacterial effects. By improving the utilization efficiency of active components and protecting the intestines, it improves the growth performance and intestinal health of beef cattle.

[0062] This embodiment provides a method for preparing a fermented herbal antibiotic-free feed additive for beef cattle, specifically including the following steps:

[0063] S1. Mix the residues of Astragalus membranaceus, Acanthopanax senticosus, Codonopsis pilosula, Taraxacum mongolicum, Dioscorea opposita, Plantago asiatica, and Poria cocos to obtain the Chinese herbal medicine residues for later use. Inoculate 1.0g of Bacillus subtilis and 1.0-2.0g of Lactobacillus plantarum into LB medium for activation. After culturing in a shaker at 37℃ for 2 days, the viable count of the bacterial suspension is 3×10⁻⁶. 9CFU / mL, add Chinese herbal medicine residue, corn flour, and soybean meal powder to an equal volume of pure water, mix well, sterilize at 100℃ for 30 min, adjust the pH of the material to 7.0, cool to room temperature, and then add 3% Bacillus subtilis suspension, 1% Lactobacillus plantarum suspension, and 4.0g of compound enzyme. In the compound enzyme, the mass ratio of neutral protease, alkaline protease, and cellulase is 0.75:0.25:1. Cellulase can directionally degrade fibrous components, making the cell wall structure loose, directly releasing small molecule active ingredients such as flavonoids, polysaccharides, and saponins from the cells, and also reducing the crude fiber content and relatively increasing the crude protein ratio, thereby improving the overall nutritional value and digestibility of the herbal residue. Protease breaks down the large molecule proteins in the Chinese herbal medicine residue that are difficult to utilize into smaller molecule peptides and free amino acids that are easier to absorb. Aerobic fermentation was carried out at 37℃ for 72 hours. During the fermentation process, the material was 3cm thick and covered with gauze. The material was turned over once a day and finally freeze-dried to obtain the fermented base material of Chinese herbal medicine residue. Through the synergistic effect of microorganisms and enzymes, the plant cell walls of the Chinese herbal medicine residue were "disassembled" and "recombined" to form a fermented base material with a looser fiber structure that has the functions of nutritional supplementation, intestinal flora regulation and anti-diarrheal function. This transformed the fibrous medicinal residue, which was originally difficult for animals to directly utilize, into a functional feed base material rich in active metabolites. By maintaining the balance of intestinal microecology and exerting the immune regulation function of active ingredients of Chinese herbal medicine, the risk of diarrhea is systematically reduced and production performance is improved. At the same time, the released active ingredients of Chinese herbal medicine have natural antibacterial, anti-inflammatory and immune regulation functions, which enhance the animal's disease resistance and reduce the risk of diarrhea caused by harmful bacteria or stress.

[0064] S2. Weigh 50.0g of the fermented herbal residue substrate mentioned in step S1 and mix it with 10.0g of polyacrylic acid resin II modified composite hydrogel balls at 20 rpm for 10 minutes, controlling the moisture content to 30%. Transfer the mixture to a granulator for granulation. The screen aperture is 1.5mm, the mixing speed is 20 rpm, and the shearing speed is 50 rpm. After granulation, dry the mixture with hot air at 40℃ for 2 hours to obtain a fermented herbal antibiotic-free feed additive for beef cattle. The fermented herbal residue substrate serves as the main component of the granules, providing nutrition and active ingredients, while the polyacrylic acid resin II modified composite hydrogel serves as the functional component. The fortified components are mixed with the fermentation base in a wet form, and after granulation and low-temperature drying, they form a "skeleton-functional" composite granule with good binding and molding properties. After feeding, the granule structure enables the gradual release of nutrients and active ingredients, which helps maintain a relatively stable nutrient supply environment in the rumen. At the same time, the targeted delivery function of the hydrogel spheres allows the composite granules to maintain structural integrity during the passage of the rumen. After entering the intestine, they release active ingredients in response, precisely targeting the intestinal targets with antibacterial and anti-inflammatory effects, improving bioavailability, and effectively alleviating diarrhea caused by mycotoxins and other harmful substances in the feed.

[0065] Comparative Example 1

[0066] This comparative example provides a fermented herbal antibiotic-free feed additive for beef cattle, which differs from Example 1 in that the polyacrylic acid resin II modified composite hydrogel spheres do not contain copper nitrate; copper nitrate is not added in step (1) of the preparation method of the polyacrylic acid resin II modified composite hydrogel spheres; and the preparation method of the fermented herbal antibiotic-free feed additive for beef cattle is the same as that of Example 1.

[0067] Comparative Example 2

[0068] This comparative example provides a fermented herbal antibiotic-free feed additive for beef cattle, which differs from Example 1 in that the polyacrylic acid resin II modified composite hydrogel spheres do not contain copper [N2-(N-glycyl-L-histyl)-L-lysine]; the preparation method of the polyacrylic acid resin II modified composite hydrogel spheres does not include the addition of copper [N2-(N-glycyl-L-histyl)-L-lysine] aqueous solution in step (2); and the preparation method of the fermented herbal antibiotic-free feed additive for beef cattle is the same as that in Example 1.

[0069] Comparative Example 3

[0070] This comparative example provides a fermented herbal antibiotic-free feed additive for beef cattle, which differs from Example 1 in that the polyacrylic acid resin II modified composite hydrogel spheres do not contain polyacrylic acid resin II; polyacrylic acid resin II is not added in step (3) of the preparation method of polyacrylic acid resin II modified composite hydrogel spheres; and the preparation method of the fermented herbal antibiotic-free feed additive for beef cattle is the same as that of Example 1.

[0071] Comparative Example 4

[0072] This comparative example provides a fermented herbal antibiotic-free feed additive for beef cattle, which differs from Example 1 in that the polyacrylic acid resin II modified composite hydrogel spheres do not contain glucono-δ-lactone; the glucono-δ-lactone solution is not added in step (3) of the preparation method of the polyacrylic acid resin II modified composite hydrogel spheres; and the preparation method of the fermented herbal antibiotic-free feed additive for beef cattle is the same as that of Example 1.

[0073] Experimental Example 1

[0074] Gut Health Experiment

[0075] Test samples: Fermented Chinese herbal antibiotic-free feed additives for beef cattle prepared in Examples 1-3 and Comparative Examples 1-4.

[0076] Test Method: Thirty-five healthy beef cattle with an initial weight of (300±10) kg were randomly divided into seven groups of five cattle each. A 14-day pre-feeding period was conducted before the experiment to allow the cattle to acclimatize to the experimental environment. Feed intake during the pre-feeding period was recorded to determine the feed intake for the formal experimental period. During the experiment, all groups of cattle maintained consistent feeding and management conditions, including temperature and ventilation. The cattle pens were cleaned and disinfected before the formal experiment began. The test sample was mixed with the basal feed at a mass ratio of 3:7 and fed daily at 7:00 AM. Feeding was conducted twice daily, at 12:00 and 18:00. The daily feed intake was determined based on 110% of the average feed intake over the first three days of the trial period. Leftover feed was collected before the next day's feeding. Cattle had free access to water, and manure was removed mechanically. The experiment lasted 30 days. During this period, diarrhea was observed and recorded in the cattle (the condition of the cattle's feces was observed twice daily, before feeding at 7:00 and 18:00, and a fecal score was recorded for each animal. If diarrhea was diagnosed in either of the two observations, that day was counted as one day of diarrhea). The diarrhea rate was calculated using the following formula:

[0077] Diarrhea rate (%) = Total number of days with diarrhea / (Total number of experimental cattle × Number of experimental days) × 100%;

[0078] The total number of days with diarrhea refers to the sum of the cumulative number of days with diarrhea in each group of beef cattle during the trial period;

[0079] Stool scoring criteria:

[0080] 1 point: Normal, strip-shaped or granular;

[0081] 2 points: Soft stool, unformed but able to retain its shape;

[0082] 3 points: Loose stool, liquid or semi-liquid, unable to retain its shape;

[0083] 4 points: Watery stool, completely liquid;

[0084] Diarrhea is diagnosed when a stool score of ≥3 is recorded.

[0085] Figure 1The diagram shows the diarrhea rate results for Examples 1-3 and Comparative Examples 1-4. As shown, the diarrhea rate for Examples 1-3 was 2-5%, indicating relatively low diarrhea rates; the diarrhea rate for Comparative Examples 1-4 was 8-21%, indicating relatively high diarrhea rates. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 1 lacked copper nitrate, thus lacking the direct antibacterial effect of copper ions, leading to higher diarrhea rates. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 2 lacked [N2-(N-glycyl-L-histyl)-L-lysine] copper, failing to provide a highly efficient bioactive copper source through copper peptides and also failing to assist in repairing damaged intestinal mucosa, resulting in higher diarrhea rates. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 3 lacked polyacrylic acid resin II, causing the active component to be released prematurely in the rumen, hindering its localization and effectiveness in the intestine, leading to higher diarrhea rates. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 4 lacked gluconate-δ-lactone, preventing the hydrogel from cross-linking and ensuring effective protection and delivery of the active component, resulting in higher diarrhea rates.

[0086] Experimental Example 2

[0087] Growth performance experiment

[0088] Test samples: Fermented Chinese herbal antibiotic-free feed additives for beef cattle prepared in Examples 1-3 and Comparative Examples 1-4.

[0089] Test Method: Thirty-five healthy beef cattle with an initial weight of (300±10) kg were randomly divided into seven groups of five cattle each. A 14-day pre-feeding period was conducted before the experiment to allow the cattle to acclimatize to the experimental environment. Feed intake during the pre-feeding period was recorded to determine the feed intake for the formal experimental period. During the experiment, all groups of cattle maintained consistent feeding and management conditions, including temperature and ventilation. The pens were cleaned and disinfected before the formal experiment began. The test sample was mixed with the basal feed at a mass ratio of 3:7 and fed three times daily at 7:00, 12:00, and 18:00. The daily feed intake was determined based on 110% of the average feed intake over the first three days of the pre-feeding period. Leftover feed was collected before the next day's feeding. The cattle had free access to water, and manure was removed mechanically. The experiment lasted 60 days. On the first and sixth days of the experiment, each cattle was weighed and the average weight was calculated before the morning feeding. The average daily feed intake, average daily weight gain, and feed conversion ratio were then calculated using the following formulas:

[0090] Average daily feed intake (ADFI): During the experiment, the amount of feed given to the experimental beef cattle and the amount of leftover feed were recorded, and the average daily feed intake (kg / d) was calculated.

[0091] Average daily weight gain (ADG) (kg / d) = (final weight - initial weight) / 60;

[0092] Material weight ratio = ADFI / ADG.

[0093] Figure 2 The figures show the growth performance results of Examples 1-3 and Comparative Examples 1-4. As shown, the average daily feed intake, average daily weight gain, and feed conversion ratio of Examples 1-3 were 8.47-8.65 kg / d, 1.26-1.32 kg / d, and 6.55-6.72, respectively, indicating good growth performance. The average daily feed intake, average daily weight gain, and feed conversion ratio of Comparative Examples 1-4 were 8.43-8.61 kg / d, 1.09-1.18 kg / d, and 7.30-7.73, respectively, indicating average growth performance. The polyacrylic acid resin II modified composite hydrogel spheres of Comparative Example 1 do not contain copper nitrate, lacking the direct antibacterial effect of copper ions, which is detrimental to intestinal health and reduces the digestion and absorption of nutrients, resulting in average growth performance. Comparative Example 2... The polyacrylic acid resin II modified composite hydrogel spheres do not contain [N2-(N-glycyl-L-histyl)-L-lysine] copper, thus losing their efficient copper source and anti-inflammatory repair function. They cannot maintain the intestinal environment through bioactivity, which is not conducive to ensuring nutrient absorption, resulting in mediocre growth performance. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 3 do not contain polyacrylic acid resin II, thus losing their targeted delivery function. The active components are partially degraded in the rumen and cannot respond to release activity in the intestine, resulting in mediocre growth performance. The polyacrylic acid resin II modified composite hydrogel spheres in Comparative Example 4 do not contain glucono-δ-lactone, thus losing their cross-linking and curing ability. The hydrogel spheres cannot be formed, and the active components are prematurely released or destroyed in gastric acid, resulting in mediocre growth performance.

[0094] The above experimental results show that the intestinal health and growth performance of Examples 1-3 of the present invention are significantly better than those of Comparative Examples 1-4. Among them, Example 1, which uses polyacrylic acid resin II to modify the composite hydrogel spheres, has less diarrhea and better growth performance.

[0095] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.

[0096] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A fermented herbal antibiotic-free feed additive for beef cattle, characterized in that: The antibiotic-free feed additive for beef cattle made from fermented traditional Chinese medicine comprises the following components in parts by weight: 10-20 parts of polyacrylic acid resin II modified composite hydrogel spheres, and 50-60 parts of fermented traditional Chinese medicine residue substrate. The polyacrylic acid resin II modified composite hydrogel spheres are supported by a three-dimensional framework formed by the cross-linking of sodium alginate and calcium ions. The reinforcing network, composed of sodium alginate and gelatin, enhances mechanical strength. The introduced polyacrylic acid resin II acts as a pH-responsive modification layer, imparting targeted release characteristics to the system. The three-layer network works synergistically to physically encapsulate the sodium carboxymethyl cellulose / copper-modified montmorillonite complex loaded with copper peptides, thereby achieving rumen protection and intestinal protection of the active components for ruminants. The feed material has a targeted delivery function; the fermented base material of the Chinese herbal medicine residue is a functional feed base material with loose fiber structure and rich in active metabolites, which is made by using Chinese herbal medicine residue as the main raw material, supplemented by corn flour and soybean meal to provide carbon and nitrogen sources. Under the synergistic fermentation of Bacillus subtilis and Lactobacillus plantarum, and with the assistance of enzymatic hydrolysis by neutral protease, alkaline protease and cellulase, and by aerobic fermentation and freeze drying process; the Chinese herbal medicine residue includes the following components in parts by weight: 5-10 parts of Astragalus membranaceus residue, 5-10 parts of Acanthopanax senticosus residue, 5-10 parts of Codonopsis pilosula residue, 5-10 parts of Taraxacum mongolicum residue, 5-10 parts of Dioscorea opposita residue, 5-10 parts of Plantago asiatica residue, and 5-10 parts of Poria cocos residue.

2. A method for preparing a fermented herbal antibiotic-free feed additive for beef cattle according to claim 1, characterized in that: Specifically, the following steps are included: S1. Mix the residues of Astragalus membranaceus, Acanthopanax senticosus, Codonopsis pilosula, Taraxacum mongolicum, Dioscorea opposita, Plantago asiatica, and Poria cocos to obtain the Chinese herbal medicine residues for later use. Inoculate 1.0-2.0g of Bacillus subtilis and 1.0-2.0g of Lactobacillus plantarum into LB medium for activation. After incubation at 37℃ in a shaker for 1-2 days, the viable count of the bacterial suspension is 3×10⁻⁶. 9 CFU / mL, add Chinese herbal medicine residue, corn flour, and soybean meal powder to 1-2 times the amount of pure water, mix evenly, sterilize at 100℃ for 30 min, adjust the pH of the material to 7.0-7.5, cool to room temperature, add 3-5% Bacillus subtilis suspension, 1-3% Lactobacillus plantarum suspension and 4.0-6.0g compound enzyme, carry out aerobic fermentation at 37℃ for 72 h, during the fermentation process, the material thickness is 3-5cm, cover with gauze, turn the material 1-2 times a day, and finally freeze dry to obtain the fermentation base material of Chinese herbal medicine residue; S2. Weigh 50.0-60.0g of the fermented herbal residue base material mentioned in step S1 and mix it with 10.0-20.0g of polyacrylic acid resin II modified composite hydrogel balls at 20rpm for 10-15min, with the moisture content controlled at 30-35%. Transfer the mixture to a granulator for granulation. The screen aperture is 1.5mm, the mixing speed is 20-30rpm, and the shearing speed is 50-60rpm. After granulation, dry the mixture with hot air at 40℃ for 2h to obtain a fermented herbal antibiotic-free feed additive for beef cattle.

3. The method for preparing the fermented herbal antibiotic-free feed additive for beef cattle according to claim 2, characterized in that: In step S1, the mass ratio of neutral protease, alkaline protease, and cellulase in the complex enzyme is 0.75:0.25:

1.

4. The method for preparing the fermented herbal antibiotic-free feed additive for beef cattle according to claim 3, characterized in that: The preparation method of the polyacrylic acid resin II modified composite hydrogel spheres specifically includes the following steps: (1) Montmorillonite K-10 was dispersed in a mixed solvent of 30 mL deionized water and 10 mL anhydrous ethanol and magnetically stirred at room temperature for 24 h to obtain a montmorillonite suspension. Then, 0.3-0.6 g copper nitrate and 0.2 g sodium carboxymethyl cellulose were added sequentially and stirred for 30 min. The suspension was then transferred to a 100 mL hydrothermal reactor and reacted at 180 °C for 12 h. After cooling to room temperature, the mixture was centrifuged at 10000 rpm for 10 min. The precipitate was washed three times each with deionized water and anhydrous ethanol and vacuum dried at 60 °C for 12 h. The resulting powder was heated to 450 °C at a heating rate of 5 °C / min in air atmosphere, kept at the temperature for 5 h, and ground to obtain copper-modified montmorillonite composite powder. (2) Weigh 1.0g of the copper-modified montmorillonite composite powder described in step (1) and disperse it in 100mL of deionized water. Stir magnetically for 1h to form a suspension. Then, add 0.03mol / L of [N2-(N-glycyl-L-histyl)-L-lysine] copper aqueous solution and 0.3-0.5g of sodium carboxymethyl cellulose to the suspension in sequence. Continue stirring until the mixture is uniform. Adjust the pH of the system to 7.0-7.5 with sodium hydroxide solution and continue stirring for 30min. Then, quickly add 5mL of 0.03-0.05mol / L ascorbic acid solution and continue stirring magnetically for 10min. Seal and let stand at room temperature for 3h. Centrifuge at 10000rpm for 5min. Wash the precipitate repeatedly with deionized water 3 times. Finally, dry it in an oven at 60-80℃ to obtain sodium carboxymethyl cellulose / copper-modified montmorillonite composite loaded with copper peptide. (3) Add polyacrylic acid resin II to 100 mL of sodium alginate aqueous solution with a mass fraction of 1.5% and stir magnetically at 55°C until completely dissolved. Then, add 0.75-0.85 g of gelatin and continue stirring at the same temperature until the gelatin is fully swollen. After the composite sol is naturally cooled to room temperature, add 1.0-2.0 g of sodium carboxymethyl cellulose / copper modified montmorillonite composite loaded with copper peptide described in step (2) and stir magnetically for 30 min. Add 0.3-0.5 g of calcium carbonate powder and stir magnetically for 20 min. Then add 5 mL of gluconate-δ-lactone solution with a mass fraction of 0.6% and mix rapidly within 2 min. Use a syringe to draw up the mixed sol and push it into deionized water. Let it stand for cross-linking and curing for 30 min. Collect the obtained hydrogel balls to obtain polyacrylic acid resin II modified composite hydrogel balls.

5. The method for preparing the fermented herbal antibiotic-free feed additive for beef cattle according to claim 4, characterized in that: In step (1), the amount of montmorillonite used is 0.4-0.8g, with a specific surface area of ​​240m². 2 / g.

6. The method for preparing the fermented traditional Chinese medicine antibiotic-free feed additive for beef cattle according to claim 5, characterized in that: In step (2), the amount of copper [N2-(N-glycyl-L-histyl)-L-lysine] aqueous solution added is 5-10 mL.

7. The method for preparing fermented herbal antibiotic-free feed additive for beef cattle according to claim 6, characterized in that: In step (3), the amount of polyacrylic acid resin II added is 0.1-0.3g.

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