A photosensitizer, its preparation method and application; a method for preparing antibacterial fibers and their application.

Abstract

This invention provides a photosensitizer, its preparation method and application, and a method and application for preparing antibacterial fibers. The method for preparing antibacterial fibers includes the following steps: adding a photosensitizer and cellulose powder to a spinning solution, and then preparing antibacterial fibers through wet spinning. The method for preparing antibacterial fibers of this invention, by adding a photosensitizer to the wet spinning solution, enables it to generate reactive oxygen species (ROS) under light irradiation, thereby destroying bacteria around the spun fibers and achieving a good antibacterial effect. Textile antibacterial performance tests on the spun fibers show that the inhibition rate against Escherichia coli and Staphylococcus aureus can reach 100%.

Description

Technical Field

[0001] This invention relates to the field of textile technology, and in particular to a photosensitizer, its preparation method and application, and a method for preparing and applying antibacterial fibers. Background Technology

[0002] Textiles, as an important part of people's daily lives, are closely related to healthy living. Today, people crave healthier textiles and are increasingly focused on new technologies such as antibacterial and antiviral properties. Therefore, textiles with antibacterial and antimicrobial effects have become products of long-term consumer interest. Currently, antibacterial materials used in the textile industry are mainly divided into three types: natural antibacterial materials, organic antibacterial materials, and inorganic antibacterial materials. Natural antibacterial materials include chitosan, traditional Chinese medicine, and copper sulfate pentahydrate, but their extraction processes are complex, their chemical stability is poor, and their antibacterial effect is short-lived. Organic antibacterial materials, such as quaternary ammonium salts and thiazoles, have low thermal stability and are easily decomposed and inactivated by heat, producing toxic substances. Low-molecular-weight antibacterial materials, in particular, are highly toxic and generate a large number of drug-resistant bacteria during use. Commonly available inorganic antibacterial materials are basically made from metal ions such as zinc, silver, and copper, which have strong antibacterial capabilities, and are synthesized into carriers through electrostatic adsorption. These inorganic antibacterial materials have poor wash resistance, and their antibacterial effect is time-limited.

[0003] Photodynamic therapy (PDT) is a new technology that utilizes the photodynamic effect produced by light and photosensitizers for disease diagnosis and treatment, and it is currently widely used in the medical field. Photodynamic antibacterial agents have advantages such as rapid and efficient antibacterial action; broad applicability to fungi, bacteria, and viruses; no induction of bacterial resistance; and low toxicity. However, a technical solution for preparing antibacterial fibers using photosensitizers has not yet been publicly disclosed. Summary of the Invention

[0004] In view of this, the present invention provides a photosensitizer and its preparation method and application, as well as a method for preparing antibacterial fibers and their application, to overcome the deficiencies existing in the prior art.

[0005] In a first aspect, the present invention provides a photosensitizer, the structural formula of which is shown below:

[0006]

[0007] Where A is selected from Any one of them;

[0008] X is selected from I - ,Br - Cl - or PF6 - Any one of them.

[0009] Secondly, the present invention also provides a method for synthesizing the photosensitizer, comprising the following steps:

[0010] The third compound was synthesized using the first and second compounds;

[0011] The fifth compound was synthesized using the third and fourth compounds;

[0012] A photosensitizer was obtained by reacting the fifth compound with iodomethane.

[0013] Thirdly, the present invention also provides an application of the photosensitizer described above or the photosensitizer prepared by the preparation method described above as an antibacterial agent.

[0014] Fourthly, the present invention also provides a method for preparing antibacterial fibers, comprising the following steps: adding the photosensitizer and cellulose powder to a spinning solution, and preparing antibacterial fibers by wet spinning.

[0015] Fifthly, the present invention also provides an application of the antibacterial fiber prepared by the preparation method described above as a bacteriostatic agent.

[0016] The present invention has the following advantages over the prior art:

[0017] 1. The photosensitizer of the present invention can generate toxic ROS under light irradiation. ROS can oxidize the bacterial cell membrane, thereby causing the destruction of bacteria and achieving an antibacterial effect.

[0018] 2. The method for preparing antibacterial fibers of the present invention involves adding a photosensitizer to the wet spinning solution, which enables the solution to generate reactive oxygen species (ROS) under light irradiation, thereby destroying bacteria around the spun fibers and achieving a good antibacterial effect. The antibacterial performance test of the spun fibers shows that the inhibition rate against Escherichia coli and Staphylococcus aureus can reach 100%. Attached Figure Description

[0019] 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.

[0020] Figure 1 The NMR spectrum of the third compound prepared in Example 1;

[0021] Figure 2 The NMR spectrum of the fifth compound prepared in Example 1;

[0022] Figure 3 The NMR spectrum of the photosensitizer prepared in Example 1;

[0023] Figure 4 Fluorescence spectra of a mixed solution of photosensitizer and DCFH under white light irradiation at different times;

[0024] Figure 5 This is a photograph of the antibacterial fiber prepared in Example 2 of the present invention.

[0025] Figure 6 Results of antibacterial performance tests on agar plates with and without photosensitizers;

[0026] Figure 7 The results show the antibacterial performance test results of the antibacterial fibers in Example 2 and Comparative Example 1. Detailed Implementation

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

[0028] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single digits within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0029] This application provides a photosensitizer, the structural formula of which is shown below:

[0030]

[0031] Where A is selected from Any one of them;

[0032] X is selected from I - ,Br - Cl - or PF6 - Any one of them.

[0033] In some embodiments, the photosensitizer has the following structural formula:

[0034]

[0035] Based on the same inventive concept, the present invention also provides a method for synthesizing a photosensitizer, characterized by comprising the following steps:

[0036] S1. A third compound is synthesized using the first and second compounds;

[0037] S2. Compound 5 is synthesized using the third and fourth compounds;

[0038] S3. A photosensitizer is obtained by reacting the fifth compound with iodomethane.

[0039] The structural formula of the first compound is:

[0040]

[0041] The structural formula of the second compound is:

[0042] The structural formula of the third compound is:

[0043]

[0044] The structural formula of the fourth compound is:

[0045] The structural formula of the fifth compound is:

[0046]

[0047] In some embodiments, a first compound, a second compound, an inorganic base, and a catalyst are added to a first solvent and reacted at 58–62°C to obtain a third compound.

[0048] In some embodiments, the third compound, the fourth compound, the inorganic base, and the catalyst are added to the second solvent and reacted at 64–68°C to obtain the fifth compound.

[0049] In some embodiments, the fifth compound and iodomethane are added to the third solvent and reacted at 78–82°C to obtain a photosensitizer.

[0050] In some embodiments, the catalyst is metallic palladium, for example, tetra(triphenylphosphine)palladium.

[0051] In some embodiments, the first solvent includes at least one of toluene, tetrahydrofuran, and dioxane.

[0052] In some embodiments, the second solvent comprises a mixture of tetrahydrofuran and water.

[0053] In some embodiments, the third solvent includes at least one of dioxane, ethanol, and methanol.

[0054] In some embodiments, the third solvent includes at least one of dioxane, ethanol, and methanol.

[0055] In some embodiments, the molar ratio of the first compound and the second compound is 1:(1 to 2).

[0056] In some embodiments, the molar ratio of the third compound to the fourth compound is 1:(1 to 2).

[0057] In some embodiments, the molar ratio of the fifth compound to iodomethane is 1:(2-3).

[0058] Based on the same inventive concept, the present invention also provides an application of the above-mentioned photosensitizer or the photosensitizer prepared by the above-mentioned preparation method as an antibacterial agent.

[0059] Based on the same inventive concept, the present invention also provides a method for preparing antibacterial fibers, comprising the following steps: adding the above-mentioned photosensitizer and cellulose powder to a spinning solution, and preparing antibacterial fibers by wet spinning.

[0060] The photosensitizer synthesized in this invention utilizes its ability to generate reactive oxygen species (ROS) under sunlight irradiation. By blending this photosensitizer with cellulose powder using wet spinning technology, the spun yarn has a long-lasting antibacterial effect.

[0061] Specifically, the wet spinning process is as follows: add spinning solution to the spinning tank → press the solution out from the spinneret to form a fine stream → the fine stream of solution solidifies into nascent fibers in the coagulation bath (water) → apply a traction machine (to stretch and wind the spun yarn (nascent fibers)) → air dry naturally.

[0062] Specifically, cellulose powder, also known as microcrystalline, microcrystalline cellulose, wood powder, etc., has the molecular formula: (C6H 10 O5) n .

[0063] In some embodiments, the spinning solution comprises a mixture of an ionic liquid and dimethyl sulfoxide (DMSO) in a volume ratio of (1-3):(1-2).

[0064] Specifically, the ionic liquids are imidazole-based ionic liquids. The cations include three main categories: 1-alkylimidazolium, 1-alkyl-3-methylimidazolium, and 1-alkyl-2,3-dimethylimidazolium. The alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. The anions include: chlorine, bromine, iodine, tetrafluoroboric acid, hexafluorophosphate, acetic acid, bis(trifluoromethanesulfonyl)imide, nitric acid, perchloric acid, hydrogen sulfate, dihydrogen phosphate, trifluoromethanesulfonic acid, trifluoroacetic acid, and p-toluenesulfonic acid.

[0065] In some embodiments, photosensitizer and cellulose powder are added to the spinning solution and stirred at 80-120°C until clear to obtain cellulose spinning solution; wherein the mass fraction of cellulose powder in the cellulose spinning solution is 4-8%, and the mass ratio of photosensitizer to cellulose powder is 1:(90-110).

[0066] The method for preparing antibacterial fibers of the present invention involves adding a photosensitizer to the wet spinning solution, which enables the solution to generate reactive oxygen species (ROS) under light irradiation, thereby destroying bacteria around the spun fibers and achieving a good antibacterial effect. The antibacterial performance of the spun fibers was tested, and the results showed that the inhibition rate against Escherichia coli and Staphylococcus aureus could reach 100%.

[0067] Based on the same inventive concept, the present invention also provides an application of the antibacterial fiber prepared by the above-mentioned preparation method as a bacteriostatic agent. Specifically, the antibacterial fiber exhibits excellent antibacterial effects against Staphylococcus aureus and Escherichia coli.

[0068] The following specific embodiments further illustrate the photosensitizer and its preparation method and application, as well as the preparation method and application of antibacterial fibers. This section further illustrates the content of the present invention in conjunction with specific embodiments, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0069] Example 1

[0070] This application provides a photosensitizer with the following structural formula:

[0071]

[0072] The method for synthesizing the above photosensitizer includes the following steps:

[0073] S1. Compound 1 (250 mg, 0.71 mmol), compound 2 (420 mg, 1.4 mmol), potassium carbonate (590 mg, 4.25 mmol), and tetra(triphenylphosphine)palladium (42 mg, 0.036 mmol) were added to a 250 mL double-necked round-bottom flask. The flask was then evacuated and purged twice with nitrogen. The first solvent (tetrahydrofuran (30 mL) and water (10 mL)) was added to the flask, and the mixture was stirred overnight at 60 °C. The reaction process was monitored by thin-layer chromatography (TLC). After the reactants had reacted completely, the mixture was extracted with dichloromethane. An appropriate amount of 200-300 mesh silica gel was added to the organic layer, and the solvent was thoroughly evaporated using a vacuum rotary evaporator. The mixture was then separated and purified by silica gel column chromatography using petroleum ether and dichloromethane as eluents. The eluent containing the product was evaporated to obtain an orange-red solid powder compound (271 mg, 70.9%), which is the third compound.

[0074] S2. Compound 3 (200 mg, 0.376 mmol), compound 4 (400 mg, 0.753 mmol), potassium carbonate (1200 mg, 8.696 mmol), and tetra(triphenylphosphine)palladium (23 mg, 0.02 mmol) were added to a 250 mL double-necked round-bottom flask. The flask was evacuated and cleaned twice with nitrogen. Then, tetrahydrofuran (30 mL) and water (10 mL) were added to the flask as a second solvent. The mixture was refluxed overnight at 66 °C under nitrogen. The reaction process was monitored by thin-layer chromatography (TLC). After the reactants had reacted completely, the mixture was extracted three times with dichloromethane and washed with water. The dichloromethane layer was separated and dried with anhydrous sodium sulfate. An appropriate amount of 200-300 mesh silica gel was added to the organic layer, and the solvent was thoroughly evaporated using a vacuum rotary evaporator. After evaporating the solvent, the crude product was purified by silica gel column chromatography. Petroleum ether / dichloromethane (volume ratio of petroleum ether to dichloromethane was 1:3) was used as the eluent for elution. The eluent containing the product was evaporated to dryness to obtain a red powder (150 mg, 77.3%), which is the fifth compound.

[0075] S3. Add the fifth compound (100 mg, 0.1 mmol) and iodomethane (16 mg, 0.1 mmol) to a 50 mL double-necked round-bottom flask. Vacuum the flask and clean it twice with nitrogen. Reflux the mixture overnight at 80 °C under nitrogen atmosphere using methanol as solvent. Monitor the reaction progress using thin-layer chromatography (TLC). After the reactants have reacted completely, filter to obtain a deep purple filtrate. Add an appropriate amount of 200-300 mesh silica gel, and evaporate the solvent thoroughly using a vacuum rotary evaporator. Purify the crude product using alumina column chromatography, eluting with dichloromethane and methanol. Elute the product-containing eluent to obtain a novel photosensitizer, a reddish-purple powder (72 mg, 38.9%), which is the photosensitizer of this invention.

[0076] The synthetic route of the photosensitizer in this application embodiment is shown below (where 1, 2, 3, 4, and 5 represent the first compound, the second compound, the third compound, the fourth compound, and the fifth compound, respectively):

[0077]

[0078] Example 2

[0079] This application provides a method for preparing antibacterial fibers, comprising the following steps:

[0080] S1. Add 4 mg of the photosensitizer and cellulose powder from Example 1 to the spinning solution, and stir at 100°C until clear to obtain a cellulose spinning solution; the spinning solution includes a mixture of an ionic liquid and dimethyl sulfoxide (DMSO) in a volume ratio of 2:1; wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride.

[0081] S2. Add spinning solution to the spinning tank and press it out from the spinneret to form a fine stream. The original solution fine stream solidifies into nascent fibers in the coagulation bath (water), is drawn and wound, and air-dried naturally to obtain antibacterial fibers.

[0082] The cellulose powder in the spinning solution has a mass fraction of 6% and a photosensitizer mass fraction of 1% of the cellulose powder mass.

[0083] Comparative Example 1

[0084] This comparative example provides a method for preparing antibacterial fibers, which is the same as in Example 2, except that no photosensitizer is added in step S1, and the remaining process parameters are the same as in Example 2.

[0085] Performance testing

[0086] Figure 1 The NMR spectrum is that of the third compound prepared in Example 1.

[0087] Figure 2 The NMR spectrum is that of the fifth compound prepared in Example 1.

[0088] Figure 3 The image shows the NMR spectrum of the photosensitizer prepared in Example 1.

[0089] The photosensitizer in Example 1 of this invention was tested to determine whether it could generate ROS (i.e., reactive oxygen species).

[0090] Photosensitizers that produce ROS are non-toxic in the dark, but can produce toxic ROS under light. ROS can oxidize bacterial cell membranes, leading to bacterial destruction and thus achieving an antibacterial effect.

[0091] To visually detect whether the photosensitizer prepared in Example 1 has the ability to generate ROS, DCFH (2',7'-dichlorofluorescein diacetate) was used as an indicator. When ROS is generated, the non-fluorescent DCFH will be oxidized to the fluorescent DCF. The generation of ROS was detected by measuring the change in fluorescence intensity.

[0092] Dissolve 1.35 mg of the photosensitizer from Example 1 in 10 mL of DMSO to prepare a 200 μM stock solution. Take 2 mL of the stock solution and add it to 50 μL of the activated DCFH solution. Mix well and then use 10 mW cm -2 The light was applied under white light, and the fluorescence intensity was measured every 10 seconds. The excitation wavelength was 488 nm, and the fluorescence signal in the range of 500–600 nm was recorded. The fluorescence intensity values ​​in the experiment were compared as the basis for reactive oxygen species testing. The test results are as follows: Figure 4 As shown.

[0093] from Figure 4 As can be seen, the fluorescence intensity of the photosensitizer continuously increases with the increase of illumination time. This proves that the photosensitizer synthesized in this invention can generate ROS that destroys bacteria under illumination.

[0094] Figure 5 This is a photograph of the antibacterial fiber prepared in Example 2 of the present invention.

[0095] Antibacterial performance test of agar plates with and without photosensitizer

[0096] Two 0.15 mM solid culture media were prepared using the photosensitizer from Example 1. The cultured and activated Staphylococcus aureus and Escherichia coli were then serially diluted 10-fold to the appropriate dilution factor (the concentration of Staphylococcus aureus and Escherichia coli after dilution was 10). 6 CFU mL -1 Using a pipette, 100 μL of each dilution was transferred into a sterile agar plate containing the photosensitizer from Example 1, and then incubated in a CO2 bio-incubator at 37°C for 24-36 hours.

[0097] Prepare a solid culture medium without photosensitizer. Then, serially dilute the activated Staphylococcus aureus and Escherichia coli to the appropriate dilution factor using the 10-fold dilution method. Use a pipette to transfer 100 μL from each dilution tube into a sterile agar plate without the photosensitizer from Example 1, and then incubate in a CO2 bio-incubator at 37°C for 24-36 hours.

[0098] The antibacterial performance test results of agar plates with and without photosensitizers are as follows: Figure 6 As shown. Figure 6In the table, a represents Escherichia coli cultured on an agar plate without photosensitizer; b represents Escherichia coli cultured on an agar plate with photosensitizer; c represents Staphylococcus aureus cultured on an agar plate without photosensitizer; and d represents Staphylococcus aureus cultured on an agar plate with photosensitizer.

[0099] from Figure 6 As can be seen, when cultured on agar plates with added photosensitizer, the photosensitizer exhibits excellent antibacterial effects against Staphylococcus aureus and Escherichia coli, and the antibacterial effect is long-lasting and non-toxic to humans.

[0100] The antibacterial properties of the antibacterial fibers in Example 2 and Comparative Example 1 were tested.

[0101] Take two 0.75g portions of the antibacterial fiber obtained in Example 2 and place them separately into Erlenmeyer flasks containing 70mL PBS buffer. Add 5mL of Staphylococcus aureus and 5mL of Escherichia coli to each flask and co-culture on a shaker for 18 hours. After the specified time, pipette 100μL of the solution from each Erlenmeyer flask into a test tube containing 900μL PBS buffer and mix thoroughly. Serially dilute to the appropriate dilution factor using the 10-fold dilution method. Use a pipette to transfer 100μL from each dilution tube into a sterile agar plate, and then incubate at 37°C in a CO2 bio-incubator for 18 hours.

[0102] Take two 0.75g portions of the antibacterial fiber obtained in Comparative Example 1 and place them separately into Erlenmeyer flasks containing 70mL PBS buffer. Add 5mL of Staphylococcus aureus and 5mL of Escherichia coli to each flask and co-incubate on a shaker for 18 hours. After the specified time, pipette 100μL of the solution from each Erlenmeyer flask into a test tube containing 900μL PBS buffer and mix thoroughly. Serially dilute to the appropriate dilution using the 10-fold dilution method. Using a pipette, pipette 100μL from each dilution tube into sterile agar plates, creating two parallel plates for each dilution. Then incubate at 37℃ in a CO2 bioincubator for 18 hours.

[0103] The antibacterial performance test results of the antibacterial fibers in Example 2 and Comparative Example 1 are as follows: Figure 7 As shown. Figure 7 In the table, a is an agar plate after co-culturing Escherichia coli with the antimicrobial fiber obtained in Comparative Example 1; b is an agar plate after co-culturing Escherichia coli with the antimicrobial fiber obtained in Example 2; c is an agar plate after co-culturing Staphylococcus aureus with the antimicrobial fiber obtained in Comparative Example 1; and d is an agar plate after co-culturing Staphylococcus aureus with the antimicrobial fiber obtained in Example 2.

[0104] from Figure 7As can be seen from the example, the number of bacterial colonies in the antibacterial fibers obtained by wet spinning of photosensitizer and cellulose powder in Example 2 was significantly reduced, and the calculated inhibition rate against Escherichia coli and Staphylococcus aureus could reach 100%.

[0105] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The application of an antibacterial fiber in the preparation of an antibacterial agent, said antibacterial agent being used to inhibit the growth of Staphylococcus aureus and Escherichia coli; The method for preparing the antibacterial fiber includes the following steps: Photosensitizer and cellulose powder are added to the spinning solution, and antibacterial fibers are prepared by wet spinning. The spinning solution comprises a mixture of an ionic liquid and dimethyl sulfoxide, wherein the volume ratio of the ionic liquid to dimethyl sulfoxide is (1~3):(1~2); The structural formula of the photosensitizer is shown below: ； The ionic liquid is 1-butyl-3-methylimidazolium chloride.

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