An anesthesia reservoir with long-lasting antibacterial and antiviral functions
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-03
- Publication Date
- 2026-08-14
AI Technical Summary
然而,现有的麻醉储气囊多采用普通的医用硅胶或乳胶材质制成,其表面及基体本身并不具备抑菌或抗病毒的特性
本申请通过表面活化、引发剂锚定及共聚接枝,在麻醉储气囊内外表面形成稳定的抗菌抗病毒共聚物刷层。该功能层与弹性囊体表面形成牢固结合,相较于普通涂覆或浸渍型抗菌层,不易在清洗过程中脱落,可实现持久的抑菌和抗病毒效果。
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Figure CN122563150A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of anesthesia reservoir technology, specifically to anesthesia reservoir with long-lasting antibacterial and antiviral functions. Background Technology
[0002] In clinical general anesthesia and respiratory support, the anesthesia reservoir, as a crucial component of the breathing circuit, is primarily used to store anesthetic gas mixtures, buffer airway pressure, and assist with artificial ventilation. However, most existing anesthesia reservoirs are made of ordinary medical-grade silicone or latex, whose surfaces and substrates do not possess antibacterial or antiviral properties. In practical applications, patients' exhaled air is often rich in moisture and may carry various bacteria and viruses. Coupled with the complex and open operating environment, pathogenic microorganisms can easily adhere to, colonize, and multiply on the inner and outer surfaces of the reservoir, significantly increasing the risk of iatrogenic cross-infection and respiratory complications. Furthermore, the few medical devices currently available with antibacterial functions often employ surface coatings or short-acting antibacterial agents. These coatings are easily peeled off or become ineffective during the frequent inflation and deflation of the reservoir, gas erosion, and routine cleaning and disinfection processes, failing to provide a durable biological protective barrier.
[0003] Chinese invention patent application CN118165385A discloses a polyisoprene rubber gas reservoir, which comprises the following raw materials in parts by weight: polyisoprene latex: 100 parts, stabilizer: 1-2 parts, sodium vinyl sulfonate aqueous solution: 1-2 parts, nano silica suspension dispersion: 3-6 parts, modified antioxidant: 1-2 parts, conductive graphite: 0.8-1.5 parts, and vulcanizing agent: 3-6 parts. The polyisoprene rubber gas reservoir provided by this invention has excellent mechanical properties, electrical conductivity, and anti-aging properties, but poor antibacterial and antiviral properties.
[0004] Therefore, there is an urgent need to develop an anesthesia reservoir that combines antibacterial and antiviral active substances with a polymer substrate and has long-lasting antibacterial and antiviral functions, so as to effectively block the transmission routes of pathogens during clinical anesthesia and ensure the safety of both doctors and patients. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide an anesthesia reservoir with long-lasting antibacterial and antiviral functions.
[0006] An anesthesia reservoir with long-lasting antibacterial and antiviral functions is prepared by the following method: S1: The elastic capsule is cleaned, dried and subjected to plasma surface activation treatment to obtain a surface-activated elastic capsule; S2: Immerse the surface-activated elastic capsules in the initiator solution to obtain initiator-anchored elastic capsules; S3: The initiator-anchored elastic capsule is placed in a polymerization system containing antibacterial and antiviral functional monomers, 2-methacryloyloxyethyl phosphocholine, catalyst and ligand to react and obtain copolymer brush-grafted elastic capsules; S4: The copolymer-grafted elastic capsule is cleaned, dried and sterilized to obtain anesthesia reservoir with long-lasting antibacterial and antiviral functions.
[0007] In step S1, the elastic capsule is made of natural rubber.
[0008] In step S1, the processing power of the plasma surface activation treatment is 50-100W.
[0009] In step S2, the polymerization initiator is one of propyl 2-bromo-2-methylpropionic acid (3-trimethoxysilyl) ester.
[0010] In step S3, the molar ratio of the antibacterial and antiviral functional monomer: 2-methacryloyloxyethyl phosphocholine: catalyst: ligand is (10-30):(70-90):1:2.
[0011] In step S3, the catalyst is one of CuBr and CuCl.
[0012] In step S3, the ligand is one of 2,2'-bipyridine, N,N,N',N'',N''-pentamethyldiethylenetriamine, and tris(2-pyridinemethyl)amine.
[0013] In step S3, the antibacterial and antiviral functional monomer is prepared by the following method: A1: 5,8,11-trioxa-2-azatridecane-13-ol reacts with sodium 5-chloropentane-1-sulfonate in the presence of a nucleophile to form an intermediate; A2: The intermediate reacts with glycidyl methacrylate to generate an antibacterial and antiviral functional monomer.
[0014] In step S3, the reaction temperature is 40-60℃ and the reaction time is 4-6h.
[0015] In step A1, the nucleophile is potassium iodide.
[0016] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: This application utilizes surface activation, initiator anchoring, and copolymer grafting to form a stable antibacterial and antiviral copolymer brush layer on the inner and outer surfaces of the anesthesia reservoir. This functional layer forms a strong bond with the surface of the elastic bladder, and compared to ordinary coated or impregnated antibacterial layers, it is less likely to fall off during cleaning, thus achieving a long-lasting antibacterial and antiviral effect. Attached Figure Description
[0017] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the antibacterial and antiviral functional monomer prepared in Example 1.
[0018] Figure 2 The high-resolution mass spectrum of the antibacterial and antiviral functional monomer prepared in Example 1 is shown.
[0019] Figure 3 The Fourier transform infrared (FTIR) spectra are compared for the surface modification process of the anesthesia reservoir prepared in Example 2.
[0020] Figure 4 The image shows the X-ray photoelectron spectroscopy (XPS) spectrum of the anesthesia reservoir prepared in Example 2. Detailed Implementation
[0021] Example 1: Preparation of antibacterial and antiviral functional monomers A1: Under nitrogen protection, add 200 mL of N,N-dimethylformamide, 0.10 mol of 5,8,11-trioxa-2-azatridecane-13-ol, and 0.21 mol of... to the reaction flask. Sodium 5-chloropentane-1-sulfonate, 0.13 mol anhydrous potassium carbonate, and 0.005 mol potassium iodide were mixed and stirred. The mixture was heated to 75°C and reacted for 16 h. After cooling to room temperature, the mixture was filtered and concentrated under reduced pressure at 60°C for 3 h. 150 mL of anhydrous ethanol was added, and the mixture was stirred for 30 min and then filtered. The precipitate was then slowly added dropwise to 500 mL of anhydrous acetone and stirred to precipitate. The precipitate was filtered, and the filter cake was washed three times with anhydrous acetone (50 mL each time), followed by two times with anhydrous diethyl ether (30 mL each time). The precipitate was redissolved in 150 mL of anhydrous methanol and slowly added dropwise to 200 mL of anhydrous acetone for a second precipitation. The precipitate was filtered, washed three times with anhydrous acetone (50 mL each time), and dried under vacuum at 45°C for 12 h to obtain the intermediate. The reaction equation is shown below: .
[0022] Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d6) δ 4.62 (t, J = 6.3 Hz,1H), 3.79 – 3.74 (m, 2H), 3.72 – 3.56 (m, 14H), 3.41 (t, J = 8.6 Hz, 4H), 3.16 (s, 3H), 2.45 (dd, J = 10.9, 10.4 Hz, 4H), 1.77 – 1.60 (m, 8H), 1.51(tddd, J = 7.2, 6.4, 5.8, 1.3 Hz, 4H); HRMS (m / z): 506.2096[M-Na] - .
[0023] A2: Under nitrogen protection, 120 mL of anhydrous N,N-dimethylformamide, 0.05 mol of intermediate, 0.25 mmol of 2,6-di-tert-butyl-p-methylphenol, and 2.5 mmol of triethylamine were added to a reaction flask. The mixture was stirred and homogenized. The temperature was raised to 60 °C under light-protected conditions, and 0.055 mol of glycidyl methacrylate was slowly added dropwise over 20 min. After stirring for 18 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 60 °C for 3 h. 600 mL of anhydrous acetone / anhydrous diethyl ether mixed solvent (anhydrous acetone to anhydrous diethyl ether volume ratio of 2:1) was slowly added, and the mixture was stirred to precipitate. The precipitate was filtered, washed three times with anhydrous acetone (50 mL each time), and then washed twice with anhydrous diethyl ether (30 mL each time). The precipitate was dried under vacuum at 45 °C for 12 h to obtain the antibacterial and antiviral functional monomer. The reaction equation is shown below:
[0024] Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d6) δ 5.80 (dq, J = 1.8, 1.2Hz, 1H), 5.56 (dq, J = 2.1, 1.4 Hz, 1H), 4.31 (dd, J = 12.1, 5.9 Hz, 1H), 4.09 – 3.93 (m, 2H), 3.90 – 3.86 (m, 2H), 3.79 – 3.74 (m, 2H), 3.72 – 3.61(m, 12H), 3.52 – 3.42 (m, 6H), 3.36 (d, J = 6.6 Hz, 1H), 3.21 (s, 3H), 2.56(t, J = 10.6 Hz, 4H), 1.93 (dd, J = 1.4, 1.3 Hz, 3H), 1.77 – 1.63 (m, 8H), 1.57 – 1.48 (m, 4H); HRMS (m / z): 648.2733[M-Na] - .
[0025] Example 2: Preparation of an anesthesia reservoir with long-lasting antibacterial and antiviral functions S1: Take a natural rubber anesthesia reservoir (CH-CQN-BF-0.5L type anesthesia reservoir manufactured by Shandong Chuangke Huanhai Medical Technology Co., Ltd., specification 0.5L) as the elastic reservoir body. Place the elastic reservoir body in a 500mL beaker and use 300mL of deionized water to ultrasonically clean it for 10 minutes at 100W ultrasonic power. Then use 300mL of anhydrous ethanol to ultrasonically clean it for another 10 minutes at 100W ultrasonic power. Rinse it twice with deionized water (100mL each time). Place the cleaned elastic reservoir body in a vacuum drying oven at 50℃ and a vacuum degree of -0. The elastic capsule was dried at 0.8 MPa for 2 hours. After drying, the inner and outer surfaces of the elastic capsule were subjected to plasma surface activation treatment. During the outer surface treatment, the elastic capsule was kept in an expanded state within the plasma chamber. During the inner surface treatment, the open end of the elastic capsule was connected to the air inlet of the plasma treatment device, and the inside of the capsule was connected to the pumping system. The capsule was kept in a low-tension expanded state by adjusting the air inlet flow rate and pumping rate. The treatment conditions were: oxygen flow rate 30 mL / min, treatment pressure 100 Pa, treatment power 50 W, and treatment time 100 s. After the treatment, the surface-activated elastic capsule was obtained.
[0026] S2: Under nitrogen protection, 1000 mL of anhydrous n-hexane / anhydrous ethyl acetate mixed solvent (anhydrous n-hexane / anhydrous ethyl acetate volume ratio of 5:1) was added to a 2 L covered glass polymerization reactor, followed by the addition of 29 g of... 2-Bromo-2-methylpropionic acid (3-trimethoxysilyl)propyl ester; The surface-activated elastic capsule obtained in step S1 was placed in a polytetrafluoroethylene (PTFE) mesh basket, and the entire PTFE mesh basket was immersed in the above reaction solution. The glass polymerization reactor was placed in an ice-water bath and reacted for 30 min. Then the temperature was raised to 25°C and the reaction was continued for 2 h. During the reaction, the PTFE mesh basket was gently shaken for 1 min every 20 min. After the reaction was completed, the capsule was washed three times with anhydrous n-hexane (200 mL each time, 5 min each time), three times with isopropanol (200 mL each time, 5 min each time), three times with anhydrous ethanol (200 mL each time, 5 min each time), and three times with deionized water (200 mL each time, 5 min each time). The capsule was then dried at 45°C and a vacuum of -0.08 MPa for 6 h to obtain the initiator-anchored elastic capsule.
[0027] S3: Under nitrogen protection, 1000 mL of methanol / deionized water mixed solvent (methanol to deionized water volume ratio of 3:2) was added to a 2 L covered glass polymerization reactor. 5.0 mmol of antibacterial and antiviral functional monomer, 45.0 mmol of 2-methacryloyloxyethyl phosphocholine and 1.0 mmol of 2,2'-bipyridine were added to the mixed solvent and stirred until completely dissolved. Then, 0.5 mmol of CuBr was added and stirred until homogeneous to obtain a polymerization solution. The initiator-anchored elastic capsule obtained in step S2 was placed in a polytetrafluoroethylene mesh basket and the entire basket was immersed in the polymerization solution. The polymerization reactor was then sealed and placed in a 40 °C constant temperature water bath for 6 h. During the reaction, the mesh basket was gently shaken for 1 min every 30 min. After the reaction, a copolymer brush-grafted elastic capsule was obtained.
[0028] S4: The copolymer brush-grafted elastic capsule obtained in step S3 was placed in a 2L cleaning tank, and 1000mL of 0.05mol / L disodium ethylenediaminetetraacetate aqueous solution was added. The capsule was soaked and cleaned for 30min. Then, it was successively rinsed with deionized water 3 times (300mL each time, 5min each time), anhydrous ethanol 3 times (300mL each time, 5min each time), and deionized water 2 times (300mL each time, 5min each time). After rinsing, the capsule was placed in a vacuum drying oven and dried at 45℃ and -0.08MPa for 8h. Then, it was sterilized with ethylene oxide at 45℃, relative humidity of 55%, ethylene oxide concentration of 600mg / L, and sterilization time of 6h. After sterilization, the capsule was desorbed for 72h to obtain anesthesia reservoir with long-lasting antibacterial and antiviral functions.
[0029] Figure 3 Fourier transform infrared (FTIR) spectra comparisons of the surface modification process of the anesthesia reservoir bladder. After plasma activation, the characteristic peaks of the natural rubber matrix did not show significant shifts or disappearance, indicating that the activation treatment did not cause significant damage to the rubber matrix structure. After initiator anchoring, the peaks at 1750 cm⁻¹... -1 Nearby and 1000-1150cm -1 The regions can be attributed to vibrational absorptions of C=O, Si-OC / Si-O-Si, and CO structures, indicating that the initiator has bound to the capsule surface. After the copolymer was brush-grafted, no completely separated new peaks were observed in the spectrum; the main peaks were at 1750 cm⁻¹. -1 Nearby and 1000-1150cm -1 The absorption peak in the region is further enhanced, indicating the introduction of more oxygen-containing structures such as ester groups, ether bonds, phosphate esters, and sulfonates into the grafted layer. Specifically, the absorption peak at 1750 cm⁻¹ is particularly prominent. -1 The absorption in the vicinity may be related to the C=O ester group in the methacrylate structure; 1000-1150 cm⁻¹ -1 The enhancement of the region can be attributed to the superposition of COC, POC, S=O and Si-O related vibrations, indicating that antibacterial and antiviral functional monomers and 2-methacryloyloxyethyl phosphocholine have been grafted onto the surface of the anesthesia reservoir.
[0030] Figure 4 The XPS spectrum of the anesthesia reservoir with long-lasting antibacterial and antiviral functions is shown in the figure. As can be seen from the figure, there are obvious characteristic peaks of C 1s, O 1s, N 1s, P 2p and S 2p on the sample surface. Among them, the C 1s peak is the strongest, mainly originating from the polyisoprene structure in the natural rubber matrix and the organic carbon skeleton in the surface grafted copolymer brush; the O 1s peak originates from the oxygen-containing functional groups introduced after plasma activation, the phosphorocholine structure, and the ether bond oxygen in the polyether segment; the N 1s peak is mainly attributed to the quaternary ammonium salt structure in the antibacterial and antiviral functional monomer, the nitrogen-containing groups in the copolymer segment, and the quaternary ammonium nitrogen in the 2-methacryloyloxyethyl phosphorocholine structure; the P 2p peak corresponds to the phosphate ester group in 2-methacryloyloxyethyl phosphorocholine; and the S 2p peak originates from the sulfonate structure introduced in the antibacterial and antiviral functional monomer. The XPS results indicate that, after plasma activation, initiator anchoring, and surface-initiated copolymerization, a copolymer brush layer containing quaternary ammonium salt, phosphocholine, and sulfonate structures has been successfully grafted onto the surface of the anesthesia reservoir.
[0031] Example 3: Preparation of an anesthesia reservoir with long-lasting antibacterial and antiviral functions S1: Use a natural rubber anesthesia reservoir (CH-CQN-BF-0.5L type anesthesia reservoir manufactured by Shandong Chuangke Huanhai Medical Technology Co., Ltd., specification 0.5L) as the elastic reservoir body. Place the elastic reservoir body in a 500mL beaker and ultrasonically clean it for 10 minutes at 100W ultrasonic power using 300mL of deionized water. Then ultrasonically clean it for another 10 minutes at 100W ultrasonic power using 300mL of anhydrous ethanol. Rinse it twice with deionized water (100mL each time). Place the cleaned elastic reservoir body in a vacuum drying oven at 50℃ and a vacuum degree of -0. The elastic capsule was dried at 0.08 MPa for 2 hours. After drying, the inner and outer surfaces of the elastic capsule were subjected to plasma surface activation treatment. During the outer surface treatment, the elastic capsule was kept in an expanded state within the plasma chamber. During the inner surface treatment, the open end of the elastic capsule was connected to the air inlet of the plasma treatment device, and the inside of the capsule was connected to the pumping system. The capsule was kept in a low-tension expanded state by adjusting the air inlet flow rate and pumping rate. The treatment conditions were: oxygen flow rate 30 mL / min, treatment pressure 100 Pa, treatment power 80 W, and treatment time 80 s. After the treatment, the surface-activated elastic capsule was obtained.
[0032] S2: Under nitrogen protection, 1000 mL of anhydrous n-hexane / anhydrous ethyl acetate mixed solvent (anhydrous n-hexane / anhydrous ethyl acetate volume ratio of 5:1) was added to a 2 L covered glass polymerization reactor, followed by the addition of 29 g of... 2-Bromo-2-methylpropionic acid (3-trimethoxysilyl)propyl ester; The surface-activated elastic capsule obtained in step S1 was placed in a polytetrafluoroethylene (PTFE) mesh basket, and the entire PTFE mesh basket was immersed in the above reaction solution. The glass polymerization reactor was placed in an ice-water bath and reacted for 30 min. Then the temperature was raised to 25°C and the reaction was continued for 2 h. During the reaction, the PTFE mesh basket was gently shaken for 1 min every 20 min. After the reaction was completed, the capsule was washed three times with anhydrous n-hexane (200 mL each time, 5 min each time), three times with isopropanol (200 mL each time, 5 min each time), three times with anhydrous ethanol (200 mL each time, 5 min each time), and three times with deionized water (200 mL each time, 5 min each time). The capsule was then dried at 45°C and a vacuum of -0.08 MPa for 6 h to obtain the initiator-anchored elastic capsule.
[0033] S3: Under nitrogen protection, 1000 mL of methanol / deionized water mixed solvent (methanol to deionized water volume ratio of 3:2) was added to a 2 L covered glass polymerization reactor. 10.0 mmol of antibacterial and antiviral functional monomer, 40.0 mmol of 2-methacryloyloxyethyl phosphocholine and 1.0 mmol of N,N,N',N'',N''-pentamethyldiethylenetriamine were added to the mixed solvent and stirred until completely dissolved. Then, 0.5 mmol of CuBr was added and stirred until homogeneous to obtain a polymerization solution. The initiator-anchored elastic capsule obtained in step S2 was placed in a polytetrafluoroethylene mesh basket and the entire basket was immersed in the polymerization solution. The polymerization reactor was then sealed and placed in a 50 °C constant temperature water bath for 5 h. During the reaction, the mesh basket was gently shaken for 1 min every 30 min. After the reaction, a copolymer brush-grafted elastic capsule was obtained.
[0034] S4: The copolymer brush-grafted elastic capsule obtained in step S3 was placed in a 2L cleaning tank, and 1000mL of 0.05mol / L disodium ethylenediaminetetraacetate aqueous solution was added. The capsule was soaked and cleaned for 30min. Then, it was successively rinsed with deionized water 3 times (300mL each time, 5min each time), anhydrous ethanol 3 times (300mL each time, 5min each time), and deionized water 2 times (300mL each time, 5min each time). After rinsing, the capsule was placed in a vacuum drying oven and dried at 45℃ and -0.08MPa for 8h. Then, it was sterilized with ethylene oxide at 45℃, relative humidity of 55%, ethylene oxide concentration of 600mg / L, and sterilization time of 6h. After sterilization, the capsule was desorbed for 72h to obtain anesthesia reservoir with long-lasting antibacterial and antiviral functions.
[0035] Example 4: Preparation of an anesthesia reservoir with long-lasting antibacterial and antiviral functions S1: Take a natural rubber anesthesia reservoir (CH-CQN-BF-0.5L type anesthesia reservoir manufactured by Shandong Chuangke Huanhai Medical Technology Co., Ltd., specification 0.5L) as the elastic reservoir body. Place the elastic reservoir body in a 500mL beaker and use 300mL of deionized water to ultrasonically clean it for 10 minutes at 100W ultrasonic power. Then use 300mL of anhydrous ethanol to ultrasonically clean it for another 10 minutes at 100W ultrasonic power. Rinse it twice with deionized water (100mL each time). Place the cleaned elastic reservoir body in a vacuum drying oven at 50℃ and a vacuum degree of -0. The elastic capsule was dried at 0.8 MPa for 2 hours. After drying, the inner and outer surfaces of the elastic capsule were subjected to plasma surface activation treatment. During the outer surface treatment, the elastic capsule was kept in an expanded state within the plasma chamber. During the inner surface treatment, the open end of the elastic capsule was connected to the air inlet of the plasma treatment device, and the inside of the capsule was connected to the pumping system. The capsule was kept in a low-tension expanded state by adjusting the air inlet flow rate and pumping rate. The treatment conditions were: oxygen flow rate 30 mL / min, treatment pressure 100 Pa, treatment power 100 W, and treatment time 60 s. After the treatment, the surface-activated elastic capsule was obtained.
[0036] S2: Under nitrogen protection, 1000 mL of anhydrous n-hexane / anhydrous ethyl acetate mixed solvent (anhydrous n-hexane / anhydrous ethyl acetate volume ratio of 5:1) was added to a 2 L covered glass polymerization reactor, followed by the addition of 29 g of... 2-Bromo-2-methylpropionic acid (3-trimethoxysilyl)propyl ester; The surface-activated elastic capsule obtained in step S1 was placed in a polytetrafluoroethylene (PTFE) mesh basket, and the entire PTFE mesh basket was immersed in the above reaction solution. The glass polymerization reactor was placed in an ice-water bath and reacted for 30 min. Then the temperature was raised to 25°C and the reaction was continued for 2 h. During the reaction, the PTFE mesh basket was gently shaken for 1 min every 20 min. After the reaction was completed, the capsule was washed three times with anhydrous n-hexane (200 mL each time, 5 min each time), three times with isopropanol (200 mL each time, 5 min each time), three times with anhydrous ethanol (200 mL each time, 5 min each time), and three times with deionized water (200 mL each time, 5 min each time). The capsule was then dried at 45°C and a vacuum of -0.08 MPa for 6 h to obtain the initiator-anchored elastic capsule.
[0037] S3: Under nitrogen protection, 1000 mL of methanol / deionized water mixed solvent (methanol to deionized water volume ratio of 3:2) was added to a 2 L covered glass polymerization reactor. 15.0 mmol of antibacterial and antiviral functional monomer, 35.0 mmol of 2-methacryloyloxyethyl phosphocholine and 1.0 mmol of tris(2-pyridinemethyl)amine were added to the mixed solvent and stirred until completely dissolved. Nitrogen gas was then introduced into the polymerization reactor for 30 min, followed by the addition of 0.5 mmol of CuCl and stirring to obtain a polymerization solution. The initiator-anchored elastic capsule obtained in step S2 was placed in a polytetrafluoroethylene mesh basket and the entire basket was immersed in the polymerization solution. The polymerization reactor was then sealed and placed in a 60 °C constant temperature water bath for 4 h. During the reaction, the basket was gently shaken for 1 min every 30 min. After the reaction, a copolymer brush-grafted elastic capsule was obtained.
[0038] S4: The copolymer brush-grafted elastic capsule obtained in step S3 was placed in a 2L cleaning tank, and 1000mL of 0.05mol / L disodium ethylenediaminetetraacetate aqueous solution was added. The capsule was soaked and cleaned for 30min. Then, it was successively rinsed with deionized water 3 times (300mL each time, 5min each time), anhydrous ethanol 3 times (300mL each time, 5min each time), and deionized water 2 times (300mL each time, 5min each time). After rinsing, the capsule was placed in a vacuum drying oven and dried at 45℃ and -0.08MPa for 8h. Then, it was sterilized with ethylene oxide at 45℃, relative humidity of 55%, ethylene oxide concentration of 600mg / L, and sterilization time of 6h. After sterilization, the capsule was desorbed for 72h to obtain anesthesia reservoir with long-lasting antibacterial and antiviral functions.
[0039] Comparative Example 1 The preparation method of the anesthesia reservoir with long-lasting antibacterial and antiviral functions is basically the same as that in Example 3, except that plasma treatment is not performed in step S1.
[0040] Comparative Example 2 The preparation method of the anesthesia reservoir with long-acting antibacterial and antiviral functions is basically the same as that in Example 3, except that 2-methacryloyloxyethyl phosphocholine is not added in step S3.
[0041] Comparative Example 3 The preparation method of the long-acting antibacterial and antiviral anesthesia reservoir is basically the same as that in Example 3, except that in step S3, the amount of antibacterial and antiviral functional monomers is replaced with 2.5 mmol, the amount of 2-methacryloyloxyethyl phosphocholine is replaced with 47.5 mmol, the amount of CuBr is replaced with 0.5 mmol, and the amount of N,N,N',N'',N''-pentamethyldiethylenetriamine is replaced with 0.75 mmol.
[0042] Comparative Example 4 The preparation method of the long-acting antibacterial and antiviral anesthesia reservoir is basically the same as that in Example 3, except that the antibacterial and antiviral functional monomer is replaced with an equal weight of antibacterial and antiviral functional monomer prepared by the following method: The preparation method of the antibacterial and antiviral functional monomer is basically the same as that in Example 1, except that 5,8,11-trioxa-2-azatridecane-13-ol in step A1 is replaced with an equimolar amount of 6-methylamino-1-hexanol.
[0043] Comparative Example 5 The preparation method of the long-acting antibacterial and antiviral anesthesia reservoir is basically the same as that in Example 3, except that the antibacterial and antiviral functional monomer is replaced with an equal weight of antibacterial and antiviral functional monomer prepared by the following method: The preparation method of the antibacterial and antiviral functional monomer is basically the same as that in Example 1, except that the sodium 5-chloropentane-1-sulfonate in step A1 is replaced with an equimolar amount of sodium 3-chloropropane-1-sulfonate.
[0044] Comparative Example 6 The preparation method of the long-acting antibacterial and antiviral anesthesia reservoir is basically the same as that in Example 3, except that the antibacterial and antiviral functional monomer is replaced with an equal weight of antibacterial and antiviral functional monomer prepared by the following method: The preparation method of the antibacterial and antiviral functional monomer is basically the same as that in Example 1, except that the sodium 5-chloropentane-1-sulfonate in step A1 is replaced with an equimolar amount of 1-chloropentane.
[0045] The performance of the anesthesia reservoirs prepared in the embodiments and comparative examples of this application was tested, and the test results are shown in Table 1.
[0046] Tensile strength test: Tested according to ASTM D412-16(2021).
[0047] Antibacterial properties: The anesthesia reservoirs prepared in the examples and comparative examples were cut into uniformly sized circular samples (9 mm in diameter and 2 mm in thickness), placed in capped glass bottles containing PBS buffer (0.1 M, pH=7.4), and then sterilized with ethylene oxide at a temperature of 45°C, a relative humidity of 55%, an ethylene oxide concentration of 600 mg / L, and a sterilization time of 2 h. After sterilization, the samples were analyzed for 72 h. The tested bacterial species was Staphylococcus aureus (ATCC 6538). Individual colonies were picked from the test strain and diluted with physiological saline to a bacterial concentration of 10. 6 CFU / ml. Place the sterilized sample pieces flat in a sterile petri dish; add 100 μL of Staphylococcus aureus suspension to the surface of each sample piece, then cover with a sterilized polyethylene film to ensure the bacterial suspension spreads evenly on the sample surface and is in full contact with the sample surface. Seal the petri dish and incubate at 37℃ for 24 h. After incubation, transfer the sample pieces along with the covering film to a sterile centrifuge tube containing 10 mL of neutralization eluent (PBS buffer containing 0.1 wt% Tween 80, 0.3 wt% lecithin, and 0.1 wt% histidine); vortex the centrifuge tube for 2 min to fully elute any remaining bacteria from the sample surface into the neutralization eluent. Perform a 10-fold serial dilution of the eluent, and spread 100 μL of each appropriate dilution onto the surface of LB agar medium. Incubate at 37℃ for 24 h, then count the colonies and calculate the viable bacteria count on the sample surface. Using unmodified anesthesia reservoir sample as a blank control group, the antibacterial rate was calculated using the following formula: , in: B represents the viable bacterial count of the blank control sample after 24 hours of treatment; the unit is CFU / ml. C represents the number of viable bacteria in the sample after 24 hours of treatment; the unit is CFU / ml.
[0048] Antiviral performance: MS2 phage (ATCC 15597-B1) was used as a virus surrogate model, and the antiviral performance of the anesthesia reservoir samples was evaluated by plaque reduction assay. First, *Escherichia coli* (ATCC 15597) was inoculated into LB medium and cultured at 37°C and 110 rpm until the logarithmic growth phase. 5 mL of logarithmic-phase *E. coli* culture was taken, and 500 μL of MS2 phage stock solution was added. The mixture was cultured at 37°C and 110 rpm for 10 h, followed by centrifugation at 8000 rpm for 10 min and filtration through a 0.22 μm sterile filter to remove *E. coli*, yielding the MS2 phage stock solution. The MS2 phage stock solution was diluted to 10 μL with PBS buffer. 6 PFU / ml was used as the working solution for phage testing.
[0049] A 0.1g sample (2cm × 2cm) was cut from the middle of the anesthesia reservoir and placed in a sterile petri dish. 200μL of a 10-1 solution was then inoculated onto the sample surface. 6 MS2 phage working solution (PFU / ml) was incubated at 37°C for 1 hour. After incubation, 4.5 mL of neutralization and elution buffer (PBS buffer containing 0.1 wt% Tween 80, 0.3 wt% lecithin, and 0.1 wt% histidine) was added, and residual phage on the sample surface was eluted by vortexing for 2 minutes to obtain phage eluent. The eluent was serially diluted 10-fold. 50 μL of each appropriately diluted phage solution was added to 100 μL of logarithmic-phase *E. coli* culture and mixed with 5 mL of LB semi-solid agar at 45°C. The mixture was vortexed and poured onto LB solid agar plates to form a double-layer agar plate, which was then incubated at 37°C for 6 hours. After incubation, the number of phage plaques was counted, and the MS2 phage titer was calculated. An unmodified anesthesia reservoir sample was used as a blank control group. The MS2 phage inhibition rate was calculated using the following formula: , in: The phage titer is for the blank control group; the unit is PFU / ml. The phage titer for the experimental group is expressed in PFU / ml.
[0050] Long-term effectiveness test: Samples (2cm × 2cm) weighing 0.1g were cut from the middle of the anesthesia reservoir, with 3 samples per group, and subjected to simulated cleaning and disinfection cycles. Each cycle included the following steps: immersing the sample in 500mL deionized water for 5min; soaking in 500mL medical neutral cleaning solution for 5min; rinsing twice with 500mL deionized water, 5min each time; soaking in 500mL 75wt% ethanol for 2min; removing the sample and allowing it to air dry naturally in a sterile environment for 12h, repeating the cleaning and disinfection cycle 20 times. After the cycle, the antibacterial and antiviral rates of the samples were tested according to the aforementioned antibacterial and antiviral performance testing methods.
[0051] Table 1. Performance test data of the anesthesia reservoir bag
[0052] As can be seen from the data in Examples 2-4 in Table 1, the anesthesia reservoir prepared in this application has high tensile strength, excellent antibacterial rate, antiviral rate, and performance retention rate after cyclic treatment.
[0053] This invention first introduces active groups such as hydroxyl and carboxyl groups onto the surface of the gas storage bladder through plasma treatment, enhancing surface reactivity. Subsequently, an initiator is anchored to the bladder surface, allowing the subsequent copolymerization reaction to grow in situ from the substrate surface, forming a copolymer brush layer firmly bonded to the bladder. This brush layer contains cationic antibacterial and antiviral structures. Its positively charged quaternary ammonium salt groups can electrostatically adsorb negatively charged components on the surface of bacterial cell membranes and viral capsid proteins, disrupting membrane integrity and causing leakage of cell contents, thereby inhibiting bacterial reproduction and reducing viral infectivity. Simultaneously, the polyether chains and sulfonate structures introduced into the antibacterial and antiviral functional monomers improve surface hydrophilicity and ion hydration capacity, enhancing the extensibility of functional groups in an aqueous environment, making them more easily contacted and captured by pathogenic microorganisms. The 2-methacryloyloxyethylphosphocholine structure forms a stable hydration layer on the surface, reducing the adhesion of proteins, cell debris, and contaminants, minimizing biofilm formation, and thus preventing the active sites from being covered and rendered ineffective. Since the above-mentioned functional layer is formed by surface-induced polymerization in situ growth rather than simple physical coating, it is not easy to fall off during repeated cleaning. Therefore, after 20 simulated cleaning and disinfection, it can still maintain a high level of antibacterial and antiviral effects, demonstrating good long-term protective performance.
[0054] In Comparative Example 1, no plasma treatment was performed. The surface of the natural rubber anesthesia reservoir lacked active oxygen-containing groups such as hydroxyl and carboxyl groups, making it difficult for subsequent initiators to be stably anchored, reducing surface-initiated polymerization efficiency, and significantly decreasing the amount of antibacterial and antiviral copolymers grafted onto the surface. Simultaneously, the bonding force between the unactivated surface and the functional layer was weak, making it more prone to detachment during repeated cleaning, thus hindering the long-term stable function of the cationic antibacterial groups, sulfonate groups, and phosphocholine hydration layer. Therefore, its antibacterial rate, antiviral rate, and retention rate after cycling were all significantly reduced.
[0055] In Comparative Example 3, the dosage of antibacterial and antiviral functional monomers was reduced to 2.5 mmol, while the proportion of 2-methacryloyloxyethyl phosphocholine was increased, resulting in insufficient density of cationic antibacterial and antiviral active groups in the copolymer brush. With fewer cationic groups, the electrostatic interaction between these groups and the negative charges on the bacterial cell membrane and viral capsid surface weakened, thus reducing their ability to disrupt microbial structures. Although phosphocholine can improve hydrophilic antifouling properties, its direct bactericidal and viral inactivation abilities are limited; therefore, the antibacterial rate, antiviral rate, and cycle retention rate all decreased.
[0056] The antibacterial and antiviral functional monomers prepared in Comparative Example 4 lack polyether segments and terminal hydroxyl-derived structures, resulting in decreased molecular hydrophilicity and chain flexibility. The graft copolymers have weakened water-repellent properties and are difficult to form a stable anti-water-repellent layer. At the same time, the extension and exposure of functional groups on the surface are reduced, making it easier for bacteria and viruses to adhere and reducing the contact inactivation efficiency. Therefore, the antibacterial and antiviral durability is worse.
[0057] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.
Claims
1. An anesthesia reservoir with long-lasting antibacterial and antiviral functions, characterized in that, Prepared by the following method: S1: The elastic capsule is cleaned, dried and subjected to plasma surface activation treatment to obtain a surface-activated elastic capsule; S2: Immerse the surface-activated elastic capsules in the initiator solution to obtain initiator-anchored elastic capsules; S3: The initiator-anchored elastic capsule is placed in a polymerization system containing antibacterial and antiviral functional monomers, 2-methacryloyloxyethyl phosphocholine, catalyst and ligand to react and obtain copolymer brush-grafted elastic capsules; S4: The copolymer-grafted elastic capsule is cleaned, dried and sterilized to obtain anesthesia reservoir with long-lasting antibacterial and antiviral functions.
2. The anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S1, the elastic capsule is made of natural rubber.
3. The anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S1, the processing power of the plasma surface activation treatment is 50-100W.
4. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S2, the polymerization initiator is propyl 2-bromo-2-methylpropionic acid (3-trimethoxysilyl) ester.
5. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S3, the molar ratio of the antibacterial and antiviral functional monomer: 2-methacryloyloxyethyl phosphocholine: catalyst: ligand is (10-30):(70-90):1:
2.
6. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S3, the catalyst is one of CuBr and CuCl.
7. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S3, the ligand is one of 2,2'-bipyridine, N,N,N',N'',N''-pentamethyldiethylenetriamine, and tris(2-pyridinemethyl)amine.
8. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S3, the antibacterial and antiviral functional monomer is prepared by the following method: A1: 5,8,11-trioxa-2-azatridecane-13-ol reacts with sodium 5-chloropentane-1-sulfonate in the presence of a nucleophile to form an intermediate; A2: The intermediate reacts with glycidyl methacrylate to generate an antibacterial and antiviral functional monomer.
9. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 1, characterized in that, In step S3, the reaction temperature is 40-60℃ and the reaction time is 4-6h.
10. An anesthesia reservoir with long-lasting antibacterial and antiviral function according to claim 8, characterized in that, In step A1, the nucleophile is potassium iodide.
Citation Information
Patent Citations
Polyisoprene rubber anesthesia air storage bag
CN118165385A