A multi-mode photo-driven antibacterial fabric based on functional intermolecular assembly and its preparation method

Abstract

This invention belongs to the field of functional antibacterial fabrics, and more specifically relates to an antibacterial fabric based on functional intermolecular assembly-induced multimode photodriven technology and its preparation method. The antibacterial fabric based on functional intermolecular assembly-induced multimode photodriven technology is formed by first grafting photosensitive molecules onto the surface of a cotton, wool, or silk substrate, and then assembling fluorescent molecules; the photosensitive molecule is tetracarboxylate-modified zinc phthalocyanine, and the fluorescent molecule is a cationic 1,8-naphthalimide fluorescent compound. This invention employs a simple covalent grafting and assembly method on the fabric surface, which is easy to prepare in large quantities, ensuring good moisture absorption and breathability. The prepared fabric possesses highly efficient, wide-spectrum visible-spectrum driven, photodynamic / photothermal synergistic antibacterial properties, and has great application potential in home textiles, outdoor products, and personal protective equipment.

Description

Technical Field

[0001] This invention belongs to the field of functional antibacterial fabrics, and more specifically relates to a multi-mode light-driven antibacterial fabric based on functional intermolecular assembly-induced multimode light and its preparation method. Background Technology

[0002] Due to their unique physicochemical structure, textile fibers become excellent carriers for bacteria, viruses, and other microorganisms, easily posing a threat to human health and facilitating cross-infection. With increasing public awareness of hygiene, antibacterial fabrics possess enormous development potential, with significant market applications in home textiles, bedding, outdoor sportswear, and personal protective equipment. Commonly used antibacterial agents on the market include metal ions, organosilicon quaternary ammonium salts, and antibiotics, primarily applied to the fabric surface through coating. However, metal ions, lacking reactivity, are difficult to load and tend to detach during use; overuse of antibiotics leads to antibiotic resistance in bacteria. Functional fabrics prepared using coating methods also suffer from problems such as poor breathability and unpleasant hand feel.

[0003] Photodynamic antibacterial technology utilizes organic photosensitizers to generate oxidizing reactive oxygen species under light irradiation, thereby exhibiting a specific sterilization effect. It boasts advantages such as high efficiency, controllability, and no induction of drug resistance. The structure of organic photosensitizers is easily modified, making them easier to load onto fiber surfaces using chemical grafting methods compared to inorganic and polymeric materials. Currently, photosensitizers such as benzophenone, anthraquinone, and porphyrin derivatives have been used to prepare photodynamic antibacterial cotton, wool, and polyester fabrics. However, these photodynamic antibacterial fabrics can only be excited by ultraviolet light or narrow-band visible light, resulting in low photon utilization and limited photodynamic antibacterial effects, thus restricting practical applications. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing multi-mode photodynamic antibacterial fabrics based on functional intermolecular assembly-induced antibacterial fabrics. This method is simple, mild, and produces antibacterial fabrics with long-lasting effects, thus solving the technical problems of narrow-band excitation and weak antibacterial effects in existing photodynamic antibacterial fabrics.

[0005] The technical solution adopted by this invention to solve its technical problem is:

[0006] A multi-mode light-driven antibacterial fabric based on functional molecular assembly-induced multi-mode light-driven antibacterial fabric is formed by first grafting a photosensitive dye onto the surface of a fabric made of cotton, wool, or silk substrate and then assembling a fluorescent dye; wherein the photosensitive dye is a tetracarboxylate-modified zinc phthalocyanine and the fluorescent dye is a cationic 1,8-naphthalimide fluorescent molecule.

[0007] This invention is the first to apply two functional molecules to the textile field, especially in the preparation of functional fabrics. Tetracarboxylated zinc phthalocyanine can form covalent bonds with fibers through chemical reactions and be grafted onto the fiber surface. Cationic fluorescent molecules can electrostatically adsorb and assemble with anionic carboxylated zinc phthalocyanine on the fiber surface. The assembly-induced fluorescence resonance energy transfer mechanism between fluorescent dyes and photosensitive dyes broadens the absorption spectrum, improves photon utilization and photodynamic effect, and the π-π coupling between the two dye planar parent molecules promotes vibrational relaxation, generating a photothermal effect, thus achieving the purpose of multi-mode visible light driven antibacterial.

[0008] A method for preparing the aforementioned antibacterial fabric based on functional intermolecular assembly-induced multimode photodriven processes, comprising the following steps:

[0009] S1. Add tetracarboxylated modified zinc phthalocyanine and N,N-carbonyl diimidazole (CDI) to DMF and activate at 70-100℃ for 2-6 hours to obtain the activated solution;

[0010] In the activation solution, the molar ratio of tetracarboxylated modified zinc phthalocyanine to CDI is 1:1-3, and the concentration of tetracarboxylated modified zinc phthalocyanine is 1-20 g / L;

[0011] S2. The fabric is immersed in the activation solution for a shaking reaction grafting, then taken out and soaped, washed with water and dried to obtain zinc phthalocyanine grafted fabric; the shaking reaction temperature is 80-100℃ and the shaking time is 6-12h.

[0012] S3. Add cationic 1,8-naphthalimide fluorescent molecules to an appropriate amount of solvent, heat and stir to dissolve, add the zinc phthalocyanine grafted fabric described in S2, and assemble by shaking at 90℃±5℃ for 4-10h. Then wash and dry to obtain multimode light-driven antibacterial fabric.

[0013] The technical challenges of this invention lie in two aspects: first, the use of esterification to graft zinc phthalocyanine photosensitive material onto the surface of a fabric (such as cotton) for the first time; and second, the first preparation of cationic 1,8-naphthalimide fluorescent molecules and their assembly for application in the preparation of functional fabrics. The assembly conditions are particularly important, with the selection of assembly temperature and time directly affecting the success of the assembly. Under the assembly conditions described in this invention, the cationic 1,8-naphthalimide fluorescent molecules electrostatically adsorb onto the carboxyl-modified zinc phthalocyanine on the surface of the fabric fibers, achieving assembly. The light-driven antibacterial fabric obtained by this invention exhibits a significantly improved antibacterial effect compared to conventional methods.

[0014] Preferably, in S1, the molar ratio of tetracarboxylated modified zinc phthalocyanine to CDI is 1:2, and the concentration of tetracarboxylated modified zinc phthalocyanine is 10 g / L. The molar ratio of carboxylated modified zinc phthalocyanine to CDI directly affects the degree of activation of the carboxyl groups, and thus affects the grafting rate and extent of the dyes onto the fabric; if the molar ratio is too high or too low, the assembly effect will be poor.

[0015] Preferably, in S1, the activation time is 4 hours and the temperature is 80°C.

[0016] Preferably, in step S2, the bath ratio of the fabric to the activating solution is 1:10-30. The bath ratio, temperature, and time of the reaction between the textile and the dye activating solution have a significant impact on the grafting effect of the dye.

[0017] Preferably, in S3, the cationic 1,8-naphthalimide fluorescent molecule is a cationic 4-NH-1,8-naphthalimide derivative, and the solvent is water or ethanol.

[0018] Preferably, the amount of cationic 1,8-naphthalimide fluorescent molecules used is 1-5 g / 100 mL of solvent.

[0019] Preferably, in step S3, the ratio of the zinc phthalocyanine grafted fabric to the assembly solution is 1:10-30.

[0020] As a preferred method, the preparation of tetracarboxylated modified zinc phthalocyanine is as follows: under nitrogen protection, using n-pentanol as solvent, 2 moles of 2-(4-(3,4-dicyanophenoxy)phenyl)acetic acid, 1 mole of zinc acetate dihydrate and 2 moles of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are mixed and the reaction is maintained at 137±5℃. After the reaction is completed, an appropriate amount of ethyl acetate is added to the system, the mixture is allowed to stand, the filter cake is collected by suction filtration, dried, and purified by alkaline dissolution and acid precipitation to obtain a blue-green powder, namely tetracarboxylated modified zinc phthalocyanine.

[0021] Preparation method of cationic 1,8-naphthalimide fluorescent molecule: 1 mole of 4-bromo-N-(dimethylamino)propyl-1,8-naphthalimide and 2 moles of n-dodecylamine were added to ethylene glycol monomethyl ether solvent and stirred under reflux for 20 ± 2 hours. After the reaction was completed, the mixture was poured into water and dilute HCl solution was added dropwise to adjust the pH to 2-4, preferably 2-3. The product was purified using dichloromethane as an extractant to obtain the intermediate compound 4-n-dodecylamino-N-(dimethylamino)propyl-1,8-naphthalimide. Then, 1 mole of 4-dodecylamino-N-(dimethylamino)propyl-1,8-naphthalimide was reacted with 2 moles of benzyl chloride in acetone. After the reaction was completed, the system was cooled and filtered to obtain the crude product. The crude product was recrystallized and purified using ethanol as a solvent to obtain a yellow powder, i.e., cationic 1,8-naphthalimide fluorescent molecule.

[0022] The beneficial effects of this invention are:

[0023] 1. This invention uses ordinary textiles as the substrate and employs photosensitive molecule grafting and fluorescent molecule assembly methods to prepare fabrics with a photodynamic / photothermal synergistic antibacterial effect driven by sunlight. Under light irradiation, zinc phthalocyanine's molecular ground state is excited to a singlet excited state, then through intersystem crossing to a triplet excited state, subsequently reacting with oxygen in the air to generate singlet oxygen, thus exhibiting strong oxidizing properties.

[0024] 2. In this invention, cationic fluorescent molecules can electrostatically adsorb and assemble with carboxyl-modified zinc phthalocyanine on the fiber surface. The absorption spectrum is broadened by the fluorescence resonance energy transfer mechanism induced by intermolecular assembly, which improves photon utilization and photodynamic effect. Furthermore, the π-π coupling between the two planar parent compounds promotes vibrational relaxation and generates a photothermal effect, thereby achieving the purpose of multi-mode visible light-driven antibacterial activity.

[0025] 3. This preparation method is simple, has virtually no impact on the breathability and comfort of the fabric, requires no special equipment, and is easy to mass-produce. The prepared fabric exhibits a 99.99% photo-induced bactericidal rate against Staphylococcus aureus and Escherichia coli, demonstrating a significant improvement in antibacterial effect, while similar products on the market only achieve an antibacterial rate of 60-80%. This invention employs a simple covalent grafting and assembly method on the fabric surface, facilitating mass production and ensuring excellent moisture absorption and breathability. The prepared fabric possesses highly efficient, wide-spectrum visible-drive, photodynamic / photothermal synergistic antibacterial properties, showing great application potential in home textiles, outdoor products, and personal protective equipment. Attached Figure Description

[0026] Figure 1 The images (a) and (b) are of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1 of this invention.

[0027] Figure 2 The photothermal temperature-time diagrams are shown for the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1 of this invention.

[0028] Figure 3 Singlet oxygen detection diagrams of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1 of the present invention;

[0029] Figure 4 The diagram shows the photo-driven antibacterial properties of the photo-driven antibacterial fabrics prepared in Example 1 and Comparative Examples 1 and 2 of this invention against Staphylococcus aureus and Escherichia coli. Detailed Implementation

[0030] The technical solution of the present invention will be further described in detail below through specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any modifications and / or alterations made to the present invention will fall within the protection scope of the present invention.

[0031] In this invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0032] Unless otherwise specified, the reagents used in the following examples can be purchased from a regular biochemical reagent store.

[0033] Preparation method of tetracarboxylated modified zinc phthalocyanine: 2 moles of 2-(4-(3,4-dicyanophenoxy)phenyl)acetic acid and 1 mole of zinc acetate dihydrate were placed in a three-necked flask. n-Pentanol solvent and 2 moles of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were added, and the reaction was carried out at 137°C under nitrogen protection. After the reaction was complete, ethyl acetate was added to the three-necked flask, and the mixture was allowed to stand. The filter cake was collected by suction filtration and dried in a 70°C oven. Purification was achieved by alkali dissolution and acid precipitation to obtain a blue-green powder, i.e., tetracarboxylated modified zinc phthalocyanine.

[0034] Preparation method of cationic 1,8-naphthalimide fluorescent molecule: 1 mole of 4-bromo-N-(dimethylamino)propyl-1,8-naphthalimide and 2 moles of n-dodecylamine were added to ethylene glycol monomethyl ether solvent and stirred under reflux for 20 hours. After the reaction was complete, the mixture was poured into water and dilute HCl solution was added dropwise to adjust the pH to approximately 2.0. The product was purified using dichloromethane (30 mL × 3) as an extractant to obtain the intermediate compound 4-n-dodecylamino-N-(dimethylamino)propyl-1,8-naphthalimide. Then, 1 mole of 4-dodecylamino-N-(dimethylamino)propyl-1,8-naphthalimide was reacted with 2 moles of benzyl chloride in acetone. After the reaction was complete, the system was cooled and filtered to obtain the crude product. The crude product was purified by recrystallization using ethanol as a solvent to obtain a yellow powder, i.e., the cationic 1,8-naphthalimide fluorescent molecule.

[0035] Example 1

[0036] A method for preparing a multi-mode photo-driven antibacterial fabric based on functional intermolecular assembly induction, comprising the following steps:

[0037] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, add 0.008 g of catalyst CDI, stir and activate at 80 °C for 2 h to obtain the activated solution.

[0038] In this embodiment, the molar ratio of tetracarboxylated zinc phthalocyanine to CDI is 1:2.

[0039] (2) Add 3g of cotton fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0040] (3) Take 0.3g of cationic 1,8-naphthalimide fluorescent molecules and add them to 30mL of water. Heat and dissolve them. Add zinc phthalocyanine grafted cotton fabric to the solution and shake at 90℃ for 4h. Then take it out and wash it with water to obtain multimode light-driven antibacterial cotton fabric.

[0041] Example 2

[0042] A method for preparing a multi-mode photo-driven antibacterial fabric based on functional intermolecular assembly induction, comprising the following steps:

[0043] (1) Measure 30 mL of DMF, add 0.3 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 10 g / L, and then add 0.08 g of catalyst CDI to it. Stir and activate at 80 °C for 4 h.

[0044] (2) Add 1.5g of cotton fabric to the above activation solution at a liquor ratio of 1:20, place it in a shaking dyeing machine, shake it at 90℃ for 10h, then take out the cotton fabric, wash and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0045] (3) Take 0.3g of cationic 1,8-naphthalimide fluorescent molecules and add them to 30mL of water. Heat and dissolve them. Add zinc phthalocyanine grafted cotton fabric to the solution and shake at 90℃ for 4h. Then take it out and wash it with water to obtain multimode light-driven antibacterial cotton fabric.

[0046] Example 3

[0047] A method for preparing a multi-mode photo-driven antibacterial fabric based on functional intermolecular assembly induction, comprising the following steps:

[0048] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, and then add 0.012 g of catalyst CDI to it. Stir and activate at 80 °C for 2 h.

[0049] In this embodiment, the molar ratio of tetracarboxylated zinc phthalocyanine to CDI is 1:3.

[0050] (2) Add 3g of wool fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the wool fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted wool fabric.

[0051] (3) Take 1.5g of cationic 1,8-naphthalimide fluorescent molecules and add them to 30mL of water. Heat and dissolve them. Add zinc phthalocyanine grafted wool fabric to the solution and shake at 90℃ for 6h. Then take it out and wash it with water to obtain multimode light-driven antibacterial wool fabric.

[0052] Comparative Example 1 (without the addition of cationic 1,8-naphthalimide fluorescent molecules, otherwise the same as Example 1)

[0053] A method for preparing an antibacterial fabric, comprising the following steps:

[0054] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, and then add 0.008 g of catalyst CDI to it. Stir and activate at 80 °C for 2 h.

[0055] (2) Add 3g of cotton fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0056] Comparative Example 2 (without the catalyst CDI, otherwise the same as Example 1)

[0057] A method for preparing an antibacterial fabric, comprising the following steps:

[0058] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, and stir at 80 °C for 2 h.

[0059] (2) Add 3g of cotton fabric to the above solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it.

[0060] (3) Take 0.3g of cationic 1,8-naphthalimide fluorescent molecules and add them to 30mL of water. Heat to dissolve. Add the above cotton fabric to the solution and shake at 90℃ for 4h. Then take it out and wash it with water. The phenomenon shows that the obtained cotton fabric is almost colorless, the zinc phthalocyanine molecule grafting failed, and therefore the fluorescent molecules could not be adsorbed onto the cotton fabric.

[0061] Comparative Example 3 (assembly temperature was 25–30°C, otherwise the same as Example 1)

[0062] A method for preparing an antibacterial fabric, comprising the following steps:

[0063] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, add 0.008 g of catalyst CDI, stir and activate at 80 °C for 2 h to obtain the activated solution.

[0064] In this embodiment, the molar ratio of tetracarboxylated zinc phthalocyanine to CDI is 1:2.

[0065] (2) Add 3g of cotton fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0066] (3) Dissolve 0.3g of cationic 1,8-naphthalimide fluorescent molecules in 30mL of water, add zinc phthalocyanine-grafted cotton fabric to the solution, and shake at 25-30℃ for 1h. Then remove and wash with water to obtain antibacterial cotton fabric. According to the observation of the fabric surface and solution color, it was found that the cationic 1,8-naphthalimide fluorescent molecules were not successfully assembled on the zinc phthalocyanine-grafted cotton fabric.

[0067] Comparative Example 4 (assembly time was 1 hour, otherwise the same as Example 1)

[0068] A method for preparing an antibacterial fabric, comprising the following steps:

[0069] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, add 0.008 g of catalyst CDI, stir and activate at 80 °C for 2 h to obtain the activated solution.

[0070] In this embodiment, the molar ratio of tetracarboxylated zinc phthalocyanine to CDI is 1:2.

[0071] (2) Add 3g of cotton fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0072] (3) Dissolve 0.3g of cationic 1,8-naphthalimide fluorescent molecules in 30mL of water, add zinc phthalocyanine-grafted cotton fabric to the solution, and shake at 90℃ for 1h. Then remove and wash with water to obtain antibacterial cotton fabric. According to the observation of the fabric surface and solution color, it was found that the cationic 1,8-naphthalimide fluorescent molecules were not successfully assembled on the zinc phthalocyanine-grafted cotton fabric.

[0073] Comparative Example 5 (fluorescent molecule concentration was 0.1 g / 100 mL, otherwise the same as in Example 1)

[0074] A method for preparing an antibacterial fabric, comprising the following steps:

[0075] (1) Measure 30 mL of DMF, add 0.03 g of tetracarboxylated modified zinc phthalocyanine, prepare a dye solution of 1 g / L, add 0.008 g of catalyst CDI, stir and activate at 80 °C for 2 h to obtain the activated solution.

[0076] In this embodiment, the molar ratio of tetracarboxylated zinc phthalocyanine to CDI is 1:2.

[0077] (2) Add 3g of cotton fabric to the above activation solution at a liquor ratio of 1:10, place it in a shaking dyeing machine, shake at 90°C for 10 hours, then take out the cotton fabric, soap it, wash it with water and dry it to obtain zinc phthalocyanine grafted cotton fabric.

[0078] (3) Dissolve 0.03g of cationic 1,8-naphthalimide fluorescent molecules in 30mL of water, add zinc phthalocyanine-grafted cotton fabric to the solution, and shake at 90℃ for 4h. Then remove and wash with water. The antibacterial rate of the cotton fabric prepared in this way is less than 30%, which is not effective.

[0079] like Figure 1 The images show (a) and (b) absorption spectra of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1, respectively. The sample in Comparative Example 1 appears blue-green, while the sample in Example 1 appears yellow. The sample in Example 1 exhibits characteristic absorption peaks of zinc phthalocyanine and 1,8-naphthalimide, indicating successful loading of the photosensitive dye and fluorescent dye, and broadening the fabric's absorption spectrum to the entire visible range. The cotton fabric prepared in Comparative Example 2 is almost colorless, indistinguishable from the blank sample, indicating that the grafting of tetracarboxylic acid-modified zinc phthalocyanine must be catalyzed by CDI, and it also plays a bridging role in the assembly of the cationic fluorescent dye.

[0080] like Figure 2 The image shows the photothermal temperature-time graphs of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1. It can be seen that after 80 seconds of visible light irradiation, the surface temperature of the fabric in Example 1 rose from 24.5℃ to 53.5℃, while that in Comparative Example 1 only rose to 44.8℃.

[0081] like Figure 3 The image shows the singlet oxygen detection diagram of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1. After being exposed to visible light for 10 minutes, the singlet oxygen production of the sample in Example 1 was 99%, while the singlet oxygen production of the sample in Comparative Example 1 was only 56%.

[0082] like Figure 4The diagram shows the antibacterial properties of the light-driven antibacterial fabrics prepared in Example 1 and Comparative Example 1 against Staphylococcus aureus and Escherichia coli. After 60 minutes of light irradiation, the fabric prepared in Example 1 showed a light-induced bactericidal rate of 99.99% against Staphylococcus aureus and Escherichia coli. The fabric prepared in Comparative Example 1 showed light-induced bactericidal rates of 67.34% and 60.21% against Staphylococcus aureus and Escherichia coli, respectively. The fabric prepared in Comparative Example 2 showed almost no antibacterial properties.

[0083] All the above results demonstrate that the assembly of photosensitive dyes and fluorescent dyes on the fabric surface promotes photothermal and photodynamic effects, and the absorption spectrum of the fabric is broadened to a wide visible region with high photon utilization, resulting in a multi-mode synergistic antibacterial effect.

[0084] The above embodiments of the present invention are merely illustrative examples and are not intended to limit the implementation of the invention. Those skilled in the art can make other variations and modifications based on the above description. It is impossible to exhaustively list all possible implementations here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A multi-mode photo-driven antibacterial fabric based on functional intermolecular assembly-induced antibacterial properties, characterized in that, This multi-mode light-driven antibacterial fabric is an antibacterial fabric formed by first grafting a photosensitive dye onto the surface of a fabric made of cotton, wool, or silk substrate and then assembling a fluorescent dye; the photosensitive dye is a tetracarboxylate-modified zinc phthalocyanine, and the fluorescent dye is a cationic 1,8-naphthalimide fluorescent molecule. Preparation method of cationic 1,8-naphthylimide fluorescent molecule: 1 mole of 4-bromo-N-(dimethylamino)propyl-1,8-naphthylimide and 2 moles of n-dodecylamine were added to ethylene glycol monomethyl ether solvent and stirred under reflux for 20 ± 2 hours. After the reaction was completed, the mixture was poured into water and dilute HCl solution was added dropwise to adjust the pH to 2-4. The product was purified using dichloromethane as an extractant to obtain the intermediate compound 4-n-dodecylamino-N-(dimethylamino)propyl-1,8-naphthylimide. Then, 1 mole of 4-dodecylamino-N-(dimethylamino)propyl-1,8-naphthylimide was reacted with 2 moles of benzyl chloride in acetone. After the reaction was completed, the system was cooled and filtered to obtain the crude product. The crude product was recrystallized and purified using ethanol as a solvent to obtain a yellow powder, i.e., cationic 1,8-naphthylimide fluorescent molecule.

2. A method for preparing a multi-mode photodriven antibacterial fabric based on functional intermolecular assembly induced as described in claim 1, characterized in that... The method includes the following steps: S1. Add tetracarboxylated modified zinc phthalocyanine and N,N-carbonyl diimidazole (CDI) to DMF and activate at 70-100 °C for 2-6 h to obtain the activated solution; In the activation solution, the molar ratio of tetracarboxylated modified zinc phthalocyanine to CDI is 1:1-3, and the concentration of tetracarboxylated modified zinc phthalocyanine is 1-20 g / L; S2. The fabric is immersed in the activation solution for a shaking reaction grafting, then taken out and soaped, washed with water and dried to obtain zinc phthalocyanine grafted fabric; the shaking reaction temperature is 80-100 ℃ and the shaking time is 6-12 h. S3. Add cationic 1,8-naphthalimide fluorescent molecules to an appropriate amount of solvent, heat and stir to dissolve, add the zinc phthalocyanine grafted fabric described in S2, and assemble by shaking at 90 ℃±5 ℃ for 4-10 h, then wash and dry to obtain multimode light-driven antibacterial fabric.

3. The method for preparing the multi-mode photodriven antibacterial fabric based on functional intermolecular assembly as described in claim 2, characterized in that, In S1, the molar ratio of tetracarboxylated modified zinc phthalocyanine to CDI is 1:2, and the concentration of tetracarboxylated modified zinc phthalocyanine is 10 g / L.

4. The method for preparing the antibacterial fabric based on multimode photodriven assembly induced by functional intermolecular assembly as described in claim 2, characterized in that, In S1, the activation time is 4 hours and the temperature is 80 ℃.

5. The method for preparing antibacterial fabric based on multimode photo-driven assembly induced by functional intermolecular assembly as described in claim 2, characterized in that, In S2, the bath ratio of the fabric to the activating liquid is 1:10-30.

6. The method for preparing antibacterial fabric based on multimode photo-driven assembly induced by functional intermolecular assembly as described in claim 2, characterized in that, In S3, the cationic 1,8-naphthalimide fluorescent molecule is a cationic 4-NH-1,8-naphthalimide derivative, and the solvent is water or ethanol.

7. The method for preparing the multi-mode photodriven antibacterial fabric based on functional intermolecular assembly induced as described in claim 2 or 6, characterized in that, The amount of cationic 1,8-naphthalimide fluorescent molecules used is 1-5 g / 100 mL solvent.

8. The method for preparing antibacterial fabric based on multimode photo-driven assembly induced by functional intermolecular assembly as described in claim 2, characterized in that, In S3, the ratio of the zinc phthalocyanine grafted fabric to the assembly solution is 1:10-30.

9. The method for preparing the antibacterial fabric based on functional intermolecular assembly-induced multimode photodriven process as described in claim 2, characterized in that, Preparation method of tetracarboxylated modified zinc phthalocyanine: Under nitrogen protection, using n-pentanol as solvent, 2 moles of 2-(4-(3,4-dicyanophenoxy)phenyl)acetic acid, 1 mole of zinc acetate dihydrate and 2 moles of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were mixed and the reaction was maintained at 137 ± 5℃. After the reaction was completed, an appropriate amount of ethyl acetate was added to the system, and the mixture was allowed to stand. The filter cake was collected by vacuum filtration, dried, and purified by alkaline dissolution and acid precipitation to obtain a blue-green powder, namely tetracarboxylated modified zinc phthalocyanine.

Images