Preparation method of bio-based photosensitive dye synergistic antibacterial wool fabric

Abstract

This invention discloses a method for preparing a bio-based photosensitive dye synergistic antibacterial wool fabric, belonging to the field of functional textile materials technology. The method first prepares polyethylene glycol-modified molybdenum disulfide, then encapsulates the bio-based photosensitive dye in a zeolite imidazole framework material ZIF-8, and subsequently combines the two to obtain a Bio-Dye@ZIF-8 / PEG-MoS2 synergistic antibacterial component. The wool fabric is then subjected to an amination pretreatment, and the synergistic antibacterial component is loaded onto the surface of the wool fabric, resulting in a wool fabric with both dyeing and antibacterial functions. This method utilizes the porous structure of ZIF-8 to inhibit photosensitizer aggregation and quenching, improves antibacterial efficiency through photodynamic and photothermal synergy, and integrates the dyeing and antibacterial functions of the wool fabric. The resulting wool fabric achieves an inhibition rate of over 99% against Staphylococcus aureus while maintaining good breathability and mechanical properties.

Description

Technical Field

[0001] This invention relates to a method for preparing a bio-based photosensitive dye synergistic antibacterial wool fabric, belonging to the field of functional textile materials technology. Background Technology

[0002] Wool, as a natural protein fiber, has advantages such as good warmth retention, strong moisture absorption, and skin-friendly comfort, and is widely used in apparel textiles. However, wool fabrics easily absorb sweat and sebum during actual wear, providing a suitable living environment for bacteria and other microorganisms, which can lead to odors and increase the risk of skin infections.

[0003] Existing antimicrobial finishing agents for wool fabrics mainly include inorganic, organic, and bio-based antimicrobial agents, but some shortcomings still exist. For example, some inorganic antimicrobial agents have potential safety issues; some organic antimicrobial agents have a single antimicrobial mechanism, which may lead to drug resistance risks; and traditional finishing agents have poor compatibility with dyes, often requiring dyeing before finishing, resulting in a longer process and higher energy consumption.

[0004] Photodynamic antibacterial technology utilizes photosensitizers to generate reactive oxygen species under light, exhibiting high efficiency, broad spectrum, and low likelihood of inducing drug resistance. Bio-based photosensitive dyes possess both natural sources and coloring capabilities, but they are prone to self-aggregation and self-quenching during use, thus reducing photodynamic efficiency. Molybdenum disulfide exhibits good photothermal conversion properties, but nano-molybdenum disulfide is prone to aggregation, limiting its application. Therefore, it is necessary to develop a method for preparing wool fabrics that combines dyeing and antibacterial functions and achieves synergistic photodynamic / photothermal effects. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a method for preparing a bio-based photosensitive dye synergistic antibacterial wool fabric. The method first constructs a Bio-Dye@ZIF-8 / PEG-MoS2 synergistic antibacterial component, then stably loads it onto the surface of a wool fabric pretreated with amination, thereby obtaining a wool fabric with both dyeing and antibacterial functions.

[0006] This invention is achieved through the following technical solution: The first objective of this invention is to provide a method for preparing a bio-based photosensitive dye synergistic antibacterial wool fabric, comprising the following steps: S1. Add ammonium molybdate tetrahydrate, thiourea and polyethylene glycol to deionized water, adjust the pH to acidic and carry out hydrothermal reaction, then centrifuge, wash and dry to obtain polyethylene glycol modified molybdenum disulfide PEG-MoS2. S2. Zinc nitrate hexahydrate, 2-methylimidazole and bio-based photosensitive dye were mixed in methanol solution, and the bio-based photosensitive dye was encapsulated in zeolite imidazole framework material ZIF-8 through self-assembly reaction to obtain Bio-Dye@ZIF-8. S3. Combine the PEG-MoS2 obtained in step S1 with the Bio-Dye@ZIF-8 obtained in step S2 to obtain the Bio-Dye@ZIF-8 / PEG-MoS2 synergistic antibacterial component. S4. Place the wool fabric in an ethanol solution to remove surface grease and impurities, and then use 3-aminopropyltriethoxysilane hydrolysate to perform amination pretreatment on the wool fabric. S5. Add the synergistic antibacterial component obtained in step S3 to a polyvinylpyrrolidone solution to form a dispersion. Then, immerse the wool fabric pretreated in step S4 into the dispersion and shake it at a constant temperature. Wash and dry to obtain a bio-based photosensitive dye synergistic antibacterial wool fabric.

[0007] In one embodiment of the present invention, the mass ratio of polyethylene glycol to molybdenum disulfide in step S1 is 1:3~5, the hydrothermal reaction temperature is 180~220℃, and the reaction time is 20~28 h.

[0008] In one embodiment of the present invention, the bio-based photosensitive dye in step S2 is at least one of bamboo red pigment, curcumin, or chlorophyll. In this invention, the porous structure of ZIF-8 is used to spatially confine the photosensitive dye to mitigate aggregation and quenching phenomena.

[0009] In one embodiment of the present invention, the mass ratio of zinc nitrate hexahydrate, 2-methylimidazole and bio-based photosensitive dye in step S2 is 3~4:3.5~4.5:0.4~0.8, the self-assembly reaction temperature is 50~70℃, and the reaction time is 4~8 h.

[0010] In one embodiment of the present invention, in step S3, the mass ratio of PEG-MoS2 to Bio-Dye@ZIF-8 is 10~30:100, and the composite is carried out by a combination of ultrasonic dispersion and room temperature stirring.

[0011] In one embodiment of the present invention, the 3-aminopropyltriethoxysilane hydrolysate in step S4 is prepared from ethanol and water, with a volume ratio of ethanol to water of 8-10:1. The pH is adjusted to 3-5 using acetic acid, and the mixture is treated at 30-50°C for 30-60 min. In this invention, 3-aminopropyltriethoxysilane is used to pre-treat wool fabric with an amination process to improve the binding stability of the synergistic antibacterial components on the wool surface.

[0012] In one embodiment of the present invention, in step S5, the mass ratio of the synergistic antibacterial component to polyvinylpyrrolidone is 1~2:2, the mass concentration of the polyvinylpyrrolidone solution is 0.3~0.5 wt%, the isothermal shaking temperature is 30~50℃, and the time is 8~12 h.

[0013] The second objective of this invention is to provide a bio-based photosensitive dye synergistic antibacterial wool fabric obtained using the aforementioned preparation method.

[0014] In one embodiment of the present invention, the wool fabric has photodynamic / photothermal synergistic antibacterial properties under light conditions, and the antibacterial rate against Staphylococcus aureus is not less than 99%.

[0015] A third objective of this invention is to provide the application of the aforementioned bio-based photosensitive dye synergistic antibacterial wool fabric in functional textiles for clothing.

[0016] The beneficial effects of this invention are: This invention involves first preparing polyethylene glycol-modified molybdenum disulfide, then encapsulating a bio-based photosensitive dye within a zeolite imidazole framework material ZIF-8, and subsequently combining the two to obtain a Bio-Dye@ZIF-8 / PEG-MoS2 synergistic antibacterial component. Next, wool fabric undergoes an amination pretreatment, and the synergistic antibacterial component is loaded onto the surface of the wool fabric, resulting in a wool fabric with both dyeing and antibacterial functions. This method utilizes the porous structure of ZIF-8 to inhibit photosensitizer aggregation and quenching, improves antibacterial efficiency through photodynamic and photothermal synergy, and integrates the dyeing and antibacterial functions of the wool fabric. The resulting wool fabric exhibits an inhibition rate of over 99% against Staphylococcus aureus while maintaining good breathability and mechanical properties. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a scanning electron microscope image of PEG-MoS2 prepared in Example 1.

[0019] Figure 2 This is a scanning electron microscope image of the Bio-Dye@ZIF-8 prepared in Example 1.

[0020] Figure 3 This is a scanning electron microscope image of Bio-Dye@ZIF-8 / PEG-MoS2 prepared in Example 1.

[0021] Figure 4 This is a scanning electron microscope image of the aminated wool fabric prepared in Example 2.

[0022] Figure 5 This is a scanning electron microscope image of the synergistic antibacterial wool fabric prepared in Example 3. Detailed Implementation

[0023] The present invention will be further illustrated below with specific examples. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0024] Source of raw materials Ammonium molybdate tetrahydrate, thiourea, polyethylene glycol, zinc nitrate hexahydrate, methanol, hydrochloric acid, ethanol, and acetic acid were all purchased from Sinopharm Chemical Reagent Co., Ltd.; 2-methylimidazole, bamboo red fungicide, curcumin, and chlorophyll were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; 3-aminopropyltriethoxysilane and polyvinylpyrrolidone were all purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; the wool grey fabric was purchased from Jiangsu Sunshine Group Co., Ltd., and was 100% pure wool worsted wool grey fabric with a yarn count of 60 / 2Nm to 80 / 2Nm, a finished width of 150 to 156cm, and a weight of 220 to 260g / m².

[0025] The performance of the samples was tested using the following methods: 1. Photothermal performance test: The surface temperature rise ΔT (°C) of the sample was measured using infrared thermography to characterize the photothermal conversion and temperature rise performance of the sample. The sample was placed under a xenon lamp light source with a wavelength of 400 nm. 800 nm, optical power density is 100 mW / cm² 2 The sample was vertically irradiated for 10 minutes, and the highest surface temperature was recorded using an infrared thermal imager. The temperature rise ΔT (°C) of the sample surface was calculated by the difference between the initial temperature and the highest temperature.

[0026] 2. Reactive oxygen species generation capacity test: The reactive oxygen species (ROS) generation capacity of the samples was characterized by measuring the photodynamic activity and singlet oxygen yield using the DPBF fluorescence probe method. A wavelength of 532 nm and a light intensity of 85 ± 1 mW / cm² were employed. 2 The sample was irradiated with a laser for 10 min, and the change in absorbance at 411 nm was measured using a UV-Vis spectrophotometer. The quenching rate R (%) was calculated using the following formula:

[0027] In the formula: R – DPBF quenching rate (%) R0 — Original absorbance without light; R t — The absorbance at time t when the light is applied.

[0028] The reactive oxygen species generation capacity was measured using a UV-Vis spectrophotometer, and the performance requirement was a quenching rate R ≥ 45%.

[0029] 3. Antibacterial performance test: Antibacterial performance is characterized by the inhibition rate test, which measures the sample's ability to inhibit Staphylococcus aureus. The inhibition rate E (%) is calculated using the following formula:

[0030] In the formula: E – Sample antibacterial rate (%); A0 – Colonies in the control group; A – Colonies in the experimental group.

[0031] The antibacterial properties can be determined using a constant temperature incubator and a plate counting device. The performance index requirement is an inhibition rate of ≥98% against Staphylococcus aureus.

[0032] 4. Breathability test Air permeability was characterized according to GB / T 5453 standard, measuring the air transmission performance of the fabric. First, the sample fabric underwent pre-conditioning treatment to reach equilibrium in a standard atmospheric pressure environment with a temperature of 20±2℃ and a relative humidity of 65%±2%. During testing, 10 measuring points of equal area but different locations were selected for measurement. The air permeability values ​​at each measuring point were recorded, and the average value and error range were calculated. Air permeability was measured using a fabric air permeability meter under standard atmospheric conditions (temperature 20±2℃, relative humidity 65%±2%), with a required air permeability rate ≥70 mm / s.

[0033] 5. Fracture strength test: The warp breaking strength F_warp (N) is characterized by the tensile strength of the fabric in the warp direction, as determined by GB / T 3923.1 standard. The warp breaking strength can be measured using an electronic tensile testing machine, with a performance requirement of ≥800N. The testing environment is standard atmospheric conditions (temperature 20±2°C, relative humidity 65±4%).

[0034] The technical solution of the present invention will be described in detail below with reference to specific embodiments. In the following embodiments, unless otherwise specified, the reagents, materials and equipment used can be purchased commercially, prepared by conventional methods, or commonly used in the industry.

[0035] Example 1: Wool fabric was selected as the substrate and cut into 5 cm × 5 cm samples. First, 0.884 g of ammonium molybdate tetrahydrate, 1.522 g of thiourea, and 0.2 g of polyethylene glycol 2000 were weighed and added to 60 mL of deionized water. After stirring until completely dissolved, the pH of the system was adjusted to 2 with 1 mol / L dilute hydrochloric acid, and the mixture was hydrothermally reacted at 200℃ for 24 h. After the reaction, the mixture was centrifuged at 8000 rpm for 10 min, and the black precipitate was collected. It was washed three times with ethanol and then dried at 70℃ for 12 h to obtain PEG-MoS2. As shown in the scanning electron microscope image in Figure 1, the obtained PEG-MoS2 exhibits a layered nanostructure, is uniformly dispersed, and shows no obvious agglomeration, indicating a significant modification effect.

[0036] Subsequently, 3.39 g of zinc nitrate hexahydrate was added to 75 mL of methanol to prepare solution A, and 3.94 g of 2-methylimidazole and 0.6 g of bamboo red fungicide were added to 75 mL of methanol to prepare solution B. Solution B was then slowly poured into solution A, and the reaction was carried out at 60 °C for 6 h. After the reaction was completed, the precipitate was collected by centrifugation at 9000 rpm for 10 min, washed three times with methanol, and then dried at 70 °C for 12 h to obtain HB@ZIF-8. As shown in the scanning electron microscope image in Figure 2, HB@ZIF-8 has a typical rhombic dodecahedral morphology, uniform crystal size, complete structure, and effective encapsulation of bamboo red fungicide.

[0037] 10 mg of PEG-MoS2 was dispersed in 20 mL of methanol and sonicated for 30 min. Then, 100 mg of HB@ZIF-8 was added, and sonication continued for 1 h. The mixture was then stirred at room temperature for 24 h. After the reaction was complete, the precipitate was collected by centrifugation and dried at 70 °C for 12 h to obtain the HB@ZIF-8 / PEG-MoS2 (10%) composite. As shown in Figure 3 (SEM image), PEG-MoS2 nanosheets were uniformly attached to the surface of HB@ZIF-8 crystals, indicating a stable composite structure without detachment or aggregation.

[0038] Wool fabric was washed in an ethanol solution to remove surface grease and impurities, and then dried for later use. 9 g of 3-aminopropyltriethoxysilane was added to a mixed solution of 90 mL ethanol and 10 mL deionized water, the pH was adjusted to 4 with acetic acid, and the mixture was ultrasonically hydrolyzed for 30 min to obtain a silane coupling agent hydrolysate. The washed wool fabric was immersed in the hydrolysate and treated at 40°C for 45 min, then dried at 60°C to obtain aminated wool fabric (AWF). 200 mg of polyvinylpyrrolidone was weighed and added to 50 mL of deionized water. After stirring until completely dissolved, 100 mg of HB@ZIF-8 / PEG-MoS2 (10%) complex was added, and the mixture was vigorously stirred and ultrasonicated for 30 min to obtain a dispersion. The AWF was immersed in the dispersion and kept at 40°C with constant temperature shaking for 10 h. After removal, it was washed 5 times with deionized water and then dried at 60°C for 2 h to obtain synergistic antibacterial wool fabric HZM1-AWF.

[0039] Results: The modified wool fabric exhibited excellent photodynamic / photothermal synergistic antibacterial properties. Its surface temperature rose to 48.8℃ after light exposure, indicating that the composite components had good photothermal conversion capabilities. The DPBF scavenging rate reached 85%, indicating that the material had a strong ability to generate reactive oxygen species. The inhibition rate against Staphylococcus aureus was as high as 99.98%, demonstrating excellent antibacterial effects. Simultaneously, the fabric maintained good breathability, with a breathability rate of 77.40 mm / s. The warp and weft breaking strengths were 355.42 N and 237.67 N, respectively, indicating that this invention, while imparting highly efficient antibacterial properties to the wool fabric, also effectively maintained its original physical properties and wearing comfort.

[0040] Example 2: Wool fabric was selected as the substrate and cut into 5 cm × 5 cm samples. First, 0.884 g of ammonium molybdate tetrahydrate, 1.522 g of thiourea, and 0.2 g of polyethylene glycol 2000 were weighed and added to 60 mL of deionized water. After stirring until completely dissolved, the pH of the system was adjusted to 2 with 1 mol / L dilute hydrochloric acid, and the mixture was subjected to hydrothermal reaction at 200℃ for 24 h. After the reaction, the mixture was centrifuged at 8000 rpm for 10 min, and the black precipitate was collected. It was washed three times with ethanol and then dried at 70℃ for 12 h to obtain PEG-MoS2. Subsequently, 3.39 g of zinc nitrate hexahydrate was added to 75 mL of methanol to prepare solution A, and 3.94 g of 2-methylimidazole and 0.6 g of bamboo red fungicide were added to 75 mL of methanol to prepare solution B. Solution B was then slowly poured into solution A, and the mixture was subjected to self-assembly reaction at 60℃ for 6 h. After the reaction was completed, the precipitate was collected by centrifugation at 9000 rpm for 10 min, washed three times with methanol, and then dried at 70℃ for 12 h to obtain HB@ZIF-8. 20 mg of PEG-MoS2 was dispersed in 20 mL of methanol, sonicated for 30 min, and then 100 mg of HB@ZIF-8 was added. Sonication was continued for 1 h, and the mixture was stirred at room temperature for 24 h. After the reaction was completed, the precipitate was collected by centrifugation and dried at 70℃ for 12 h to obtain the HB@ZIF-8 / PEG-MoS2 (20%) complex. Wool fabric was washed in an ethanol solution to remove surface grease and impurities, and then dried for later use. Next, 9 g of 3-aminopropyltriethoxysilane was added to a mixed solution of 90 mL ethanol and 10 mL deionized water, the pH was adjusted to 4 with acetic acid, and the mixture was ultrasonically hydrolyzed for 30 min to obtain a silane coupling agent hydrolysate. The washed wool fabric was then immersed in the hydrolysate and treated at 40°C for 45 min, followed by drying at 60°C to obtain aminated wool fabric (AWF). As shown in the scanning electron microscope image in Figure 4, the surface of the wool fibers was clean and the scale structure was intact after amination treatment, successfully introducing amino active sites, which is beneficial for subsequent loading of functional components.

[0041] Weigh 200 mg of polyvinylpyrrolidone and add it to 50 mL of deionized water. Stir until completely dissolved, then add 100 mg of HB@ZIF-8 / PEG-MoS2 (20%) complex. Stir vigorously and sonicate for 30 min to obtain a dispersion. Immerse AWF in the dispersion and shake at 40℃ for 10 h. Remove and wash 5 times with deionized water, then dry at 60℃ for 2 h to obtain synergistic antibacterial wool fabric HZM2-AWF.

[0042] Results: The modified wool fabric exhibited superior comprehensive photothermal antibacterial properties. Its surface temperature after light irradiation increased to 53.6 °C, a further increase compared to Example 1, indicating that the photothermal conversion capacity of the system was enhanced with the increase of PEG-MoS2 introduction. The DPBF scavenging rate was 71.3%, maintaining good photodynamic activity. The antibacterial rate against Staphylococcus aureus reached 99.99%, indicating that the material has excellent synergistic antibacterial effect at this component ratio. This demonstrates that by optimizing the composite ratio of HB@ZIF-8 and PEG-MoS2, this invention can further improve the antibacterial properties and thermal response of wool fabric, giving it higher application value in the field of functional textiles.

[0043] Example 3: Wool fabric was selected as the substrate and cut into 5 cm × 5 cm samples. First, 0.884 g of ammonium molybdate tetrahydrate, 1.522 g of thiourea, and 0.2 g of polyethylene glycol 2000 were weighed and added to 60 mL of deionized water. After stirring until completely dissolved, the pH of the system was adjusted to 2 with 1 mol / L dilute hydrochloric acid, and the mixture was subjected to a hydrothermal reaction at 200 ℃ for 24 h. After the reaction, the mixture was centrifuged at 8000 rpm for 10 min, and the black precipitate was collected. The precipitate was washed three times with ethanol and then dried at 70 ℃ for 12 h to obtain PEG-MoS2. Subsequently, 3.39 g of zinc nitrate hexahydrate was added to 75 mL of methanol to prepare solution A, and 3.94 g of 2-methylimidazole and 0.6 g of bamboo red fungicide were added to 75 mL of methanol to prepare solution B. Solution B was then slowly poured into solution A, and the mixture was subjected to a self-assembly reaction at 60 ℃ for 6 h. After the reaction was completed, the precipitate was collected by centrifugation at 9000 rpm for 10 min, washed three times with methanol, and then dried at 70 ℃ for 12 h to obtain HB@ZIF-8. 30 mg of PEG-MoS2 was dispersed in 20 mL of methanol, sonicated for 30 min, and then 100 mg of HB@ZIF-8 was added. Sonication was continued for 1 h, and the mixture was stirred at room temperature for 24 h. After the reaction was completed, the precipitate was collected by centrifugation and dried at 70 ℃ for 12 h to obtain the HB@ZIF-8 / PEG-MoS2 (30%) complex. Wool fabric was washed in an ethanol solution to remove surface grease and impurities, and then dried for later use. 9 g of 3-aminopropyltriethoxysilane was added to a mixed solution of 90 mL ethanol and 10 mL deionized water, the pH was adjusted to 4 with acetic acid, and the mixture was ultrasonically hydrolyzed for 30 min to obtain a silane coupling agent hydrolysate. The washed wool fabric was immersed in the hydrolysate and treated at 40 °C for 45 min, then dried at 60 °C to obtain aminated wool fabric (AWF). 200 mg of polyvinylpyrrolidone was weighed and added to 50 mL of deionized water. After stirring until completely dissolved, 100 mg of HB@ZIF-8 / PEG-MoS2 (30%) complex was added, and the mixture was vigorously stirred and ultrasonicated for 30 min to obtain a dispersion. The AWF was immersed in the dispersion and kept at 40 °C with constant temperature shaking for 10 h. After removal, it was washed 5 times with deionized water and then dried at 60 °C for 2 h to obtain synergistic antibacterial wool fabric HZM3-AWF. As shown in the scanning electron microscope image in Figure 5, the synergistic antibacterial components are uniformly and continuously coated on the surface of the wool fibers, with a firm bond and no obvious accumulation or shedding, resulting in excellent finishing effect.

[0044] Results: The modified wool fabric still exhibited certain photothermal antibacterial properties, with its surface temperature rising to 54.9 ℃ after light irradiation, indicating a strong photothermal response capability. However, the DPBF scavenging rate decreased to 47.5%, and the inhibition rate against Staphylococcus aureus was 70.5%, lower than in Examples 1 and 2. This suggests that while the photothermal properties of the material were enhanced when the PEG-MoS2 content was further increased, the photodynamic effect weakened due to the decrease in the relative content of HB@ZIF-8, thus reducing the synergistic antibacterial effect of photodynamic / photothermal action. These results indicate that there is an optimal range for the ratio of PEG-MoS2 to HB@ZIF-8 in this invention, and a suitable composite ratio is more conducive to achieving excellent comprehensive antibacterial performance.

[0045] Comparative Example 1 (without amination pretreatment): The 3-aminopropyltriethoxysilane amination pretreatment step of wool fabric in Example 1 was omitted. Instead, the wool fabric, which had been washed and dried with ethanol, was directly immersed in a dispersion containing the HB@ZIF-8 / PEG-MoS2 (10%) complex for loading treatment. The remaining steps and parameters were exactly the same as in Example 1.

[0046] Results: The obtained wool fabric still exhibited certain antibacterial properties under light exposure, but the overall effect was significantly lower than that of the present invention. After light exposure, its surface temperature increased to 43.1 °C, the DPBF removal rate was 62.4%, and the inhibition rate against Staphylococcus aureus was 78.6%. After five washes, the inhibition rate further decreased to 58.3%. This indicates that the wool fabric without amination pretreatment has insufficient surface active sites, resulting in a lower loading and binding strength of the composite antibacterial components on the fiber surface, which is detrimental to improving the fabric's antibacterial properties and durability.

[0047] Comparative Example 2 (without PEG-MoS2): The preparation and compounding steps of PEG-MoS2 in Example 1 are omitted. Only HB@ZIF-8 is used as a functional component and loaded onto the surface of aminated wool fabric. The remaining steps and parameters are exactly the same as in Example 1.

[0048] Results: The obtained wool fabric exhibits some photodynamic antibacterial ability, but its overall antibacterial effect is lower than that of this invention. Its surface temperature after light irradiation only increased to 41.5℃, significantly lower than in Example 1, indicating a lack of effective photothermal conversion ability in the system. The DPBF scavenging rate reached 97.7%, indicating that the material still possesses a strong ability to generate reactive oxygen species; however, the inhibition rate against Staphylococcus aureus was only 89.1%. These results indicate that while HB@ZIF-8 alone can achieve a certain photodynamic antibacterial effect, the lack of photothermal synergistic effect from PEG-MoS2 makes it difficult to achieve the highly efficient synergistic antibacterial effect described in this invention.

[0049] Comparative Example 3 (without HB@ZIF-8): The preparation and compounding steps of HB@ZIF-8 in Example 1 are omitted. Only PEG-MoS2 is used as a functional component and loaded onto the surface of aminated wool fabric. The remaining steps and parameters are exactly the same as in Example 1.

[0050] Results: The obtained wool fabric exhibited a certain photothermal response capability, but its photodynamic properties were significantly insufficient, resulting in poor overall antibacterial performance. Its surface temperature rose to 47.6℃ after light irradiation, indicating that PEG-MoS2 possessed good photothermal conversion capability; however, the DPBF clearance rate was only 21.8%, and the inhibition rate against Staphylococcus aureus was 72.4%, significantly lower than in Example 1. These results demonstrate that while PEG-MoS2 alone can inhibit bacterial growth through photothermal effects, it lacks the photodynamic antibacterial effect provided by HB@ZIF-8, making it difficult to achieve a synergistic enhancement effect of photodynamic / photothermal properties.

[0051] Comparative Example 4 (using unencapsulated bio-based photosensitizing dyes): In Example 1, HB@ZIF-8 was replaced with an equal mass of free bamboo red fungicide, and then directly mixed with PEG-MoS2 and loaded onto the surface of aminated wool fabric. The remaining steps and parameters were exactly the same as in Example 1.

[0052] Results: The obtained wool fabric exhibited certain antibacterial properties under light irradiation, but these were significantly lower than those of the present invention. Its surface temperature after light irradiation could rise to 46.2℃, close to that of Example 1; however, the DPBF clearance rate was only 54.8%, and the inhibition rate against Staphylococcus aureus was 82.7%. This indicates that bamboo red dyes without ZIF-8 encapsulation are more prone to aggregation and self-quenching in the system, leading to a decrease in reactive oxygen species generation and thus weakening the photodynamic antibacterial effect of the material. Therefore, encapsulating bio-based photosensitive dyes with ZIF-8 is beneficial for improving their dispersibility and photodynamic utilization efficiency.

[0053] Comparative Example 5 (using unmodified MoS2): The PEG-MoS2 in Example 1 was replaced with an equal mass of unmodified MoS2, and the remaining steps and parameters were exactly the same as in Example 1.

[0054] Results: The obtained wool fabric still exhibited certain photothermal antibacterial properties under light irradiation, but its overall performance was lower than that of the present invention. After light irradiation, its surface temperature increased to 45.3℃, the DPBF removal rate was 68.5%, and the inhibition rate against Staphylococcus aureus was 84.9%. Simultaneously, scanning electron microscopy revealed that the unmodified MoS2 was unevenly distributed on the fiber surface, exhibiting localized aggregation. These results indicate that polyethylene glycol modification can effectively improve the dispersibility and composite stability of MoS2, which is beneficial for increasing its uniform loading on the wool fiber surface and further enhancing the photothermal synergistic antibacterial effect.

[0055] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.

Claims

1. A process for the preparation of a bio-based photosensitizing dye synergistic antibacterial wool fabric characterized in that, Includes the following steps: S1. Add ammonium molybdate tetrahydrate, thiourea and polyethylene glycol to deionized water, adjust the pH to acidic and carry out hydrothermal reaction, then centrifuge, wash and dry to obtain polyethylene glycol modified molybdenum disulfide PEG-MoS2. S2. Zinc nitrate hexahydrate, 2-methylimidazole and bio-based photosensitive dye were mixed in methanol solution, and the bio-based photosensitive dye was encapsulated in zeolite imidazole framework material ZIF-8 through self-assembly reaction to obtain Bio-Dye@ZIF-8. S3. Combine the PEG-MoS2 obtained in step S1 with the Bio-Dye@ZIF-8 obtained in step S2 to obtain the Bio-Dye@ZIF-8 / PEG-MoS2 synergistic antibacterial component. S4. Place the wool fabric in an ethanol solution to remove surface grease and impurities, and then use 3-aminopropyltriethoxysilane hydrolysate to perform amination pretreatment on the wool fabric. S5. Add the synergistic antibacterial component obtained in step S3 to a polyvinylpyrrolidone solution to form a dispersion. Then, immerse the wool fabric pretreated in step S4 into the dispersion and shake it at a constant temperature. Wash and dry to obtain a bio-based photosensitive dye synergistic antibacterial wool fabric.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of polyethylene glycol to molybdenum disulfide is 1:3~5, the hydrothermal reaction temperature is 180~220℃, and the reaction time is 20~28 h.

3. The preparation method according to claim 1, characterized in that, The bio-based photosensitive dye mentioned in step S2 is at least one of bamboo red mycotoxin, curcumin, or chlorophyll.

4. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of zinc nitrate hexahydrate, 2-methylimidazole, and bio-based photosensitive dye is 3~4:3.5~4.5:0.4~0.8, the self-assembly reaction temperature is 50~70℃, and the reaction time is 4~8 h.

5. The preparation method according to claim 1, characterized in that, In step S3, the mass ratio of PEG-MoS2 to Bio-Dye@ZIF-8 is 10~30:100, and the composite is carried out by a combination of ultrasonic dispersion and room temperature stirring.

6. The preparation method according to claim 1, characterized in that, In step S4, the 3-aminopropyltriethoxysilane hydrolysate is prepared from ethanol and water in a volume ratio of 8 to 10:

1. The pH is adjusted to 3 to 5 using acetic acid, and the solution is treated at 30 to 50°C for 30 to 60 minutes.

7. The preparation method according to claim 1, characterized in that, In step S5, the mass ratio of the synergistic antibacterial component to polyvinylpyrrolidone is 1~2:2, the mass concentration of the polyvinylpyrrolidone solution is 0.3~0.5 wt%, the isothermal shaking temperature is 30~50℃, and the time is 8~12 h.

8. A bio-based photosensitive dye synergistic antibacterial wool fabric obtained by the preparation method according to any one of claims 1 to 7.

9. The bio-based photosensitive dye synergistic antibacterial wool fabric according to claim 8, characterized in that, The wool fabric exhibits photodynamic / photothermal synergistic antibacterial properties under light conditions, with an inhibition rate of no less than 99% against Staphylococcus aureus.

10. The application of the bio-based photosensitive dye synergistic antibacterial wool fabric as described in claim 9 in functional textiles for clothing.

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