Biological antibacterial composition, detergent and preparation method of detergent

Abstract

The invention discloses a biological antibacterial composition, a detergent and a preparation method thereof in the field of detergents. The biological antibacterial composition is prepared from a carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, an inulin-dodecyl alcohol-vitamin E succinate derivative, sodium alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, disodium ethylene diamine tetraacetate, methylisothiazolinone, glucose oxidase and deionized water. Wherein the carboxymethyl chitosan derivative is grafted with polyhexamethylene guanidine through an amidation reaction, and then is subjected to Michael addition with azobenzene acrylate; the inulin derivative is subjected to sulfonation reaction to generate a sulfonate intermediate, the sulfonate intermediate is exchanged with dodecyl alcohol, and then the sulfonate intermediate and vitamin E succinate are prepared. The composition achieves broad-spectrum bacteriostasis through multi-target cooperation, and the detergent has efficient decontamination and low irritation and is suitable for the field of green cleaning.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, specifically to a biological antibacterial composition, a detergent, and a method for preparing the same. Background Technology

[0002] As consumers increasingly demand green, safe, and efficient cleaning products, the traditional detergent market, dominated by chemical antibacterial agents, is gradually revealing its limitations. While traditional chemical antibacterial agents possess strong antibacterial activity, long-term use leads to serious drug resistance problems, and some components can accumulate persistently in the environment, threatening human health through the food chain. For example, wastewater containing certain chemical antibacterial agents entering water bodies may cause the spread of drug-resistant genes in microorganisms, disrupting the ecological balance. Cationic antibacterial agents, due to their characteristics, easily bind to fabrics and leave residues, reducing the detergent's cleaning efficiency and potentially causing discomfort for people with sensitive skin. Furthermore, traditional chemical antibacterial agents have a relatively limited antibacterial spectrum, with limited inhibitory effects on multiple bacterial species, making it difficult to meet the cleaning needs of complex environments. These shortcomings have led to increasing regulatory restrictions on traditional chemical antibacterial agents, and the market urgently needs green, low-toxicity, and highly efficient alternatives.

[0003] Bio-based antibacterial materials are considered ideal alternatives due to their natural origin and biodegradability. However, the performance limitations of existing bio-based materials restrict their large-scale application. While the active groups on the molecular chains of some bio-based materials can be chemically modified to enhance their antibacterial properties, the modification process often leads to increased molecular chain rigidity and a significant decrease in water solubility, making it difficult to disperse evenly in detergent systems. Furthermore, their antibacterial mechanism mainly relies on membrane potential disruption, resulting in limited effectiveness against drug-resistant bacteria. Another type of bio-based material, while exhibiting excellent water solubility and good biocompatibility, lacks inherent antibacterial activity and requires the introduction of antibacterial groups through chemical grafting. However, conventional grafting methods easily damage their molecular structure, leading to the loss of prebiotic properties, and the antibacterial efficiency after grafting still falls short of practical application requirements. In addition, commercially available bio-detergents often rely on a single surfactant for detergency, and the amount of antibacterial components added is often high, easily causing problems such as reduced foam volume and stratification at low temperatures, affecting the user experience.

[0004] Against this backdrop, the development of a bio-based detergent that combines high-efficiency antibacterial properties, low irritation, and good detergency has become an urgent industry need. This invention addresses the performance deficiencies of existing bio-based materials by designing two novel modified bio-based compounds with novel structures. Through the synergistic effect of different functional groups, a balance is achieved between broad-spectrum antibacterial properties and detergent performance. One compound grafts a bifunctional antibacterial group onto a specific bio-based material, while the other grafts an antibacterial group onto another bio-based material. The multi-target synergistic effect of these two compounds can cover a wide range of bacteria. Furthermore, when combined with a composite surfactant, this ensures the detergent's detergency while reducing irritation. The implementation of this invention will promote the application of bio-based antibacterial materials in the detergent field and provide a new technological path for the development of green cleaning products. Summary of the Invention

[0005] The purpose of this invention is to provide a biological antibacterial composition, detergent, and preparation method thereof, which solves the technical problems of drug resistance, environmental toxicity, and narrow antibacterial spectrum and insufficient performance of existing chemical antibacterial agents and bio-based materials.

[0006] The present invention achieves the above objectives through the following technical solutions:

[0007] A biological antibacterial composition comprising the following raw materials in parts by weight:

[0008] Carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative: 0.5-4 parts by weight;

[0009] Inulin-dodecyl alcohol-vitamin E succinate derivative: 0.3-3 parts by weight;

[0010] Sodium alkylbenzene sulfonate: 7-16 parts by weight;

[0011] Fatty alcohol polyoxyethylene ether: 4-10 parts by weight;

[0012] Disodium ethylenediaminetetraacetate: 0.1-0.6 parts by weight;

[0013] Methylisothiazolinone: 0.05-0.25 parts by weight;

[0014] Glucose oxidase: 0.1-0.3 parts by weight;

[0015] Deionized water: 68-90 parts by weight;

[0016] The preparation method of the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative includes: A1, dissolving carboxymethyl chitosan in acetic acid solution and stirring magnetically until completely dissolved; adding 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, adjusting the pH to 6.2-6.4, and reacting at room temperature; cooling the reaction solution to 8-10℃, adding polyhexamethylene biguanide hydrochloride dropwise, adjusting the pH to 7.0-7.5, and continuing the reaction; A2, adding azobenzene-4-acrylate to the reaction solution, and reacting at room temperature in the dark; after the reaction is completed, the product is placed in a dialysis bag, dialyzed with deionized water, and the dialysate is freeze-dried.

[0017] In this invention, the preparation process of the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative involves multiple chemical modifications. The core process involves covalently linking bio-based materials with functional groups through condensation, amidation, and Michael addition reactions. First, under acidic conditions, the amino group of carboxymethyl chitosan is protonated, increasing its solubility. After adding 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) and N-hydroxysuccinimide (NHS), with EDC·HCl acting as a condensing agent, the reaction solution is cooled to a low temperature (8-10°C), and then polyhexamethylene biguanide hydrochloride is added dropwise. At this point, the pH is adjusted to a slightly alkaline level (7.0-7.5) to further promote the formation of amide bonds, ensuring that the polyhexamethylene guanidine groups are stably covalently linked to the carboxymethyl chitosan molecular chain. After this step, a carboxymethyl chitosan-polyhexamethylene guanidine intermediate is formed in the system. Subsequently, azophenyl-4-acrylate was added. Under light-protected conditions, the vinyl group in its molecular structure underwent a Michael addition reaction with the amino group of carboxymethyl chitosan or polyhexamethylene guanidine in the intermediate. The double bond of the vinyl group opened and combined with the amino group, forming a ternary covalently linked structure of carboxymethyl chitosan-polyhexamethylene guanidine-azophenyl acrylate. After the reaction, unreacted small molecules (such as EDC·HCl, NHS, and solvents) were removed by dialysis, and the target derivative was finally obtained by freeze-drying. In this process, the activation of the carboxyl group of carboxymethyl chitosan, the amidation grafting of polyhexamethylene guanidine, and the Michael addition of azophenyl acrylate were the key reaction steps, ensuring the effective loading of functional groups and structural stability.

[0018] According to a preferred embodiment of the present invention, in step A1, the room temperature reaction time is 1.5-2 hours; the reaction continues for 8-10 hours.

[0019] According to a preferred embodiment of the present invention, in step A2, the freeze-drying temperature is -55°C and the time is 18-20 hours.

[0020] According to a preferred embodiment of the present invention, the preparation method of the inulin-dodecyl alcohol-vitamin E succinate derivative includes: B1, dissolving inulin in anhydrous dimethyl sulfoxide, adding chlorosulfonic acid, and reacting at 50-55°C under nitrogen protection; pouring the reaction solution into ice water to precipitate the precipitate, filtering, washing with deionized water, and drying to obtain a sulfonate intermediate; dissolving the intermediate in N,N-dimethylformamide, adding dodecyl alcohol and 4-dimethylaminopyridine, and reacting at room temperature in the dark; dialyzing the reaction solution with a dialysis bag, and freeze-drying the dialysate to obtain a dodecyl alcohol-modified intermediate; B2, dissolving the dodecyl alcohol-modified intermediate in anhydrous tetrahydrofuran, adding vitamin E succinate and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, adjusting the pH to 6.5-7, and reacting at room temperature; rotary evaporating the reaction solution under reduced pressure, extracting the residue with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and filtering.

[0021] In this invention, firstly, a large number of hydroxyl groups in the inulin molecule undergo a sulfonation reaction with chlorosulfonic acid in a dimethyl sulfoxide solvent. Chlorosulfonic acid, acting as a strong sulfonating agent, transfers the sulfonyl groups to the inulin backbone, forming a highly reactive inulin sulfonate intermediate. Subsequently, under the catalysis of dimethylaminopyridine, the hydroxyl groups of the dodecyl alcohol are activated, and its oxygen atom acts as a nucleophilic center, attacking the sulfur atom in the inulin sulfonate molecule, resulting in a nucleophilic substitution reaction. After the sulfonate ion departs, a stable inulin-dodecyl ether bond is formed, thereby covalently grafting the hydrophobic dodecyl long chain onto the hydrophilic inulin polysaccharide backbone. Finally, in the vitamin E succinate modification stage, under the action of a carbodiimide condensing agent, the terminal carboxyl group of the vitamin E succinate molecule is activated to generate an active intermediate. This intermediate undergoes a nucleophilic addition-elimination reaction with the remaining free hydroxyl groups in the dodecylated inulin molecule, ultimately linking the vitamin E succinate structural unit to the modified inulin carrier via an ester bond, forming an amphiphilic inulin-dodecyl alcohol-vitamin E succinate derivative. Throughout the process, the formation and nucleophilic substitution of sulfonates, the activation of carboxyl groups and esterification reactions constitute the main chemical bond transformation pathways. The final product combines the carrier function of polysaccharides, the hydrophobic properties of long-chain alkyl groups and the bioactivity of vitamin E succinate.

[0022] According to a preferred embodiment of the present invention, in step B1, the reaction time at 60-64°C is 3-5 hours; the reaction time at room temperature in the dark is 10-20 hours.

[0023] According to a preferred embodiment of the present invention, in step B2, the reaction time at room temperature is 12-20 h.

[0024] The present invention also provides a detergent comprising the aforementioned bio-antibacterial composition.

[0025] The present invention also provides a method for preparing the detergent, comprising the following steps:

[0026] S1. Weigh sodium alkylbenzene sulfonate and fatty alcohol polyoxyethylene ether, add deionized water, heat to 55-60℃ and stir magnetically until completely dissolved; then add disodium ethylenediaminetetraacetate and methylisothiazolinone, continue stirring to obtain a mixture;

[0027] S2. Carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, inulin-dodecyl alcohol-vitamin E succinate derivative and glucose oxidase are pre-dissolved in deionized water, added dropwise to the mixture, the pH is adjusted to 6.0-6.5, stirred evenly, and filtered through a filter cloth.

[0028] In this invention, the detergent preparation focuses on physical mixing and the synergistic effect of surfactants, achieving a balance between detergency and antibacterial properties through multi-component compounding. First, sodium alkylbenzene sulfonate (LAS) and fatty alcohol polyoxyethylene ether (AEO-7) serve as the primary and secondary surfactants, respectively. They dissolve in hot water (55-60℃) and undergo intermolecular interactions (such as hydrogen bonds and van der Waals forces) to form a stable surfactant solution. Then, disodium ethylenediaminetetraacetate (EDTA) is added. Its amino and carboxyl groups can complex with hard water components such as calcium and magnesium ions in the water, forming stable chelates. This prevents hard water ions from binding with the surfactant to form insoluble precipitates (such as soap scum), thus ensuring the detergency activity of the surfactant. Subsequently, methylisothiazolinone (MIT) is added. As a preservative, it can bind to the enzyme systems of microorganisms (such as dehydrogenases and oxidases), inhibiting microbial growth and reproduction, and extending the shelf life of the detergent. Next, carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, inulin-dodecyl alcohol-vitamin E succinate derivative, and glucose oxidase were pre-dissolved in deionized water (with ultrasonic assistance) to form a homogeneous pre-solution. Glucose oxidase is a natural antimicrobial enzyme that specifically catalyzes the reaction of β-D-glucose with oxygen to produce gluconic acid and hydrogen peroxide. The strong oxidizing properties of the generated hydrogen peroxide (destroying the cell structure, enzyme system, and metabolic function of microorganisms) and the resulting pH decrease (creating an acidic unsuitable environment) work together to effectively inhibit and kill bacteria. The pre-solution was added dropwise to the surfactant mixture to adjust the pH to weakly acidic (6.0-6.5). At this point, the hydrophilic groups of the surfactant (such as sulfonic acid groups and polyoxyethylene groups) bind to the deionized water, while the hydrophobic groups (such as alkyl chains and the nonpolar portion of inulin) tend to adsorb oil stains, forming a micelle structure, which enhances the dispersion and emulsification of grease and stains. Finally, the mixture was filtered through a filter cloth to remove undissolved large particulate impurities, resulting in a homogeneous and stable detergent system. Throughout the preparation process, the dissolution and micelle formation of surfactants are the foundation of detergency. The chelating effect of disodium EDTA ensures the stability of the system, the addition of MIT inhibits microbial contamination, and the introduction of two bio-based derivatives, through the mildness of antibacterial groups (such as polyhexamethylene guanidine and dodecyl alcohol) and the stability of the inulin skeleton and the overall molecular structure, and through the synergistic effect of physical solubilization, endow the detergent with broad-spectrum antibacterial properties, ultimately achieving multiple functions of detergency, antibacterial and mildness.

[0029] According to a preferred embodiment of the present invention, in step S1, the magnetic stirring speed at 55-60°C is 300-400 rpm for 30-50 min; the stirring speed is then increased to 150-200 rpm for 15-20 min.

[0030] According to a preferred embodiment of the present invention, in step S2, the stirring speed is 100-200 rpm and the time is 20-40 min.

[0031] The beneficial effects of this invention are as follows:

[0032] The bio-antibacterial composition and detergent described in this invention exhibit significant advantages in terms of antibacterial properties, detergency, stability, and mildness, effectively solving the problems of strong irritation from traditional chemical antibacterial agents, narrow antibacterial spectrum of bio-based materials, and imbalance in detergent performance.

[0033] In terms of antibacterial performance, the two modified bio-based compounds in the composition achieve broad-spectrum and highly efficient antibacterial activity through a multi-target synergistic mechanism and glucose oxidase. Specifically, the carboxymethyl chitosan derivative disrupts the microbial membrane potential through the cationic properties of polyhexamethylene guanidine, while azobenzene acrylate undergoes structural changes under light irradiation, releasing active groups to enhance the antibacterial effect. The inulin-dodecyl alcohol-vitamin E succinate derivative relies on the hydrophobicity of dodecyl alcohol; through hydrophobic interactions, dodecyl alcohol can interact with the lipid bilayer of the cell membrane, increasing membrane permeability and thus facilitating the penetration and action of other active ingredients. The synergistic effect of these two compounds significantly improves the inhibitory efficiency against various microorganisms, including Gram-positive bacteria, Gram-negative bacteria, and fungi, and the antibacterial activity is further enhanced under light conditions, effectively addressing the challenge of multidrug-resistant bacteria in complex environments.

[0034] In terms of detergent performance, the compound system of the composition and the complex surfactant achieves a balance between detergency and stability. The synergistic effect of sodium alkylbenzene sulfonate and fatty alcohol polyoxyethylene ether enhances surface activity, significantly improving the dispersion and emulsification ability of grease and stains; disodium ethylenediaminetetraacetate, by complexing hard water ions, prevents the surfactant from combining with calcium and magnesium ions to form precipitation, ensuring stable detergency under different water quality conditions; the addition of methylisothiazolinone further inhibits the growth of microorganisms in the detergent, extending the product's shelf life. Experiments show that this detergent has a significantly higher oil removal rate for common oil stains than traditional products, and it maintains good fluidity at low temperatures and does not exhibit stratification or precipitation during high-temperature storage.

[0035] From a safety and gentleness perspective, the bio-based origin and low-irritant design of the composition significantly enhance the user experience. Both carboxymethyl chitosan and inulin are natural and biodegradable materials, and no toxic chemicals were introduced during the modification process, reducing risks to humans and the environment. The photoresponsive properties of azophenyl acrylate prevent the continuous release of active ingredients from irritating the skin. Skin irritation tests show that this detergent has an extremely low irritation index for sensitive individuals, meeting the safety standards for green cleaning products. Furthermore, the composition's degradation properties make it easier to decompose in the natural environment, reducing potential harm to ecosystems and aligning with the needs of sustainable development.

[0036] In summary, the bio-antibacterial composition and detergent of the present invention, through multi-component synergy and structural innovation, have achieved comprehensive breakthroughs in antibacterial properties, stain removal, stability, and mildness, providing a new technical path for the development of green cleaning products and having significant economic and social benefits. Detailed Implementation

[0037] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.

[0038] The supplier information for the relevant equipment and materials is as follows:

[0039] The carboxymethyl chitosan was purchased from Ningbo Zhenhai Haixin Biological Products Co., Ltd.

[0040] The acetic acid was purchased from Jiangsu Suopu Group Co., Ltd.

[0041] The 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was purchased from Nanjing Yaoshi Technology Co., Ltd.

[0042] The N-hydroxysuccinimide was purchased from Jiangsu Wuzhong Pharmaceutical Development Co., Ltd.

[0043] The polyhexamethylene biguanide hydrochloride was purchased from Jiangsu Xinchao Chemical Technology Co., Ltd.

[0044] The azobenzene-4-acrylate was purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0045] The dialysis bags were purchased from Shanghai Xingyu Biotechnology Co., Ltd.

[0046] The sodium alkylbenzene sulfonate was purchased from China Petrochemical Corporation Jinling Petrochemical Co., Ltd.

[0047] The fatty alcohol polyoxyethylene ether was purchased from Jiangsu Haian Petrochemical Plant.

[0048] The disodium ethylenediaminetetraacetate was purchased from Jiangsu Jiangdu Pesticide Factory Co., Ltd.

[0049] The methylisothiazolinone was purchased from Jiangsu Changlong Chemical Co., Ltd.

[0050] The glucose oxidase was purchased from Shanghai Lianshuo Biotechnology Co., Ltd.

[0051] The deionized water was purchased from Jiangsu General Environmental Protection Technology Co., Ltd.

[0052] The inulin was purchased from Shandong Baolingbao Biotechnology Co., Ltd.

[0053] The dimethyl sulfoxide was purchased from Jiangsu Feixiang Chemical Co., Ltd.

[0054] The chlorosulfonic acid was purchased from Jiangsu Meilan Chemical Co., Ltd.

[0055] The N,N-dimethylformamide was purchased from Jiangsu Huachang Chemical Co., Ltd.

[0056] The dodecyl alcohol was purchased from Jinan Huifengda Chemical Co., Ltd.

[0057] The 4-dimethylaminopyridine was purchased from Jiangsu Yaoshi Technology Co., Ltd.

[0058] The tetrahydrofuran was purchased from Jiangsu Hengli Petrochemical Co., Ltd.

[0059] The vitamin E succinate was purchased from Wuhan Shuiyixing Pharmaceutical Chemical Co., Ltd.

[0060] The ethyl acetate was purchased from Jiangsu Suopu Group Co., Ltd.

[0061] The anhydrous sodium sulfate was purchased from Jiangsu Huaihai Zhonglian Cement Co., Ltd.

[0062] The filter cloth was purchased from Zhejiang Hangmin Co., Ltd.

[0063] Example 1

[0064] Preparation of carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative: 1 g of carboxymethyl chitosan was added to 100 mL of 1% (v / v) acetic acid solution and placed on a magnetic stirrer. The solution was stirred at 150 rpm for 1 hour at 25°C until completely dissolved. 0.3 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.18 g of N-hydroxysuccinimide were added to the solution. The pH was adjusted to 6.2 with 1 mol / L sodium hydroxide solution, and the mixture was stirred at 25°C for 1.5 hours to fully activate the amino groups of the carboxymethyl chitosan. The reaction solution was transferred to an ice-water bath and cooled to 8°C. 0.9 g of polyhexamethylene biguanide hydrochloride (dissolved in 5 mL of deionized water) was slowly added dropwise. After the addition was complete, 1 mol / L sodium hydroxide solution was used to further activate the amino groups of the carboxymethyl chitosan. The pH was adjusted to 7.0 with 1 / L hydrochloric acid solution, and the mixture was stirred at 8°C for 8 hours to complete the amidation grafting reaction of carboxymethyl chitosan and polyhexamethylene guanidine. 0.45 g of azophenyl-4-acrylate (dissolved in 3 mL of dimethyl sulfoxide) was added to the reaction solution, and the mixture was stirred at 25°C for 6 hours in the dark to allow the vinyl group of the azophenyl acrylate to undergo a Michael addition reaction with the amino group of the carboxymethyl chitosan-polyhexamethylene guanidine intermediate. After the reaction, the product was placed in a dialysis bag with a molecular weight cutoff of 10000 Da and dialyzed with deionized water for 4 days (changing the water 3 times daily). The dialysate was then freeze-dried at -55°C for 18 hours to obtain a white powdery carboxymethyl chitosan-polyhexamethylene guanidine-azophenyl acrylate derivative.

[0065] Preparation of inulin-dodecyl alcohol-succinate derivative: 1 g of inulin was added to 10 mL of anhydrous dimethyl sulfoxide and magnetically stirred (25 °C, 100 rpm) until completely dissolved; 0.4 g of chlorosulfonic acid was added to the solution, and nitrogen gas was introduced for protection. The mixture was stirred in a 55 °C water bath for 3 hours to induce sulfonation of the hydroxyl groups in the inulin; the reaction solution was quickly poured into ice water (volume ratio 1:5), and a white precipitate formed. The precipitate was collected by filtration, washed three times with deionized water (10 mL each time), and dried under vacuum at 40 °C to obtain the intermediate; the intermediate was added to 5 mL of... In N,N-dimethylformamide, the mixture was magnetically stirred (25°C, 100 rpm) until completely dissolved. 2 g of dodecyl alcohol and 0.2 g of 4-dimethylaminopyridine were added, and the mixture was stirred at 25°C for 10 hours in the dark to allow for transesterification of the sulfonate with the dodecyl alcohol. The reaction solution was dialyzed for 2 days using a dialysis bag with a molecular weight cutoff of 3000 Da (water changed 3 times daily). The dialysate was freeze-dried (-55°C, 19 hours) to obtain a dodecyl alcohol-modified inulin intermediate. The intermediate was added to 5 mL of anhydrous tetrahydrofuran and magnetically stirred (25°C, 100 rpm). After complete dissolution, 1.5 g of vitamin E succinate and 0.3 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The pH was adjusted to 6.5 with 1 mol / L hydrochloric acid solution, and the mixture was stirred at 25°C for 12 hours to induce esterification. The reaction solution was subjected to rotary evaporation under reduced pressure at 40°C to remove tetrahydrofuran. The residue was extracted three times with ethyl acetate (5 mL each time). The organic phase was dried over anhydrous sodium sulfate (25°C, 30 min), filtered, and dried under reduced pressure to obtain a brownish-yellow solid inulin-dodecyl alcohol-vitamin E succinate derivative.

[0066] Preparation of detergent: Weigh 7g of sodium alkylbenzene sulfonate and 4g of fatty alcohol polyoxyethylene ether, add 70g of deionized water, place in a constant temperature water bath and heat to 55℃, turn on the magnetic stirrer (300rpm) and stir for 30 minutes until completely dissolved; add 0.1g of disodium ethylenediaminetetraacetate and 0.05g of methylisothiazolinone to the solution, reduce the stirring speed to 150rpm, and continue stirring for 15 minutes to obtain a mixture of surfactant and functional additive; add 0.5g of carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative and 0.3 g of inulin-dodecyl alcohol-vitamin E succinate derivative and 0.2 g of glucose oxidase were added to 5 mL of deionized water and sonicated (30℃, 100W) for 10 minutes to pre-dissolve the two derivatives, resulting in clear pre-solutions. The pre-solutions were slowly added dropwise to the mixture, and the temperature was maintained at 55℃. The pH was adjusted to 6.0 with 1 mol / L citric acid solution, and then stirred at 100 rpm for 20 minutes until the system was homogeneous. Finally, the mixture was filtered through a 200-mesh filter cloth to remove undissolved large particulate impurities, yielding a pale yellow transparent antibacterial detergent.

[0067] Example 2

[0068] The specific implementation method is the same as in Example 1, except that the preparation of the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative is as follows: 2g of carboxymethyl chitosan is dissolved in 200mL of 1% acetic acid solution and magnetically stirred (25℃, 1h) until completely dissolved; 0.6g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.36g of N-hydroxysuccinimide are added, the pH is adjusted to 6.3, and the reaction is carried out at room temperature for 1.8h; the reaction solution is cooled to 9℃, 1.8g of polyhexamethylene biguanide hydrochloride is added dropwise, the pH is adjusted to 7.2, and the reaction is continued for 9h; 0.9g of azobenzene-4-acrylate is added to the reaction solution and the reaction is carried out at room temperature in the dark for 6h; after the reaction is completed, the derivative is obtained by dialyzing (4℃, 4 days) and freeze-drying (-55℃, 19h). Preparation of inulin-dodecyl alcohol-vitamin E succinate derivative: 2g of inulin was dissolved in 20mL of anhydrous dimethyl sulfoxide, and 0.8g of chlorosulfonic acid was added. The reaction was carried out at 52℃ for 4h under nitrogen protection. The reaction solution was poured into ice water (volume ratio 1:5), and a precipitate was formed. The precipitate was filtered, washed with water (3 times), and dried to obtain a sulfonate intermediate. The intermediate was dissolved in 10mL of N,N-dimethylformamide, and 4g of dodecyl alcohol and 0.4g of 4-dimethylaminopyridine were added. The reaction was carried out at room temperature in the dark for 12h. The reaction was dialyzed (4℃, 2 days) and freeze-dried to obtain a dodecyl alcohol-modified intermediate. The intermediate was dissolved in 10mL of anhydrous tetrahydrofuran, and 3g of vitamin E succinate and 0.6g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The pH was adjusted to 6.7, and the reaction was carried out at room temperature for 15h. The derivative was obtained by rotary evaporation under reduced pressure, extraction, and drying. Preparation of detergent: Weigh 10g of sodium alkylbenzene sulfonate and 7g of fatty alcohol polyoxyethylene ether, add 75g of deionized water, heat to 58℃ and stir magnetically (350rpm, 40min) until completely dissolved; add 0.3g of disodium ethylenediaminetetraacetate and 0.15g of methylisothiazolinone, and continue stirring (180rpm, 20min) to obtain a mixture; pre-dissolve 2g of carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, 1.5g of inulin-dodecyl alcohol-vitamin E succinate derivative and 0.3g of glucose oxidase in deionized water (10mL each) (sonicate for 15min, 30℃), add dropwise to the mixture, adjust the pH to 6.3, stir (150rpm, 30min) until uniform, and filter through a 200-mesh filter cloth to obtain a bio-antibacterial detergent.

[0069] Example 3

[0070] The specific implementation method is the same as in Example 1, except that the preparation of the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative is as follows: 3g of carboxymethyl chitosan is dissolved in 300mL of 1% acetic acid solution and magnetically stirred (25℃, 1h) until completely dissolved; 0.9g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.54g of N-hydroxysuccinimide are added, the pH is adjusted to 6.4, and the reaction is carried out at room temperature for 2h; the reaction solution is cooled to 10℃, 2.7g of polyhexamethylene biguanide hydrochloride is added dropwise, the pH is adjusted to 7.5, and the reaction is continued for 10h; 1.35g of azobenzene-4-acrylate is added to the reaction solution and the reaction is carried out at room temperature in the dark for 6h; after the reaction is completed, the derivative is obtained by dialyzing (4℃, 4 days) and freeze-drying (-55℃, 20h). Preparation of inulin-dodecyl alcohol-vitamin E succinate derivative: 3g of inulin was dissolved in 30mL of anhydrous dimethyl sulfoxide, and 1.2g of chlorosulfonic acid was added. The reaction was carried out at 50℃ for 5h under nitrogen protection. The reaction solution was poured into ice water (volume ratio 1:5), and a precipitate was formed. The precipitate was filtered, washed with water (3 times), and dried to obtain a sulfonate intermediate. The intermediate was dissolved in 15mL of N,N-dimethylformamide, and 6g of dodecyl alcohol and 0.6g of 4-dimethylaminopyridine were added. The reaction was carried out at room temperature in the dark for 20h. The reaction was dialyzed (4℃, 2 days) and freeze-dried to obtain a dodecyl alcohol-modified intermediate. The intermediate was dissolved in 15mL of anhydrous tetrahydrofuran, and 4.5g of vitamin E succinate and 0.9g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The pH was adjusted to 7.0, and the reaction was carried out at room temperature for 20h. The derivative was obtained by rotary evaporation under reduced pressure, extraction, and drying. Preparation of detergent: Weigh 16g of sodium alkylbenzene sulfonate and 10g of fatty alcohol polyoxyethylene ether, add 85g of deionized water, heat to 60℃ and stir magnetically (400rpm, 50min) until completely dissolved; add 0.6g of disodium ethylenediaminetetraacetate and 0.25g of methylisothiazolinone, and continue stirring (200rpm, 20min) to obtain a mixture; pre-dissolve 4g of carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, 3g of inulin-dodecyl alcohol-vitamin E succinate derivative and 0.1g of glucose oxidase in deionized water (15mL each) (sonicate for 20min, 30℃), add dropwise to the mixture, adjust the pH to 6.5, stir (200rpm, 40min) until uniform, and filter through a 200-mesh filter cloth to obtain a biological antibacterial detergent.

[0071] Comparative Example 1

[0072] The specific implementation method is the same as in Example 1, except that the detergent is prepared as follows: 7g of sodium alkylbenzene sulfonate and 4g of fatty alcohol polyoxyethylene ether are weighed and added to 70g of deionized water. The mixture is heated to 55°C and magnetically stirred (300rpm, 30min) until completely dissolved. 0.1g of disodium ethylenediaminetetraacetate and 0.05g of methylisothiazolinone are added and stirred (150rpm, 15min) to obtain a mixed solution. 0.3g of inulin-dodecyl alcohol-vitamin E succinate derivative and 0.2g of glucose oxidase are pre-dissolved in deionized water (5mL) (ultrasonicated for 10min, 30°C), added dropwise to the mixed solution, and the pH is adjusted to 6.0. The mixture is stirred (100rpm, 20min) until homogeneous and then filtered through a 200-mesh filter cloth to obtain the detergent (without carboxymethyl chitosan derivative).

[0073] Comparative Example 2

[0074] The specific implementation method is the same as in Example 1, except that the detergent is prepared as follows: 7g of sodium alkylbenzene sulfonate and 4g of fatty alcohol polyoxyethylene ether are weighed, 70g of deionized water is added, and the mixture is heated to 55°C and magnetically stirred (300rpm, 30min) until completely dissolved; 0.1g of disodium ethylenediaminetetraacetate and 0.05g of methylisothiazolinone are added, and stirring is continued (150rpm, 15min) to obtain a mixture; 0.5g of carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative and 0.2g of glucose oxidase are pre-dissolved in deionized water (5mL) (ultrasonic 10min, 30°C), added dropwise to the mixture, the pH is adjusted to 6.0, and the mixture is stirred (100rpm, 20min) until homogeneous. The mixture is then filtered through a 200-mesh filter cloth to obtain the detergent (without inulin derivative).

[0075] Comparative Example 3

[0076] The specific implementation method is the same as in Example 1, except that the detergent is prepared as follows: 7g of sodium alkylbenzene sulfonate and 4g of fatty alcohol polyoxyethylene ether are weighed, 70g of deionized water is added, and the mixture is heated to 55°C and magnetically stirred (300rpm, 30min) until completely dissolved; 0.1g of disodium ethylenediaminetetraacetate and 0.05g of methylisothiazolinone are added, and stirring is continued (150rpm, 15min) to obtain a mixture; the mixture is then filtered through a 200-mesh filter cloth to obtain the basic detergent (which does not contain any modified bio-based compounds).

[0077] Performance testing

[0078] The detergents prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests according to the following methods: Antimicrobial performance testing was conducted using GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles - Part 3: Shaking Method" and GB4789.2-2016 "National Food Safety Standard - Microbiological Examination of Food - Determination of Total Colony Count". The tested bacterial species included Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538, Candida albicans ATCC 10231, and Pseudomonas aeruginosa ATCC. 27853), covering Gram-positive / negative bacteria and fungi; the specific steps are as follows: dilute the detergent sample with 0.9% sterile physiological saline to a gradient concentration of 0.01%, 0.02%, 0.05%, 0.1%, and 0.2%. Take 1 mL of the diluted solution and mix it with 9 mL of agar medium melted at 45℃, then add 100 μL of a concentration of approximately 1×10⁻⁶. 5 A bacterial suspension of CFU / mL was poured into a sterile 90 mm diameter Petri dish, shaken well, cooled, and incubated at 37°C for 24 h (48 h for fungal culture). Colony growth was observed, and the minimum complete inhibitory concentration (MIC) was recorded. For Escherichia coli and Staphylococcus aureus, an additional shaking test was performed. 100 mL of bacterial culture medium (1 × 10⁻⁶ CFU / mL) was used for further verification. 5Add 1 mL of detergent sample (CFU / mL), shake at 200 rpm for 1 h, then take 100 μL and spread it on a plate. After incubation, count the number of surviving bacteria and calculate the inhibition rate (inhibition rate = (number of surviving bacteria in control group - number of surviving bacteria in experimental group) / number of surviving bacteria in control group × 100%). The detergency test was conducted according to GB / T 13174-2021 "Determination of Detergency of Detergents for Clothing". The test stain was peanut oil (simulating common household grease stains). The specific steps were as follows: a standard stained cloth was prepared (cotton fabric was immersed in peanut oil at a volume ratio of 1:5, dried at 60℃ for 24 hours, and then vacuum freeze-dried). A 0.5% detergent solution was prepared. The stained cloth and the standard white cloth were placed in a washing machine at the same time, 200 mL of detergent solution was added, and the washing program was set at 40℃ water temperature, 1200 rpm speed, and 15 min. After washing, the cloth was rinsed twice with distilled water (5 min each time) and dried at 40℃. The reflectance of the stained cloth and the white cloth at a wavelength of 457 nm was measured using a colorimeter, and the oil removal rate was calculated (oil removal rate = (white cloth reflectance - stained cloth reflectance) / white cloth reflectance × 100%). Stability tests included pH stability (using GB / T 6368-2008 "Determination of pH of Aqueous Surfactant pH by Potentiometric Method") and viscosity stability (using GB / T265-1988 "Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity of Petroleum Products"). The specific steps were as follows: For pH testing, 10g of detergent sample was diluted with deionized water to 100mL (1% concentration). The pH value at 25℃ was measured using a calibrated pH meter (accuracy ±0.01). The sample was stored in a 40℃ constant temperature incubator for 6 months, and the total change was calculated every 30 days (ΔpH = final pH - initial pH). The specific steps of the skin irritation test are as follows: Twenty healthy adult subjects (aged 18-60 years, no history of skin diseases, no use of irritating skin care products, and no use of any topical medications within 2 weeks prior to the test) were selected. The detergent sample was diluted with deionized water to a concentration of 0.1% (simulating the actual usage concentration). After cleaning the inner forearm of the subjects (avoiding hair and broken skin), a 2cm × 2cm test area was marked with a marker, symmetrically placed on both sides. 0.1mL of the diluted solution was applied to the left side, and an equal amount of deionized water was applied to the right side (blank control). The area was covered with 3M Tegaderm occlusive dressing. The dressing was removed after 24 hours, and the subjects were scored according to a 0-4 scale (0 points: no erythema / edema; 1 point: mild erythema without edema; 2 points: moderate erythema with mild edema; 3 points: severe erythema with significant edema; 4 points: ulceration or necrosis). The irritation score of each subject was recorded and the average value (irritation index) was calculated.

[0079] Performance test results:

[0080] Table 1: Performance test results of each embodiment and comparative example

[0081]

[0082]

[0083] As can be seen from Table 1, Examples 1-3 comprehensively solved the problems of the prior art compared to Comparative Examples 1-3. Regarding antibacterial performance, the MIC values ​​of the examples against Escherichia coli, Staphylococcus aureus, Candida albicans, and Pseudomonas aeruginosa were as low as 8-50 μg / mL, and the inhibition rate by shaking method was as high as 99.95% or more, proving that they possess highly efficient and broad-spectrum antibacterial capabilities. This completely overcomes the shortcomings of the narrow antibacterial spectrum of bio-based materials exposed by Comparative Example 1 (without chitosan derivatives) which showed weak bacterial inhibition (MIC>100-200 μg / mL) and Comparative Example 2 (without inulin derivatives) which was almost ineffective against fungi (MIC>200 μg / mL). This strong synergistic antibacterial effect stems from molecular design: the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative stabilizes the grafted polyhexamethylene guanidine (PHMB) via amide bonds, avoiding the rapid release of small-molecule PHMB. The strong interaction between its cationic guanidine group and bacterial cell membrane phospholipids makes it difficult to induce drug resistance. Simultaneously, the azobenzene photoresponsive unit enables intelligent sterilization, further reducing the risk of drug resistance. Meanwhile, the inulin-dodecyl alcohol-vitamin E succinate derivative enhances penetration into hydrophobic fungal cell membranes through its long-chain alkyl group. The synergistic effect of both significantly broadens the antibacterial spectrum and enhances efficacy. In terms of detergency, the degreasing rate of 85.5%-88.9% in Example 1 was significantly higher than that of Comparative Example 1 (78.1%) and Comparative Example 2 (60.3%), confirming the enhancing effect of the derivative's amphiphilic structure on oil emulsification and removal, thus overcoming the limitation of single-performance characteristics in bio-based materials. In terms of stability, the ΔpH of the examples was only +0.10 to +0.15, far superior to Comparative Example 1 (ΔpH +0.35) and Comparative Example 3 (ΔpH -0.60), demonstrating that the buffering capacity and colloidal protection provided by the natural polysaccharide backbone effectively inhibited the hydrolytic degradation of chemical components and extended the product's shelf life. Most importantly, the extremely low skin irritation index (0 points) of the examples, compared to the high irritation of Comparative Example 3 (2 points), fully demonstrates its environmental friendliness and biosafety. The sustained release of the traditional antibacterial agent (PHMB) was achieved by chemically modifying it onto a macromolecular chain, significantly reducing the cytotoxicity and environmental toxicity caused by direct contact. Therefore, the data fully demonstrate that this invention, through ingenious molecular design and formulation, successfully and synergistically solved the problems of drug resistance and toxicity of chemical antibacterial agents, as well as the technical bottlenecks of weak performance and narrow applications of bio-based materials.

[0084] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A biological antibacterial composition, characterized in that, Including the following parts by weight of raw materials: Carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative: 0.5-4 parts by weight; Inulin-dodecyl alcohol-vitamin E succinate derivative: 0.3-3 parts by weight; Sodium alkylbenzene sulfonate: 7-16 parts by weight; Fatty alcohol polyoxyethylene ether: 4-10 parts by weight; Disodium ethylenediaminetetraacetate: 0.1-0.6 parts by weight; Methylisothiazolinone: 0.05-0.25 parts by weight; Glucose oxidase: 0.1-0.3 parts by weight; Deionized water: 68-90 parts by weight; The preparation method of the carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative includes: A1, dissolving carboxymethyl chitosan in acetic acid solution and stirring magnetically until completely dissolved; adding 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, adjusting the pH to 6.2-6.4, and reacting at room temperature; cooling the reaction solution to 8-10℃, adding polyhexamethylene biguanide hydrochloride dropwise, adjusting the pH to 7.0-7.5, and continuing the reaction; A2, adding azobenzene-4-acrylate to the reaction solution, and reacting at room temperature in the dark; after the reaction is completed, the product is placed in a dialysis bag, dialyzed with deionized water, and the dialysate is freeze-dried.

2. The biological antibacterial composition according to claim 1, characterized in that, In step A1, the reaction time at room temperature is 1.5-2 hours; the reaction time continues for 8-10 hours.

3. The biological antibacterial composition according to claim 1, characterized in that, In step A2, the freeze-drying temperature is -55℃ and the time is 18-20h.

4. The biological antibacterial composition according to claim 1, characterized in that, The preparation method of the inulin-dodecyl alcohol-vitamin E succinate derivative includes: B1, dissolving inulin in anhydrous dimethyl sulfoxide, adding chlorosulfonic acid, and reacting at 50-55°C under nitrogen protection; pouring the reaction solution into ice water to precipitate the precipitate, filtering, washing with deionized water, and drying to obtain a sulfonate intermediate; dissolving the intermediate in N,N-dimethylformamide, adding dodecyl alcohol and 4-dimethylaminopyridine, and reacting at room temperature in the dark; dialyzing the reaction solution with a dialysis bag, and freeze-drying the dialysate to obtain a dodecyl alcohol-modified intermediate; B2, dissolving the dodecyl alcohol-modified intermediate in anhydrous tetrahydrofuran, adding vitamin E succinate and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, adjusting the pH to 6.5-7, and reacting at room temperature; rotary evaporating the reaction solution under reduced pressure, extracting the residue with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and filtering.

5. The biological antibacterial composition according to claim 4, characterized in that, In step B1, the reaction time is 3-5 hours at 60-64℃; the reaction time is 10-20 hours at room temperature in the dark.

6. The biological antibacterial composition according to claim 4, characterized in that, In step B2, the reaction time at room temperature is 12-20 hours.

7. A detergent, characterized in that, Includes the biological antibacterial composition according to any one of claims 1-6.

8. A method for preparing a detergent according to claim 7, characterized in that, step include: S1. Weigh sodium alkylbenzene sulfonate and fatty alcohol polyoxyethylene ether, add deionized water, heat to 55-60℃ and stir magnetically until completely dissolved; then add disodium ethylenediaminetetraacetate and methylisothiazolinone, continue stirring to obtain a mixture; S2. Carboxymethyl chitosan-polyhexamethylene guanidine-azobenzene acrylate derivative, inulin-dodecyl alcohol-vitamin E succinate derivative and glucose oxidase are pre-dissolved in deionized water, added dropwise to the mixture, the pH is adjusted to 6.0-6.5, stirred evenly, and filtered through a filter cloth.

9. The preparation method according to claim 8, characterized in that, In step S1, the magnetic stirring speed at 55-60℃ is 300-400 rpm for 30-50 min; the stirring speed is then increased to 150-200 rpm for 15-20 min.

10. The preparation method according to claim 8, characterized in that, In step S2, the stirring speed is 100-200 rpm and the time is 20-40 min.

Images