Synthesis and application of modified creatine antibacterial surfactant

Abstract

The application discloses synthesis and application of modified creatine monohydrate antibacterial surfactant and belongs to the technical field of daily chemical products. The modified creatine monohydrate antibacterial surfactant is a symmetrical dicationic amphiphilic surfactant formed by connecting arms of a quaternary ammonium modified creatine dicationic structure; the connecting arms are obtained by reacting hydroxyethyl ethylenediamine with glutaryl dichloride. The modified creatine monohydrate antibacterial surfactant integrates the antibacterial function and the surface activity in one body by using the creatine molecule of a natural source as a structural skeleton and through chemical modification, and is suitable for application in the fields of medical disinfection, daily chemical washing and protection, biomaterials and the like.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical product technology, specifically relating to the synthesis and application of a modified creatine monohydrate antibacterial surfactant. Background Technology

[0002] With increasing public awareness of health and growing demand for medical and health services, antimicrobial surfactants are being used more and more widely in daily chemicals, medical applications, food processing, and industrial water treatment. An ideal antimicrobial surfactant should possess characteristics such as high antimicrobial activity, good surface activity, environmental friendliness, and low likelihood of inducing microbial resistance.

[0003] Currently, the mainstream antibacterial surfactants on the market mainly include the following categories: 1. Quaternary ammonium salt cationic surfactants: such as benzalkonium chloride and hexadecyltrimethylammonium chloride. These products work by adsorbing their positively charged nitrogen atoms onto the negatively charged cell membranes of microorganisms, disrupting the membrane structure and leading to cell death, exhibiting broad-spectrum and highly effective antibacterial properties. However, traditional quaternary ammonium salts have problems such as high toxicity, poor biodegradability, and the potential for microbial resistance with long-term use.

[0004] 2. Guanidine polymers: such as polyhexamethylene biguanide, have an antibacterial mechanism similar to quaternary ammonium salts, but with a higher positive charge density, stronger antibacterial efficacy, and are less prone to developing drug resistance. However, polyhexamethylene biguanide itself has relatively weak surface activity and usually needs to be used in combination with other surfactants, and its high molecular weight limits its application to some extent.

[0005] 3. Natural and biosurfactants: such as rhamnolipids and sophorolipids. They have good biodegradability and low ecotoxicity, but they have bottlenecks such as high production costs, relatively weak antibacterial efficacy, complex chemical structures, and poor batch-to-batch stability, making large-scale commercial application difficult.

[0006] In addition, most products only focus on one of antibacterial or surface activity, making it difficult to achieve simultaneous antibacterial and decontamination. Summary of the Invention

[0007] To overcome the shortcomings of the prior art, this invention provides a modified creatine monohydrate antibacterial surfactant, which uses naturally derived creatine molecules as the structural framework and, through chemical modification, combines antibacterial function with surface activity. The technical solution to achieve the purpose of this invention is as follows: A modified creatine monohydrate antibacterial surfactant is a quaternized modified creatine dicationic structure forming a symmetrical dicationic amphiphilic surfactant through a linker arm; the linker arm is obtained by reacting hydroxyethyl ethylenediamine with glutaryl dichloro.

[0008] The structure of the modified creatine monohydrate antibacterial surfactant is shown below: , where R is selected from saturated alkyl chains with 6 to 16 carbon atoms.

[0009] A method for synthesizing a modified creatine monohydrate antibacterial surfactant includes the following steps: S1. Preparation of anhydrous creatine: 1 eq of creatine monohydrate was spread evenly on a stainless steel tray, weighed at room temperature and the initial mass was recorded. Then, it was vacuum dried in a vacuum drying oven at 40~60℃ and -0.08~-0.09 MPa for 10~12 h. The weight was measured every 30 min until two consecutive weight loss values ​​were <0.1% and the weight loss rate was ≥10%. Then, the vacuum was broken by passing dry nitrogen gas and the mixture was cooled to room temperature to obtain white anhydrous creatine with a yield ≥90%. The mixture was immediately transferred to a desiccator for use. S2. Preparation of creatine quaternary ammonium salt intermediate: Anhydrous creatine was heated to 40-50℃ in deionized water and stirred until homogeneous. Sodium hydroxide solution was added to adjust the pH to 7.5-9.5. Separately, an aqueous solution containing 2,3-epoxypropyltrimethylammonium chloride was placed in a constant pressure dropping funnel. The reaction flask was kept at 30-40℃ and stirred vigorously. The solution was added dropwise at a uniform rate over 1-2 h, with sodium hydroxide solution added during the process to maintain the pH at 7.5-9.5. After the addition was complete, the reaction was carried out at 40-50℃ for 10-15 h. After the reaction was completed, the solution was neutralized with hydrochloric acid solution to a pH of 6.5-7.5. The solution was concentrated under reduced pressure. The concentrate was poured into a solution of three times its volume of cold ethanol and acetone in a 1:1 volume ratio to precipitate. The solution was allowed to stand, filtered, and washed with a mixture of cold ethanol and acetone. The resulting solid was dried under vacuum at 40-50℃ for 5-8 h to obtain the creatine quaternary ammonium salt intermediate. S3. Preparation of modified creatine monohydrate antibacterial surfactant: S31. Preparation of hydroxyethyl ethylenediamine protected by terminal hydroxyl and amino groups: Hydroxyethyl ethylenediamine was dissolved in anhydrous dichloromethane and stirred in an ice bath. Imidazole was added all at once, and after dissolution, tert-butyldimethylchlorosilane was added dropwise. The mixture was stirred in an ice bath for 10-15 min, then the temperature was raised to room temperature for 20-30 min. After the reaction was completed, the mixture was purified. The above hydroxyethyl ethylenediamine protected by terminal hydroxyl groups was mixed with deionized water and heated to -5 to 0°C in an ice-salt bath. Sodium carbonate aqueous solution was added to adjust the pH to 9-10. Ditert-butyl dicarbonate was dissolved in 5-15 mL of tetrahydrofuran and then added dropwise to the reaction system. The mixture was stirred vigorously for 1-2 h. After the reaction was completed, the aqueous phase was separated, and the organic phases were combined. The organic phases were purified by neutral alumina column chromatography to obtain hydroxyethyl ethylenediamine protected by terminal hydroxyl and amino groups for later use. S32. Preparation of dihydroxydiamine intermediate: Under a nitrogen atmosphere, glutaryl dichlorodi ... S33. Under nitrogen atmosphere, the creatine quaternary ammonium salt intermediate obtained in step S2, a diisopropylcarbodiimide ice bath solution of dichloromethane, 4-dimethylaminopyridine, and 5-10 mL of anhydrous N,N-dimethylformamide were added to the above intermediate. The reaction was carried out at 0°C to room temperature, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, trifluoroacetic acid was added for deamination protection, and the reaction was carried out in an ice bath for 25-35 min, then at room temperature for 50-60 min. After the reaction was completed, excess acid was removed, and the mixture was concentrated and purified under reduced pressure. The above product was dissolved in anhydrous N,N-dimethylformamide, cooled to 0°C in an ice bath, and N,N-diisopropylethylamine was added. Then, a cold dichloromethane solution containing long-chain alkyl acyl chloride was slowly added dropwise. The mixture was stirred in an ice bath at 0°C for 25-30 min, then at room temperature for 1-1.5 h. After removing the solvent under reduced pressure, 5-10 mL of trifluoroacetic acid was added to the solution. The modified creatine monohydrate antibacterial surfactant was obtained by washing with wt% sodium bicarbonate aqueous solution, deionized water, and saturated brine, drying and concentrating the organic phase, purifying by neutral alumina column chromatography, and then vacuum drying at 30-40℃.

[0010] In step S2, the molar ratio of anhydrous creatine to 2,3-epoxypropyltrimethylammonium chloride is 1:(1.1~1.2); and the concentration of the aqueous solution of 2,3-epoxypropyltrimethylammonium chloride in step S2 is 20~30 wt%.

[0011] In step S31, the molar ratio of hydroxyethyl ethylenediamine and tert-butyl dimethylchlorosilane is 1:(1~1.05); in step S31, the molar ratio of hydroxyethyl ethylenediamine with terminal hydroxyl groups to ditert-butyl dicarbonate is 1:(1~1.05); in step S32, the molar ratio of glutaryl dichloro, hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups is 1:2; the molar ratio of hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups to tetrabutylammonium fluoride is 1:( 2.05~2.2); In step S33, the molar ratio of dihydroxydiamine intermediate, creatine quaternary ammonium salt intermediate, diisopropylcarbodiimide, and 4-dimethylaminopyridine is 1:(2~2.2):(2.1~2.2):(0.1~0.4); In step S33, the molar ratio of creatine quaternized dihydroxydiamine intermediate, N,N-diisopropylethylamine, and long-chain alkyl acyl chloride is 1:(2.1~2.2):(2.1~2.2).

[0012] The long-chain alkyl acyl chloride is selected from one or more of heptanyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, undecanoyl chloride, dodecanoyl chloride, tridecanoyl chloride, tetradecanoyl chloride, pentadecanoyl chloride, hexadecanoyl chloride, and heptadecanyl chloride.

[0013] The concentration of the sodium hydroxide solution is 0.5~1 mol / L; the concentration of the hydrochloric acid solution is 0.5~1.0 mol / L; the concentration of the sodium carbonate solution is 0.5~1.0 mol / L; and the concentration of the tetrabutylammonium fluoride tetrahydrofuran solution is 1~2 mol / L.

[0014] Another objective of this invention is to provide the application of the modified creatine monohydrate antibacterial surfactant prepared by the above-mentioned method as an antibacterial surfactant in the fields of medical disinfection, daily chemical care, and biomaterials.

[0015] A disinfectant cleaning agent, by weight, comprises 6-10 parts of modified creatine monohydrate antibacterial surfactant, 0-5 parts of nonionic surfactant, 5-10 parts of citric acid, 5-8 parts of ethanol, 0-1.5 parts of additives, and 65.5-84 parts of deionized water.

[0016] The additives are selected from one or two of pigments and fragrances.

[0017] The nonionic surfactant is selected from one or more of 2-propylheptanol polyoxyethylene ether, 2-hexyldecol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

[0018] Another object of the present invention is to provide a method for preparing the disinfectant cleaning agent as described above, comprising the following steps: Add 25-30 parts of deionized water to a container, heat to 30-35℃, add 6-10 parts of modified creatine monohydrate antibacterial surfactant, and stir thoroughly to dissolve completely; cool to ≤30℃, add 0-5 parts of nonionic surfactant and 5-10 parts of citric acid in sequence, and stir evenly; add 5-8 parts of ethanol, stir evenly, and slowly add 10-20% sodium hydroxide solution dropwise at 22-28℃ for ≥5 min, monitoring the pH in real time to 3.5-5.0, add the remaining deionized water, and stir evenly; cool to ≤25℃, slowly add 0-1.5 parts of additives, stir for 10-15 min, and immediately complete filling in a temperature-controlled explosion-proof filling area to obtain the disinfectant cleaning agent.

[0019] Beneficial effects

[0020] This invention designs a modified creatine monohydrate antibacterial surfactant, using naturally derived creatine molecules as the structural framework. Through chemical modification, it integrates antibacterial function and surface activity, and has the following beneficial effects: 1. Innovative design with creatine as the molecular backbone: Breaking away from the conventional approach of using petroleum derivatives or simple sugars as raw materials for traditional surfactants, this design selects creatine, which is naturally present in organisms, as the source of the hydrophilic head group, bringing inherent bioactivity and green attributes to the product.

[0021] 2. Synergistic effect of dual antibacterial groups: The guanidinium group and the trimethyl quaternary ammonium salt group of creatine exert a synergistic effect by disrupting the phospholipid bilayer of the cell membrane and penetrating the cell membrane by electrostatic adsorption, thereby improving antibacterial efficiency and making it less likely to induce drug resistance; in addition, the introduction of permanent cationic quaternary ammonium salt groups enables the surfactant of the present invention to have antibacterial effect in both weakly acidic and neutral environments.

[0022] 3. Precise construction of amphiphilic structure: Long-chain alkanes serve as hydrophobic ends, endowing surfactants with emulsifying and cleaning capabilities; quaternary ammonium salts and guanidine groups serve as hydrophilic ends, enhancing antibacterial specificity through electrostatic binding of positive charges with negatively charged phospholipids on bacterial membranes. This dual-function integration of "hydrophobic cleaning + cationic antibacterial" allows the molecule to function as both a "cleaner" and an "antibacterial agent," eliminating the need for compounding with other ingredients.

[0023] In summary, compared with traditional quaternary ammonium salt surfactants, the surfactant of this invention has stronger anti-biofilm ability; compared with single-function antibacterial agents, it also has surface activity; and compared with natural surfactants, it has stronger antibacterial activity, making it suitable for applications in medical disinfection, daily chemical care, biomaterials and other fields. Attached Figure Description

[0024] Figure 1 This describes the synthetic route for modified creatine monohydrate antibacterial surfactant.

[0025] Figure 2The 1H NMR spectrum of the modified creatine monohydrate antibacterial surfactant 1.

[0026] Figure 3 The 1H NMR spectrum of hydroxyethyl ethylenediamine protected by terminal hydroxyl and terminal amino groups. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0029] The raw materials and equipment used in the embodiments and comparative examples are described below: Anhydrous creatine: prepared in-house, the preparation method is as follows: One eq of creatine monohydrate was spread evenly on a stainless steel tray, weighed at room temperature and the initial mass was recorded. Then, it was vacuum dried in a vacuum drying oven at 45℃ and -0.08~-0.09 MPa for 12 h. The weight was measured every 30 min until two consecutive weight loss values ​​were <0.1% and the weight loss rate was ≥10%. Then, the vacuum was broken by passing dry nitrogen gas and the mixture was cooled to room temperature to obtain white anhydrous creatine with a yield of 92%. The mixture was immediately transferred to a desiccator for later use. Creatine quaternary ammonium salt intermediate: prepared in-house, the preparation method is as follows: 100 g of anhydrous creatine was heated to 45°C and stirred until homogeneous in deionized water. Sodium hydroxide solution was added to adjust the pH to 7.5–9.5. Separately, a 25 wt% aqueous solution of 2,3-epoxypropyltrimethylammonium chloride (1.1 times the molar amount of anhydrous creatine) was placed in a constant-pressure dropping funnel. The reaction flask was kept at 35°C and stirred vigorously. The solution was added dropwise over 1 h at a uniform rate, with 1 mol / L sodium hydroxide solution added during the process to maintain the pH at 7.5–9.5. After the addition was complete, the reaction was carried out at 45°C for 12 h. After the reaction was completed, the solution was neutralized to pH 6.8–7.2 with 1 mol / L hydrochloric acid solution. The solution was concentrated under reduced pressure. The concentrate was poured into a solution of three times its volume of cold ethanol and acetone in a 1:1 volume ratio to precipitate the solid. The solid was allowed to stand, filtered, and washed with a mixture of cold ethanol and acetone. The obtained solid was dried under vacuum at 45°C for 8 h to obtain the creatine quaternary ammonium salt intermediate, with a yield of 83%. Creatine monohydrate: sourced from Anyang Jialong New Energy Technology Co., Ltd.; Additives: Acid-resistant fragrance, commercially available; Nonionic surfactant: 2-propylheptanol polyoxyethylene ether, commercially available; Citric acid: commercially available; Cationic surfactant: N-decyl-N,N-dimethylbenzylammonium chloride, commercially available.

[0030] Antibacterial detergent: Commercially available antibacterial laundry detergent with a 0.3% parachlorometaxylenol content. Example Example 1

[0031] Modified creatine monohydrate antibacterial surfactant 1: self-made, preparation method as follows, eq represents molar equivalent: (1) Preparation of hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups: 1 eq of hydroxyethyl ethylenediamine was dissolved in anhydrous dichloromethane and stirred in an ice bath. 1.2 eq of imidazole was added at once, and after dissolution, 1.05 eq of tert-butyldimethylchlorosilane was added dropwise. The mixture was stirred in an ice bath for 10-15 min, and then the reaction was brought to room temperature for 20-30 min. After the reaction was completed, the mixture was purified. The above hydroxyethyl ethylenediamine with terminal hydroxyl groups was mixed with deionized water and heated to -5 to 0°C in an ice-salt bath. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH to 9-10. 1.05 eq of ditert-butyl dicarbonate was dissolved in 15 mL of tetrahydrofuran and added dropwise to the reaction system. The mixture was stirred vigorously for 1 h. After the reaction was completed, the aqueous phase was separated, and the organic phases were combined and purified by neutral alumina column chromatography to obtain hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups for later use. (2) Preparation of dihydroxydiamine intermediate: Under a nitrogen atmosphere, 1 eq glutaryl dichlorodi ... (3) Under nitrogen conditions, 2 eq of creatine quaternary ammonium salt intermediate, 2.1 eq of diisopropylcarbodiimide in ice bath dichloromethane solution, 0.2 eq of 4-dimethylaminopyridine, and 10 mL of anhydrous N,N-dimethylformamide were added to 1 eq of dihydroxydiamine intermediate. The reaction was carried out from 0°C to room temperature, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, a 1:1 solution of dichloromethane containing 4 eq of trifluoroacetic acid was added, and the reaction was carried out in an ice bath for 30 min, then in a room temperature environment for 1 h. After the reaction was completed, the mixture was filtered, washed with a 5% sodium carbonate aqueous solution, concentrated under reduced pressure, and the organic phases were combined and purified by neutral alumina column chromatography to obtain creatine quaternary ammonium salt dihydroxydiamine intermediate. 1 eq of creatine quaternary ammonium salt dihydroxydiamine intermediate was dissolved in anhydrous N,N-dimethylformamide, cooled to 0°C in an ice bath, and 2.1 eq of 4-dimethylaminopyridine and 10 mL of anhydrous N,N-dimethylformamide were added. N,N-diisopropylethylamine (eq) was added dropwise, followed by the slow addition of a cold dichloromethane solution containing 2.1 eq of dodecanoyl chloride. The mixture was stirred in an ice bath at 0°C for 30 min, then stirred at room temperature for 1 h. After removing the solvent under reduced pressure, the mixture was washed successively with 5 wt% sodium bicarbonate aqueous solution, deionized water, and saturated brine. The organic phase was dried and concentrated, purified by neutral alumina column chromatography, and then dried under vacuum at 35°C to obtain modified creatine monohydrate antibacterial surfactant 1 with a yield of 75%.

[0032] Example 2

[0033] Modified creatine monohydrate antibacterial surfactant 2: self-made. The preparation method is the same as that of modified creatine monohydrate antibacterial surfactant 1. The difference is that in step (4), dodecanoyl chloride is replaced with heptanoyl chloride, and other conditions remain unchanged, thus obtaining modified creatine monohydrate antibacterial surfactant 2.

[0034] Example 3

[0035] Modified creatine monohydrate antibacterial surfactant 3: self-made. The preparation method is the same as that of modified creatine monohydrate antibacterial surfactant 1. The difference is that in step (4), dodecanoyl chloride is replaced with heptadecanoyl chloride. All other conditions remain unchanged to obtain modified creatine monohydrate antibacterial surfactant 3.

[0036] Comparative Example Cationic surfactant: N-decyl-N,N-dimethylbenzylammonium chloride, commercially available.

[0037] Application examples Application Examples 1-5 and Comparative Application Example 1 Disinfectant cleaning agents 1-6: Homemade, preparation method as follows: Add 25-30 parts of deionized water to a container, heat to 30-35℃, add 6-10 parts of modified creatine monohydrate antibacterial surfactant 1-3 or commercially available cationic surfactant, and stir thoroughly until completely dissolved; cool to ≤30℃, add 0-5 parts of nonionic surfactant and 5-10 parts of citric acid in sequence, and stir evenly; add 5-8 parts of ethanol, stir evenly, and slowly add 10% sodium hydroxide solution at 25℃ for ≥5 min, monitoring the pH in real time to 3.5-5.0, add the remaining deionized water, and stir evenly; cool to ≤25℃, slowly add 0-1.5 parts of additives, stir for 15 min, and immediately complete filling in a temperature-controlled explosion-proof filling area to obtain disinfectant cleaning agent 1-6.

[0038] Application Comparative Example 2 Disinfectant and cleaning agent 7: Commercially available antibacterial detergent.

[0039] Table 1. Formulations for Application Examples 1-5 and Comparative Examples 1-2 (by weight)

[0040] The following are the test methods and results for the performance parameters involved in this invention: 1. Nuclear magnetic resonance hydrogen spectroscopy test: The modified creatine monohydrate antibacterial surfactant 1 and the terminal hydroxyl and terminal amino protected hydroxyethyl ethylenediamine were characterized by nuclear magnetic resonance spectroscopy instrument (Bruker AM-600, Advance 600): The single peak at 3.3 ppm proved the presence of quaternary ammonium methyl; the broad peak at 7~9 ppm proved the presence of guanidine group and amide NH. The above characteristic peaks proved the successful synthesis of modified creatine monohydrate antibacterial surfactant 1.

[0041] 2. Antibacterial performance test: The test was conducted according to section 7.2 of QB / T 2738-2012 "Evaluation Method for Antibacterial and Bacteriostatic Effects of Daily Chemical Products" (Suspension Quantitative Method); test strains: Escherichia coli ATCC25922, Candida albicans ATCC10231; action time: 15 min; action concentration: 1:100; test results are shown in Table 2.

[0042] 3. Ring of Inhibition Test: For cases 1-5 and comparative application examples, the ring of inhibition test was conducted according to section 2.1.8.2 of the "Disinfection Technical Specifications (2002 Edition)" issued by the Ministry of Health of the People's Republic of China; Test strain: Candida albicans (ATCC10231) bacterial suspension, concentration 2.0 x 10⁻⁶. 6 cfu / mL; sterilized filter paper was soaked in 70wt% ethanol aqueous solution until completely wetted, and then air-dried as a blank control group; the experimental results are shown in Table 2.

[0043] 4. Detergent power test: Place 1 g of disinfectant detergent 1-7 in a beaker, add 10 mL of tap water and stir evenly with a glass rod to obtain a disinfectant detergent solution. Drip cooking oil and milk onto a clean white cloth and let it stand for 10 minutes. Use a colorimeter to measure the whiteness value of the cloth. Then put the stained cloth into the laundry detergent solution, stir for 10 minutes, take it out, and measure the whiteness value of the cloth. Calculate the difference in whiteness value of the cloth before and after washing to obtain the whiteness improvement value. The experimental results are shown in Table 2.

[0044] 5. For cases 1 to 5, acute oral toxicity test, acute inhalation toxicity test, skin irritation test, acute eye irritation test, and skin allergy test were conducted in accordance with the "Disinfection Technical Specifications (2002 Edition)" issued by the Ministry of Health of the People's Republic of China, and the test results were all qualified.

[0045] Table 2. Test table of antibacterial effects of surfactants in application examples 1-5 and comparative examples.

[0046] As shown in Table 2, Application Example 1 exhibited good antibacterial effects against both types of bacteria. The chain length of dodecanoyl chloride optimally balances the hydrophilic-lipophilic properties of the molecule, enabling it to efficiently insert into and disrupt the cell membrane of microorganisms. Compared to Application Example 1, Application Example 2 used less antibacterial surfactant 1, resulting in slightly lower performance indicators. In Application Example 3, the amount of antibacterial surfactant 1 increased, leading to a slight improvement in performance, but the performance plateaued. In Application Example 4, the chain length shortened, weakening the hydrophobic effect and reducing the ability to penetrate the cell membrane, thus decreasing both antibacterial and detergency capabilities. In Application Example 5, the chain length increased, reducing the molecular dispersibility in the aqueous phase and slowing diffusion, resulting in a smaller inhibition ring diameter. Detergency was also slightly affected due to faster micelle formation. The conventional monoquaternary ammonium salt used in the comparative application lacked the synergistic effect of creatine molecule modification of the present invention, resulting in a significant decrease in antibacterial ability and a smaller inhibition ring, while the detergency was still acceptable. Commercially available products are compound systems, typically containing specialized high-efficiency detergency components and enzymes, but their antibacterial components may not be specific to fungi and have poor diffusion.

[0047] In summary, this invention designs a modified creatine monohydrate antibacterial surfactant, using naturally derived creatine molecules as the structural framework. Through chemical modification, it integrates antibacterial function and surface activity, with application example 1 exhibiting the best overall performance. Compared to traditional quaternary ammonium salt surfactants, the surfactant of this invention has stronger anti-biofilm ability; compared to single-function antibacterial agents, it also possesses surface activity, making it suitable for applications in medical disinfection, daily chemical care, and biomaterials.

[0048] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A modified creatine monohydrate antibacterial surfactant, characterized in that, The structure of the modified creatine monohydrate antibacterial surfactant is shown below: , where R is selected from saturated alkyl chains with 6 to 16 carbon atoms.

2. The method for synthesizing the modified creatine monohydrate antibacterial surfactant as described in claim 1, characterized in that, Includes the following steps: S1. Preparation of anhydrous creatine: Creatine monohydrate was vacuum dried to obtain white anhydrous creatine, which was then transferred to a desiccator for later use. S2. Preparation of creatine quaternary ammonium salt intermediate: Anhydrous creatine was heated to 40-50℃ in deionized water and stirred until homogeneous. The pH was adjusted to 7.5-9.

5. Separately, an aqueous solution of 2,3-epoxypropyltrimethylammonium chloride was placed in a constant pressure dropping funnel. The reaction flask was kept at 30-40℃ and stirred vigorously. The solution was added dropwise at a uniform rate over 1-2 hours, maintaining the pH at 7.5-9.

5. After the addition was complete, the reaction was carried out at 40-50℃ for 10-15 hours. After the reaction was completed, the solution was neutralized with hydrochloric acid to a pH of 6.8-7.2 and purified to obtain the creatine quaternary ammonium salt intermediate. S3. Preparation of modified creatine monohydrate antibacterial surfactant: S31. Preparation of hydroxyethyl ethylenediamine protected by terminal hydroxyl and amino groups: Hydroxyethyl ethylenediamine was dissolved in anhydrous dichloromethane and stirred in an ice bath. Imidazole was added all at once, and after dissolution, tert-butyldimethylchlorosilane was added dropwise. Stirring continued in an ice bath, and then the reaction was brought to room temperature for 20-30 min. After the reaction was completed, the hydroxyethyl ethylenediamine protected by terminal hydroxyl groups was purified to obtain hydroxyethyl ethylenediamine protected by terminal hydroxyl groups. Hydroxyethyl ethylenediamine protected by terminal hydroxyl groups was mixed with deionized water and heated to -5 to 0°C in an ice-salt bath. Sodium carbonate aqueous solution was added to adjust the pH to 9-10. Ditert-butyl dicarbonate was dissolved in tetrahydrofuran and then added dropwise to the reaction system with vigorous stirring. After the reaction was completed, the hydroxyethyl ethylenediamine protected by terminal hydroxyl and amino groups was purified and set aside. S32. Preparation of dihydroxydiamine intermediate: Under a nitrogen atmosphere, glutaryl dichlorodi ... S33. Under nitrogen atmosphere, the creatine quaternary ammonium salt intermediate obtained in step S2, a diisopropylcarbodiimide ice bath solution of dichloromethane, 4-dimethylaminopyridine, and 5-10 mL of anhydrous N,N-dimethylformamide were added to the dihydroxydiamine intermediate. The reaction was carried out at 0°C to room temperature. After the reaction was completed, trifluoroacetic acid was added for deamination protection. The reaction was carried out in an ice bath for 25-35 min and then raised to room temperature. After the reaction was completed, excess acid was removed, and the mixture was concentrated and purified under reduced pressure to obtain the creatine quaternary ammonium salted dihydroxydiamine intermediate. The creatine quaternary ammonium salted dihydroxydiamine intermediate was dissolved in anhydrous N,N-dimethylformamide and cooled to 0°C in an ice bath. N,N-diisopropylethylamine was added, and then a cold dichloromethane solution containing long-chain alkyl acyl chloride was slowly added dropwise. The reaction was carried out in an ice bath and then raised to room temperature with stirring. After the reaction was completed, the modified creatine monohydrate antibacterial surfactant was obtained by purification.

3. The method for synthesizing the modified creatine monohydrate antibacterial surfactant as described in claim 2, characterized in that, In step S2, the molar ratio of anhydrous creatine to 2,3-epoxypropyltrimethylammonium chloride is 1:(1.1~1.2); the concentration of the aqueous solution of 2,3-epoxypropyltrimethylammonium chloride is 20~30 wt%.

4. The method for synthesizing the modified creatine monohydrate antibacterial surfactant as described in claim 2, characterized in that, In step S31, the molar ratio of hydroxyethyl ethylenediamine and tert-butyl dimethylchlorosilane is 1:(1~1.05); in step S31, the molar ratio of hydroxyethyl ethylenediamine with terminal hydroxyl groups to ditert-butyl dicarbonate is 1:(1~1.05); in step S32, the molar ratio of glutaryl dichloro, hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups is 1:2; the molar ratio of hydroxyethyl ethylenediamine with terminal hydroxyl and amino groups to tetrabutylammonium fluoride is 1:( 2.05~2.2); In step S33, the molar ratio of dihydroxydiamine intermediate, creatine quaternary ammonium salt intermediate, diisopropylcarbodiimide, and 4-dimethylaminopyridine is 1:(2~2.2):(2.1~2.2):(0.1~0.4); In step S33, the molar ratio of creatine quaternized dihydroxydiamine intermediate, N,N-diisopropylethylamine, and long-chain alkyl acyl chloride is 1:(2.1~2.2):(2.1~2.2).

5. The method for synthesizing the modified creatine monohydrate antibacterial surfactant as described in claim 2, characterized in that, The long-chain alkyl acyl chloride is selected from one or more of heptanyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, undecanoyl chloride, dodecanoyl chloride, tridecanoyl chloride, tetradecanoyl chloride, pentadecanoyl chloride, hexadecanoyl chloride, and heptadecanyl chloride.

6. The creatine monohydrate antibacterial surfactant synthesized by the method of synthesizing the modified creatine monohydrate antibacterial surfactant according to claim 1 or any one of claims 2 to 5, can be used as an antibacterial surfactant in the fields of medical disinfection, daily chemical care, and biomaterials.

7. A disinfectant cleaning agent, characterized in that, By weight, it includes 6-10 parts of modified creatine monohydrate antibacterial surfactant, 0-5 parts of nonionic surfactant, 5-10 parts of citric acid, 5-8 parts of ethanol, 0-1.5 parts of additives, and 65.5-84 parts of deionized water.

8. The method for preparing the disinfectant and cleaning agent as described in claim 7, characterized in that, Includes the following steps: Add 25-30 parts of deionized water to a container, heat to 30-35℃, add 6-10 parts of modified creatine monohydrate antibacterial surfactant, and stir thoroughly to dissolve completely; cool to ≤30℃, add 0-5 parts of nonionic surfactant and 5-10 parts of citric acid in sequence, and stir evenly; add 5-8 parts of ethanol, stir evenly, and slowly add 10-20% sodium hydroxide solution dropwise at 22-28℃ for ≥5 min, monitoring the pH in real time to 3.5-5.0, add the remaining deionized water, and stir evenly; cool to ≤25℃, slowly add 0-1.5 parts of additives, stir for 10-15 min, and immediately complete filling in a temperature-controlled explosion-proof filling area to obtain the disinfectant cleaning agent.

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