Preparation method of oxime sulfonate photosensitizer with functions of acid production and active oxygen production and application of oxime sulfonate photosensitizer in construction of photoetching pattern and antibacterial coating

Abstract

The application discloses a preparation method of an oxime sulfonate photosensitizer with functions of acid production and active oxygen production and application of the oxime sulfonate photosensitizer to photoetching pattern and antibacterial coating construction, and belongs to the technical field of photosensitive materials. The photosensitizer has a D-X-A structure, the left side is an electron-donating aromatic ring derivative, the right side is a benzene derivative, and X is a sulfonate group. The preparation method comprises the following steps: an oxime intermediate is obtained through an oximation reaction of a cyano-containing aromatic compound, and then the target product is prepared through reaction of the oxime intermediate with a benzene sulfonyl chloride derivative. The photosensitizer can release acid and active oxygen simultaneously under excitation of ultraviolet light and white light, has functions of acid production and ROS production, and has an aggregation-induced emission characteristic. The photosensitizer is mixed with a polymerizable monomer to prepare a photoresist, and a fine photoetching pattern can be obtained through mask exposure and development. The photosensitizer can also be used to prepare an antibacterial polymer coating, and the antibacterial polymer coating has a high-efficiency photodynamic sterilization effect on gram-negative bacteria and gram-positive bacteria. The synthesis route of the application is short, raw materials are easy to obtain, and the application has application prospects in the fields of low-energy-consumption, wide-waveband-response photoetching pattern construction and antibacterial coating.

Description

Technical Field

[0001] This invention belongs to the field of photosensitive materials technology, and particularly relates to a method for preparing an oxime sulfonate photosensitizer that has both acid-producing and reactive oxygen-producing functions, and its application in the construction of photolithographic patterns and antibacterial coatings. Background Technology

[0002] Photopolymerization technology is an advanced manufacturing technology that uses photosensitive materials to convert light energy into chemical energy, enabling rapid curing of materials. Since its industrialization in the late 1960s, this technology has been widely used in fields such as photolithography, coatings, inks, 3D printing, microelectronics manufacturing, and dental restoration, showing broad application prospects and becoming a research hotspot in this field.

[0003] The overall performance of a photocuring system is highly dependent on the performance of the photoinitiator. In existing technologies, the absorption bands of traditional photoinitiators are mainly concentrated in specific ultraviolet regions (such as 254nm and 365nm), and their excitation light sources are mostly high-pressure mercury lamps. However, such light sources have inherent drawbacks such as high energy consumption, large heat generation, short lifespan, and potential ultraviolet radiation risks to operators, which are detrimental to green manufacturing and safe production. In recent years, photoinitiators suitable for UV-LED light sources have become an important research direction, but their usable excitation wavelengths are still mainly limited to the ultraviolet band, especially around 365nm. For longer wavelength visible light and even white light sources, existing photoinitiators generally lack effective absorption responses, making it difficult to fully utilize the more environmentally friendly and safer visible light curing process.

[0004] Furthermore, the limitation of single-function photoinitiators is also a significant factor restricting their application in high-end fields. Taking oxime sulfonate photoinitiators as an example, the function of these photoinitiators in existing technologies is limited to acid production, failing to meet the additional functional requirements arising from the expansion of photocuring technology into cross-disciplinary fields such as antibacterial coatings and biomedical materials. In these application scenarios, not only is the photoinitiator required to efficiently initiate polymerization reactions, but it is also expected to generate reactive oxygen species (ROS) in situ, thereby endowing the coating material with long-lasting antibacterial properties. However, current technologies lack a single-component photoinitiator that can be effectively excited under both ultraviolet and white light and simultaneously possesses the ability to produce both acid and ROS.

[0005] In summary, developing a photoinitiator that can simultaneously generate reactive oxygen species and produce acids under dual-band excitation of ultraviolet light (especially 365nm) and white light has significant research value and practical application significance for realizing a green, efficient, and multifunctional photocurable antibacterial coating system, which constitutes the main research motivation of this invention. Summary of the Invention

[0006] To overcome the shortcomings and deficiencies of the prior art, this invention proposes a method for preparing an oxime sulfonate photosensitizer that combines acid production and reactive oxygen species production, and its application in photolithographic patterning and antibacterial coating construction. This photosensitizer can simultaneously release acid and reactive oxygen species under ultraviolet light (especially 365 nm) and white light excitation, and correspondingly provides its specific applications in photolithographic pattern construction and antibacterial coating preparation. This method is simple, uses readily available raw materials, and has a high yield.

[0007] To achieve the above objectives, the present invention provides the following technical solution: An oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions has the following structure: Wherein, R1 is an aromatic ring derivative group with electron-donating properties, and R2 is a benzene derivative group.

[0008] Further, R1 is phenyl, triphenylamino, dimethoxytriphenylamino, naphthyl, anthraceneyl, phenanthiazinyl, phenoxazinyl, or diphenylamino.

[0009] Furthermore, R1 is one of the structures shown in equation a~i: R' is independently selected from hydrogen atoms or halogen elements (such as fluorine atoms or bromine atoms).

[0010] Furthermore, R2 is phenyl, naphthyl, phenanthryl or pyrene.

[0011] Furthermore, R2 is one of the structures shown in equations a~d: R' is independently selected from hydrogen atoms or halogen elements (such as fluorine atoms or bromine atoms).

[0012] This invention also provides a method for preparing an oxime sulfonate photosensitizer that has both acid-producing and reactive oxygen species-producing functions, comprising the following steps: An aromatic compound containing a cyano group was added to a mixed solvent of toluene and methanol, sodium hydroxide was added, the temperature was raised to 40°C, and then isoamyl nitrite was added. The mixture was stirred at a constant temperature and then post-treated to obtain the oxime intermediate. The oxime intermediate was dissolved in ultra-dry tetrahydrofuran, and triethylamine and benzenesulfonyl chloride derivative were added under a nitrogen atmosphere at 0-5°C (e.g., 0°C). The mixture was then raised to room temperature and reacted. After post-treatment, the oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions was obtained.

[0013] This invention introduces an electron-donating group (Donor) and an electron-withdrawing group (Acceptor) onto the left side of the oxime sulfonate backbone, constructing a DXA structure. The X group, a sulfonate group, is connected to the molecular backbone via a NO bond and is the core unit for acid production. The DA structure regulates the absorption band and molar absorptivity of the molecule, while simultaneously promoting the generation of reactive oxygen species (ROS). Therefore, the material of this invention possesses a high molar absorptivity, can be excited by a wide wavelength range of light, and can simultaneously generate ROS and produce acid. Based on this type of material, photoinitiators with low energy consumption, wide wavelength excitation, and dual functions of acid production and ROS generation can be prepared.

[0014] This invention also provides the application of an oxime sulfonate photosensitizer that has both acid-producing and reactive oxygen-producing functions in the construction of photolithographic patterns.

[0015] Furthermore, the method for constructing the photolithographic pattern includes: mixing an oxime sulfonate photosensitizer with a polymerizable monomer to obtain a photoresist, coating it on the surface of a substrate, exposing it through a mask, and then washing away the uncured portion with a developer to obtain the photolithographic pattern.

[0016] This invention also provides the application of an oxime sulfonate photosensitizer that has both acid-producing and reactive oxygen-producing functions in the construction of antibacterial coatings.

[0017] Furthermore, the method for constructing the antibacterial coating includes: mixing an oxime sulfonate photosensitizer with a polymerizable monomer, coating it onto the surface of a substrate, and curing it under light to obtain an antibacterial polymer coating.

[0018] Compared with the prior art, the present invention has the following advantages and technical effects: (1) This invention provides a class of organic photosensitive materials with molecular structure of oxime sulfonate esters. While maintaining the acid production performance, the material also has the ability to generate reactive oxygen species (ROS), thereby overcoming the limitation of the single function of existing similar materials.

[0019] (2) The synthesis route of the photosensitive material described in this invention is short, the reaction conditions are mild, the raw materials used are inexpensive and easy to obtain, and the total yield of the product is high, which has good prospects for industrial production and practical application value. Attached Figure Description

[0020] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 For intermediate RP1 1 H nuclear magnetic resonance spectrum (400MHz, DMSO-d6, 298K); Figure 2 For ARP1 1H nuclear magnetic resonance spectrum (600MHz, DMSO-d6, 298K); Figure 3 For ARP1 13 C nuclear magnetic resonance spectrum (101MHz, DMSO-d6, 298K); Figure 4 High-resolution mass spectrometry of ARP1; Figure 5 For intermediate RP2-1 1 H nuclear magnetic resonance spectrum (400MHz, DMSO-d6, 298K); Figure 6 For intermediate RP2-2 1 H nuclear magnetic resonance spectrum (400MHz, DMSO-d6, 298K); Figure 7 For ARP2 1 H nuclear magnetic resonance spectrum (600MHz, DMSO-d6, 298K); Figure 8 For ARP2 13 C nuclear magnetic resonance spectrum (151MHz, DMSO-d6, 298K); Figure 9 High-resolution mass spectrometry of ARP2; Figure 10 For intermediate RP3-1 1 H nuclear magnetic resonance spectrum (600MHz, DMSO-d6, 298K); Figure 11 For intermediate RP3-2 1 H nuclear magnetic resonance spectrum (600MHz, DMSO-d6, 298K); Figure 12 For ARP3 1 H nuclear magnetic resonance spectrum (600MHz, DMSO-d6, 298K); Figure 13 For ARP3 13 C nuclear magnetic resonance spectrum (151MHz, DMSO-d6, 298K); Figure 14 High-resolution mass spectrometry of ARP3; Figure 15 The ultraviolet absorption spectrum (A) and fluorescence emission spectrum (B) of the oxime sulfonate photosensitizers prepared in Examples 1-3 in tetrahydrofuran solvent are shown. Figure 16The graphs show the fluorescence intensity increase of the oxime sulfonate photosensitizers prepared in Examples 1-3 in dimethyl sulfoxide / toluene mixed solvents with toluene content (v / v) of 0%, 20%, 40%, 60%, 80%, and 90%; where (A) is ARP1, (B) is ARP2, and (C) is ARP3. Figure 17 The graph shows the fluorescence intensity changes of the oxime sulfonate photosensitizers prepared in Examples 1-3 after adding photosensitizers to DMSO / water solutions containing H2DCF-DA (abbreviated as DCFH in the figure) probe (A), ABDA probe (B), DHR123 probe (C), and HPF probe (D) and then irradiating them. Figure 18 The reaction formulas are for the acid generated by the oxime sulfonate photosensitizers prepared in Examples 1-3 and the reaction with rhodamine (RB); Figure 19 The absorbance change trends of RB after different photosensitizers (commercial photoacid generators: DPI and NHN-TF, synthetic photoacid generators: ARP1, ARP2, ARP3) are irradiated by different light sources: (A) 254 nm light source, (B) 365 nm light source, (C) white light source, (D) 365 nm light source with different irradiation doses; Figure 20 Here are the molecular structures of NHN-TF and DPI; Figure 21 This is a schematic diagram of the photolithography process for preparing a photoresist after adding the oxime sulfonate photosensitizer obtained in Example 2 to the monomer. Figure 22 The photolithography effect of the photoresist prepared by adding the oxime sulfonate photosensitizer obtained in Example 2 after adding the monomer is shown in the following figures: (A) Scanning electron microscope images of different line spacing patterns obtained by photoresist preparation, (B) Normal distribution curve of line width (designed line width is 30 micrometers). Figure 23 This is a schematic diagram of the nail polish gel preparation process after adding the oxime sulfonate photosensitizer obtained in Example 2 to the monomer; Figure 24 The following are images showing the curing effect of nail polish gel prepared with the oxime sulfonate photosensitizer obtained in Example 2 after the addition of monomer: (A) Fourier transform infrared spectrum of nail polish gel curing under different light sources, (B) Curing time and temperature curve of nail polish gel under different light sources, (C) Actual application effect of nail polish gel under different light sources, (D) Comparison of curing energy consumption of nail polish gel under different light sources. Figure 25To illustrate the growth of Escherichia coli (E. coli) colonies on agar plates before and after photodynamic antibacterial treatment of the antibacterial polymer film prepared by doping the oxime sulfonate photosensitizer obtained in Example 2 into the monomer at different mass fractions: (A) Colony count statistics of E. coli on the antibacterial plate, (B) Antibacterial plate image of E. coli; Figure 26 To illustrate the growth of methicillin-resistant Staphylococcus aureus (MRSA) colonies on agar plates before and after photodynamic antibacterial treatment of the antibacterial polymer film prepared by doping the oxime sulfonate photosensitizer obtained in Example 2 into the monomer at different mass fractions: (A) Statistical count of MRSA colonies on the antibacterial plate, (B) Antibacterial plate image of MRSA. Detailed Implementation

[0021] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0022] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0023] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0024] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0025] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0026] The oxime sulfonate photosensitizer provided in this embodiment of the invention has the following structure: In this group, R1 is an aromatic ring derivative group with electron-donating properties, and R2 is a benzene derivative group.

[0027] The preparation method of this oxime sulfonate photosensitizer includes the following steps: (1) Preparation of oxime intermediates: A cyano-containing aromatic compound substrate was added to a mixed solvent of toluene and methanol, sodium hydroxide was added, the temperature was raised to 40°C and then amyl nitrite was added, the mixture was stirred at a constant temperature, cooled to room temperature, and filtered using petroleum ether as an elution agent to obtain oxime intermediates. Among them, the aromatic compounds containing cyano groups are selected from p-bromophenylacetonitrile, 4'-(diphenylamino)-4-bromophenylacetonitrile, or 4'-(di(4-methoxyphenyl)amino)-4-bromophenylacetonitrile; The volume ratio of toluene to methanol is 3:1; The molar ratio of sodium hydroxide to substrate is 1.0~2.0:1 (e.g., 1.11:1 or 1.98:1); The molar ratio of amyl nitrite to substrate is 1.0 to 1.7:1 (e.g., 1:1, 1.1:1, or 1.2:1); (2) The obtained oxime intermediate was dissolved in ultra-dry tetrahydrofuran, and triethylamine and benzenesulfonyl chloride derivative were added at 0-5℃ and under nitrogen atmosphere. The reaction was carried out at room temperature. After extraction with dichloromethane, the organic layer was washed with brine and dried with anhydrous sodium sulfate. Then, it was distilled under reduced pressure and washed and filtered with petroleum ether to obtain oxime sulfonate photosensitizers with both acid-producing and reactive oxygen-producing functions. Among them, the benzenesulfonyl chloride derivative is selected from 4-bromobenzenesulfonyl chloride; The molar ratio of benzenesulfonyl chloride derivative to oxime intermediate is 1.0~1.2:1 (e.g., 1.08:1, 1.1:1 or 1.2:1); The molar ratio of triethylamine to oxime intermediate is 2.5 to 5.5:1 (e.g., 2.76:1, 4.38:1, or 5.39:1).

[0028] In some preferred embodiments, when the aromatic compound containing a cyano group is selected from 4'-(diphenylamino)-4-bromophenylacetonitrile or 4'-(di(4-methoxyphenyl)amino)-4-bromophenylacetonitrile, a Suzuki coupling reaction is required to attach the triphenylamine or methoxytriphenylamine group to p-bromophenylacetonitrile to prepare a phenylacetonitrile derivative (RP2-1 / RP3-1) with a strong electron-donating group, which serves as a specific substrate for subsequent oxime reactions. The specific steps are as follows: 4-boronic acid triphenylamine / 4-boronic acid-4',4'-dimethoxytriphenylamine (" / " indicates "or"), p-bromophenylacetonitrile, Pd(PPh3)4, and anhydrous potassium carbonate are added to a mixed solvent of tetrahydrofuran and water (volume ratio 30:12), and refluxed at 80°C under a nitrogen atmosphere for 12 hours. After cooling, the mixture was extracted three times with dichloromethane. The organic layer was washed with brine and dried with anhydrous sodium sulfate. Then, column chromatography was performed using ethyl acetate and petroleum ether (volume ratio 1:20) as eluents to obtain the specific substrate.

[0029] The oxime sulfonate photosensitizer prepared by the above method can be used in the construction of photolithographic patterns. The specific steps are as follows: the oxime sulfonate photosensitizer is mixed with a polymerizable monomer (such as polyethylene glycol diacrylate) to obtain a photoresist, which is then coated on the surface of the substrate. After exposure through a mask, the uncured parts are washed away with a developer to obtain the photolithographic pattern.

[0030] For example, the preparation steps of gel nail polish are as follows: Take 1 part of ARP2 (all parts are by weight) and add it to 30 parts of isobornyl acrylate (IBOA), stir until it is completely dissolved, then add 70 parts of aliphatic polyurethane acrylate oligomer YC 2200 (PUA), disperse evenly, and let it stand in the dark for 2 days to mix thoroughly to obtain gel nail polish.

[0031] The aforementioned oxime sulfonate photosensitizers can also be used in the construction of antibacterial coatings. The specific steps are as follows: mixing the oxime sulfonate photosensitizer with a polymerizable monomer (such as polyethylene glycol diacrylate), coating the mixture onto the substrate surface, and then curing it under light (light power 30mW / cm²). 2 After 30 minutes of light exposure, an antibacterial (for Gram-negative bacteria E. coli or Gram-positive bacteria MRSA) polymer coating was obtained.

[0032] Unless otherwise specified, "room temperature" in this invention refers to 25±2℃.

[0033] Unless otherwise specified, the term "parts" in this invention refers to parts by weight.

[0034] The reagents or monomers used in the following embodiments of the present invention are all commercially available.

[0035] The technical solution of the present invention will be further illustrated by the following embodiments.

[0036] Example 1 Preparation of an oxime sulfonate photosensitizer (ARP1): (1) p-Bromophenylacetonitrile (500 mg, 2.56 mmol) was added to a mixed solvent of toluene and methanol (volume ratio 6 mL: 2 mL), sodium hydroxide (114 mg, 2.85 mmol) was added, the temperature was raised to 40 °C, and then amyl nitrite (300 mg, 2.56 mmol) was added. After stirring at a constant temperature for 3 h, the mixture was cooled to room temperature, and the white precipitate was filtered using petroleum ether as an elution agent to obtain a pale yellow powder RP1 with a yield of 59.8%.

[0037] The characterization data of RP1 obtained are as follows: 1 ¹H NMR (400 MHz, DMSO-d⁶) δ 7.51 (d, J = 8.8 Hz, 2H), 7.46–7.40 (m, 2H) (see...) Figure 1 ).

[0038] (2) RP1 (200 mg, 0.89 mmol) was added to a two-necked flask. Under a nitrogen atmosphere at 0 °C, ultra-dry tetrahydrofuran (8 mL), triethylamine (248.8 mg, 2.46 mmol), and 4-bromobenzenesulfonyl chloride (273 mg, 1.07 mmol) were added, and the mixture was heated to room temperature and reacted for 2 h. The mixture was extracted three times with dichloromethane. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then distilled off the dichloromethane under reduced pressure at 60 °C. The residue was then washed with petroleum ether at 40 °C and filtered to obtain a grayish-white solid ARP1 with a yield of 77.2%.

[0039] The characterization data of ARP1 obtained are as follows: 1 H NMR (600 MHz, DMSO-d6), δ(ppm): 8.10 (d, J =8.6 Hz, 2H), 8.03 (d, J = 8.7 Hz, 2H), 7.88–7.82 (m, 2H), 7.74 (dd, J = 8.6,1.8 Hz, 2H) (see Figure 2 ). 13 C NMR (101 MHz, DMSO-d6) δ 140.43, 133.67, 133.09, 132.66, 131.32, 130.76, 129.73, 127.98, 126.51, 108.22 (see...) Figure 3 HRMS (ESI) m / z: [M - H] - calcd for C 14H7Br2N2O3S, 440.8544; found, 440.8535 (see...) Figure 4 ).

[0040] Example 2 Preparation of an oxime sulfonate photosensitizer (ARP2): (1) Triphenylamine 4-borate (1.64 g, 5.67 mmol), p-bromophenylacetonitrile (1.32 g, 6.77 mmol), Pd(PPh3)4 (129 mg, 0.11 mmol), and anhydrous potassium carbonate (2.96 g, 21.4 mmol) were added to a mixed solvent of tetrahydrofuran and water (volume ratio 30 mL: 12 mL) and refluxed at 80 °C under a nitrogen atmosphere for 12 h. After cooling, the mixture was extracted three times with dichloromethane. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then subjected to column chromatography using ethyl acetate and petroleum ether (volume ratio 1:20) as eluents to obtain a white powder RP2-1 in 80.2% yield.

[0041] The obtained RP2-1 characterization data are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 7.67 (d, J = 8.2 Hz,2H), 7.60 (d, J = 8.6 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 7.33 (t, J = 7.8 Hz,4H), 7.10 - 7.02 (m, 8H), 4.07 (s, 2H) (see Figure 5 ).

[0042] (2) RP2-1 (500 mg, 1.39 mmol) was added to a mixed solvent of toluene and methanol (volume ratio of toluene to methanol was 6 mL: 2 mL), sodium hydroxide (110 mg, 2.75 mmol) was added, the temperature was raised to 40 °C, and then amyl nitrite (264 mg, 2.25 mmol) was added. After stirring at a constant temperature for 3 h, the mixture was cooled to room temperature and extracted three times with dichloromethane. The organic layer was washed with brine and dried with anhydrous sodium sulfate. Then, column chromatography was performed using ethyl acetate and petroleum ether (volume ratio of 1:2) as eluents to obtain yellow powder RP2-2 with a yield of 51.1%.

[0043] The characterization data of RP2-2 obtained are as follows: 1 ¹H NMR (400 MHz, DMSO-d⁶) δ 7.69–7.51 (m, 6H), 7.35–7.28 (m, 4H), 7.10–6.98 (m, 8H) (see...) Figure 6 ).

[0044] (3) Intermediate RP2-2 (170 mg, 0.48 mmol) was added to a two-necked flask. Under a nitrogen atmosphere at 0 °C, ultra-dry tetrahydrofuran (8 mL), triethylamine (211 mg, 2.1 mmol), and 4-bromobenzenesulfonyl chloride (133.8 mg, 0.52 mmol) were added, and the mixture was allowed to react at room temperature for 2 h. The mixture was extracted three times with dichloromethane. The organic layer was washed with brine and dried over anhydrous sodium sulfate. Column chromatography was then performed using dichloromethane and petroleum ether (volume ratio 2:5) as eluent to obtain orange-yellow powder ARP2 in 43.1% yield.

[0045] The obtained characterization data for ARP2 are as follows: 1 H NMR (600 MHz, DMSO-d6), δ(ppm): 8.05 (s, 2H), 7.99 (s, 2H), 7.85 (s, 2H), 7.81 (s, 2H), 7.67 (s, 2H), 7.35 (t, J = 7.9 Hz, 4H), 7.13-7.08 (m, 6H), 7.03 (d, J = 8.7 Hz, 2H) (see Figure 7 ). 13 C NMR (151 MHz, DMSO-d6) δ 148.53, 147.15, 145.02, 140.78, 133.69, 132.83, 131.71, 131.36, 130.72, 128.59, 128.45, 127.35, 125.19, 124.28, 122.79, 108.47 (see...) Figure 8 HRMS(ESI) m / z: [M - H] - calcd for C 32 H 21 BrN3O3S, 606.0487; found, 606.0478 (see...) Figure 9 ).

[0046] Example 3 Preparation of an oxime sulfonate photosensitizer (ARP3): (1) 4-Borate-4',4'-dimethoxytriphenylamine (1 g, 2.86 mmol), p-bromophenylacetonitrile (616 mg, 3.14 mmol), Pd(dppf)Cl2 (62 mg, 0.08 mmol), and anhydrous potassium carbonate (4.8 g, 34.8 mmol) were added to a mixed solvent of tetrahydrofuran and water (volume ratio 40 mL: 16 mL). The mixture was refluxed at 80 °C under a nitrogen atmosphere for 12 hours. After cooling, the mixture was extracted three times with dichloromethane. The organic layer was washed with brine and dried over anhydrous sodium sulfate. Then, column chromatography was performed using ethyl acetate and petroleum ether (volume ratio 1:10) as eluents to obtain a white powder RP3-1 with a yield of 88.1%.

[0047] The obtained RP3-1 characterization data are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 7.61 (s, 2H), 7.50(s, 2H), 7.38 (d, J = 7.9 Hz, 2H), 7.05 (d, J = 8.7 Hz, 4H), 6.93 (d, J = 8.9Hz, 4H), 6.83 (d, J = 8.7 Hz, 2H), 4.05 (s, 2H), 3.75 (s, 6H) (see Figure 10 ).

[0048] (2) Intermediate RP3-1 (302 mg, 0.72 mmol) was added to a mixed solvent of toluene and methanol (6 mL: 2 mL, v / v), followed by sodium hydroxide (32 mg, 0.8 mmol). The mixture was heated to 40 °C, and then amyl nitrite (92.4 mg, 0.79 mmol) was added. The mixture was stirred at a constant temperature for 3 h, then cooled to room temperature. The mixture was extracted three times with dichloromethane. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then subjected to column chromatography using ethyl acetate and petroleum ether (v / v, 1:10, v / v) as eluents. A yellow powder, RP3-2, was obtained in 80.0% yield.

[0049] The obtained RP3-2 characterization data are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 13.74 (s, 1H), 7.75 (s, 4H), 7.56 (d, J = 8.7 Hz, 2H), 7.07 (d, J = 8.9 Hz, 4H), 6.94 (d, J = 8.9Hz, 4H), 6.83 (d, J = 8.9 Hz, 2H), 3.75 (s, 6H) (see Figure 11 ).

[0050] (3) Intermediate RP3-2 (233 mg, 0.518 mmol) was added to a two-necked flask. Under a nitrogen atmosphere at 0 °C, ultra-dry tetrahydrofuran (8 mL), triethylamine (282.5 mg, 2.79 mmol), and 4-bromobenzenesulfonyl chloride (145.7 mg, 0.57 mmol) were added sequentially, and the mixture was allowed to react at room temperature for 2 h. The mixture was extracted three times with dichloromethane. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then distilled off the dichloromethane under reduced pressure at 60 °C to obtain a reddish-brown solid. After washing with petroleum ether at 40 °C and filtration, a brown solid ARP3 was obtained, with a yield of 79.6%.

[0051] The obtained characterization data of ARP3: 1 H NMR (600 MHz, DMSO-d6) δ 8.06-7.97 (m, 3H),7.83-7.71 (m, 3H), 7.60 (d, J = 8.7 Hz, 2H), 7.52 (d, J = 6.5 Hz, 1H), 7.09(d, J = 8.9 Hz, 4H), 6.95 (d, J = 8.9 Hz, 5H), 6.81 (d, J = 8.9 Hz, 2H), 3.75(s, 6H) (see Figure 12 ). 13 C NMR (151 MHz, DMSO-d6) δ 156.71, 149.69, 145.33, 140.78, 139.91, 133.68, 132.86, 131.34, 131.06, 128.55, 128.17, 127.75, 126.96, 124.81, 119.05, 115.56, 55.75 (see...) Figure 13 HRMS (ESI) m / z: [MH] - calcd forC 34 H 25 BrN3O5S, 666.0698; found, 666.0704 (see...) Figure 14 ).

[0052] Figure 15The images show the UV absorption and fluorescence emission spectra of the oxime sulfonate photosensitizers prepared in Examples 1-3 in tetrahydrofuran solvent. The figures show that the maximum absorption peaks of ARP1, ARP2, and ARP3 are at 299 nm, 383 nm, and 399 nm, respectively, while the maximum fluorescence emission peaks are at 394 nm, 541 nm, and 507 nm, respectively. The Stokes shifts of ARP1, ARP2, and ARP3 are 95 nm, 158 nm, and 108 nm, respectively. This indicates that ARP2 and ARP3 have large Stokes shifts, which are beneficial for reducing self-absorption and improving the excitation efficiency in the long-wavelength band, such as white light.

[0053] Figure 16 The graphs show the fluorescence intensity increases of the oxime sulfonate photosensitizers prepared in Examples 1-3 in dimethyl sulfoxide / toluene mixed solvents with toluene content (v / v) of 0%, 20%, 40%, 60%, 80%, and 90%. As can be seen from the graphs, with the increase of the undesirable solvent toluene, the fluorescence intensity of both compounds ARP2 and ARP3 is significantly higher than that of the pure dimethyl sulfoxide system, indicating that both compounds ARP2 and ARP3 possess aggregation-induced emission properties.

[0054] The oxime sulfonate photosensitizers prepared in Examples 1-3 were subjected to performance testing, and the specific methods are as follows: Total reactive oxygen species (ROS) detection: H2DCF-DA probe and photosensitizer were added to a 99% (v / v) dimethyl sulfoxide / water mixed solution. Fluorescence emission changes were measured after different durations of white light irradiation. Probe concentration: 5 μM; Photosensitizer concentration: 4 μM; White light source intensity: 30 mW / cm² 2 .

[0055] Superoxide anion detection: DHR123 probe and photosensitizer were added to a 99% (v / v) dimethyl sulfoxide / water mixed solution. Fluorescence emission changes were measured after different durations of white light irradiation. Probe concentration: 1 μM; Photosensitizer concentration: 2 μM; White light source intensity: 30 mW / cm² 2 .

[0056] Hydroxyl radical detection: HPF probe and photosensitizer were added to a 99% (v / v) dimethyl sulfoxide / water mixed solution. Fluorescence emission changes were measured after different durations of white light irradiation. Probe concentration: 5 μM; Photosensitizer concentration: 2 μM; White light source intensity: 30 mW / cm² 2 .

[0057] Singlet oxygen detection: ABDA probe and photosensitizer were added to a 99% (v / v) dimethyl sulfoxide / water mixed solution. The change in UV absorption was measured after different durations of white light irradiation. Probe concentration: 20 μM; Photosensitizer concentration: 2 μM; White light source intensity: 30 mW / cm² 2 .

[0058] Acid production detection: Take 1.5 mL of acetonitrile solution containing photosensitizer, irradiate it for a specific time under different light sources, then add it to 1.5 mL of acetonitrile solution containing RB, mix thoroughly, and measure the change in UV absorption at 555 nm. RB concentration: 200 μM; photosensitizer concentration: 10 μM.

[0059] Figure 17 The graphs show the changes in fluorescence / absorbance after adding photosensitizers to dimethyl sulfoxide / aqueous solutions containing H2DCF-DA total reactive oxygen species probe, ABDA singlet oxygen probe, DHR123 superoxide anion probe, and HPF hydroxyl radical probe, respectively, and irradiating them continuously. (A) H2DCF-DA detection results show that the fluorescence intensity of ARP2 and ARP3 significantly increased with irradiation time compared to ARP1 and the control group, indicating that ARP2 and ARP3 have a stronger ability to generate reactive oxygen species; (B) ABDA probes capture singlet oxygen (…). 1 The results showed that the absorbance of ARP1, ARP2, and ARP3 was almost unchanged after illumination compared to the control group, indicating that the three substances produced virtually no change. 1 O2; (C) DHR123 probe is used to detect superoxide anion radicals (O2) ·- (D) HPF probes were used to detect hydroxyl radicals (·OH). Both sets of results showed that the fluorescence intensity increase of the ARP2 system was higher than that of ARP1 and ARP3, indicating that ARP2 has a stronger O2-detecting effect. ·- It has the ability to react with ·OH.

[0060] By introducing triphenylamine and methoxytriphenylamine electron-donating groups into the molecular backbone to construct a DA push-pull electron system, the intramolecular charge transfer (ICT) effect can be significantly enhanced, thereby improving the photosensitizer's ability to generate reactive oxygen species (ROS) under light irradiation. Therefore, ARP2 and ARP3 exhibit significantly better ROS generation performance than ARP1, which lacks a DA structure. In the comparison between ARP2 and ARP3, ARP3's O2 generation... ·- Its generation capacity is significantly weaker than ARP2, since ·OH mainly depends on O2. ·- The subsequent transformations are less efficient, therefore ARP3's ability to generate ·OH is weaker than ARP2's. In summary, ARP1, ARP2, and ARP3, the three types of photosensitizers, only generate O2 after light irradiation. ·- Free radicals such as ·OH and reactive oxygen species, without 1Based on the photodynamic mechanism, this type of material, which generates O2, belongs to the type I photosensitizer dominated by electron transfer.

[0061] Figure 18 The reaction equations are for the acids generated by the oxime sulfonate photosensitizers prepared in Examples 1-3 and the reaction with rhodamine (RB). It can be seen that when RB combines with the acid generated by the material, its lactone structure undergoes ring-opening to form a carboxylic acid structure. The higher the acidity of the system, the darker the solution color, and the absorbance at 555 nm increases simultaneously. Therefore, the acid-generating efficiency of the photosensitizer can be quantitatively tested by changes in absorbance.

[0062] Figure 19 In (A), (B), and (C), the illuminance is 1 mW / cm². 2 Different light sources (254nm, 365nm, white light) were used as test conditions. (D) Different irradiation dose gradients of a 365nm light source were used as test conditions. The RB color-changing system was used as a quantitative detection method to record the results at the characteristic absorption wavelength of 555nm. Commercially available photoacid generators NHN-TF (commercially available non-ionic photoacid generator) and DPI (commercially available ionic photoacid generator) (structural formulas are shown below) were also tested. Figure 20 The changes in absorbance of the photosensitizers ARP1, ARP2, and ARP3 after irradiation with different light sources are compared. The increase in absorbance is positively correlated with the total acid production of the photosensitizers under light irradiation, allowing for a direct comparison of the differences in acid production efficiency among the groups.

[0063] from Figure 19 As can be seen, under 254nm ultraviolet light irradiation, the acid production capacity is ARP2 > ARP3 > ARP1 > NHN-TF > DPI; when switched to 365nm ultraviolet light of the same power, the acid production capacity is ARP2 > ARP3 > NHN-TF > ARP1. The ultraviolet absorption peaks of DPI and ARP1 are concentrated in the short-wavelength region below 300nm, while the main absorption bands of NHN-TF are located in the 200-255nm and 300-365nm ranges. Therefore, DPI and ARP1 only have significant acid production effects under 254nm ultraviolet irradiation. NHN-TF, due to its extended absorption band, can produce acid under both 254nm and 365nm ultraviolet light sources. ARP2 and ARP3 can produce acid efficiently under various light sources, their ability stemming from the D-π-A conjugated skeleton formed by their triphenylamine and methoxytriphenylamine. Therefore, ARP1, lacking conjugated units, cannot produce acid through photolysis in the long-wavelength range. ARP3 has a slightly lower molar absorptivity than ARP2, resulting in lower photon utilization and a reduced ability to break bonds and produce acid, thus its acid-producing performance is slightly inferior to ARP2. Compared to traditional photoacid-producing agents DPI and NHN-TF, ARP2 can effectively produce acid under both ultraviolet and white light, has a wider light response window, and is perfectly suited for low-energy, UV-free white light curing processes.

[0064] Application Example 1 Take 5.6 mg of ARP2 prepared in Example 2 and dope it into 1 mL of polyethylene glycol diacrylate (PEGDA). Sonicate the solution until completely dissolved to obtain the photoresist. Spin-coat 100 μL of the photoresist onto a silicon wafer. Cure and image the photoresist using 365 nm UV light through a mask. Clean the uncured photoresist with ethanol as a developer to obtain the mask pattern (see process details). Figure 21 ).

[0065] Figure 22 The images show the photolithography effect of the photoresist. (A) shows the photolithography imaging effect of the ARP2-prepared photoresist under a scanning electron microscope, and (B) shows the linewidth distribution under masks with different slit widths. The scanning electron microscope microscopic images clearly show that the photolithographic pattern boundaries are regular, with no obvious edge diffusion or adhesion between the bottom residual resist and the pattern. This proves that ARP2 can efficiently trigger resin crosslinking under ultraviolet light, ensuring full curing of the exposed area and complete elution of the unexposed area after ethanol development, resulting in excellent pattern fidelity. The ARP2 photosensitizer of this invention, combined with a conventional 365nm ultraviolet lamp, can stably prepare fine photolithographic patterns with a minimum linewidth of 30μm.

[0066] Application Example 2 Add 1 part ARP2 (all parts by weight) to 30 parts isobornyl acrylate (IBOA), stir until completely dissolved, then add 70 parts aliphatic polyurethane acrylate oligomer YC2200 (PUA), disperse evenly, and let stand in the dark for 2 days to fully mix. This will yield the gel nail polish (see process details). Figure 23 ).

[0067] Figure 24 This chart compares the double bond conversion rate, temperature changes, and energy consumption of gel nail polish during curing under different light sources (white light wavelength range: 380nm-780nm; ultraviolet wavelength: 365nm). (A) shows the gel nail polish cured at a power of 20mW / cm². 2 The Fourier transform infrared spectrum changes after irradiation for the same amount of time under different light sources are shown in Figure (A). It can be seen that the curing degree of gel polish is basically the same under ultraviolet light and white light. Figure (B) shows the temperature change of gel polish under different light sources. It can be seen from Figure (B) that the highest curing temperature of gel polish under white light is only 35.0℃, which is milder than the highest curing temperature of 47.6℃ under ultraviolet light. Figure (C) shows the effect of gel polish in actual application. Ultraviolet light can damage the skin, so protective gloves must be worn during operation, while white light does not require such protection. Figure (D) tested the production of the same number of nail tips using gel polish. The energy consumption of the light source was recorded by a power monitor. It can be seen from the figure that the production of gel polish nail tips using white light can achieve lower energy consumption compared to ultraviolet light.

[0068] Figure 25 , Figure 26 ARP2 photosensitizer at different mass fractions (0.16%wt, 0.24%wt, and 0.32%wt) was doped into PEGDA monomer and cured into polymer films by white light irradiation. Photodynamic antibacterial treatment was then performed on Gram-negative bacteria E. coli and Gram-positive bacteria MRSA under a light power of 30 mW / cm². 2 Irradiation for 30 minutes. Results showed that the 0.24%wt group exhibited the best photodynamic sterilization efficiency while maintaining low dark toxicity, achieving a sterilization rate of 90% for MRSA and 99% for E. coli. Notably, the 0.16%wt group had relatively high dark toxicity. This is because at this concentration, the curing crosslinking density was low, and the membrane surface had high hydrophilicity. Residual photosensitizers or unreacted monomers within the membrane were more likely to migrate to the surface, increasing the risk of direct contact with bacteria. Although the photodynamic sterilization effect was better, the dark toxicity limitation restricted its application. The 0.32%wt group, due to its higher degree of curing and increased membrane surface hydrophobicity, avoided contact with bacteria, resulting in a decrease in dark toxicity, but the sterilization effect was weaker. Considering all factors, 0.24%wt was the optimal doping concentration for this system.

[0069] The above data shows that by introducing an electron-donating group on the left side of the oxime sulfonate structure and a benzene derivative on the right side, the present invention organically combines acid production and ROS production characteristics into one molecule, breaking through the technical limitations of traditional oxime sulfonate materials with narrow absorption bands and single functions, and providing a new design idea for developing multifunctional photocurable materials with low energy consumption and wide band response.

[0070] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions, characterized in that, It has the following structure: Wherein, R1 is an aromatic ring derivative group with electron-donating properties, and R2 is a benzene and its derivative group.

2. The oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions according to claim 1, characterized in that, R1 is phenyl, triphenylamino, dimethoxytriphenylamino, naphthyl, anthracene, phenanthryl, phenothiazinyl, phenotoxazinyl, or diphenylamino.

3. The oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions according to claim 2, characterized in that, R1 is one of the structures shown in equation a~i: R' is independently selected from hydrogen atoms or halogen elements.

4. The oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions according to claim 1, characterized in that, R2 is phenyl, naphthyl, phenanthryl or pyrene.

5. The oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions according to claim 4, characterized in that, R2 is one of the structures shown in equations a~d: R' is independently selected from hydrogen atoms or halogens.

6. A method for preparing an oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions as described in any one of claims 1 to 5, characterized in that, Includes the following steps: An aromatic compound containing a cyano group was added to a mixed solvent of toluene and methanol, sodium hydroxide was added, the temperature was raised to 40°C, amyl nitrite was added, the mixture was stirred at a constant temperature, and after post-treatment, an oxime intermediate was obtained. The oxime intermediate was dissolved in ultra-dry tetrahydrofuran, and triethylamine and benzenesulfonyl chloride derivative were added at 0°C under a nitrogen atmosphere. The mixture was then raised to room temperature and reacted. After post-treatment, the oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions was obtained.

7. The application of an oxime sulfonate photosensitizer with both acid-producing and reactive oxygen species-producing functions as described in any one of claims 1 to 5 in the construction of photolithographic patterns.

8. The application according to claim 7, characterized in that, The method for constructing the photolithographic pattern includes: mixing an oxime sulfonate photosensitizer with a polymerizable monomer to obtain a photoresist, coating it on the surface of a substrate, exposing it through a mask, and then washing away the uncured portion with a developer to obtain the photolithographic pattern.

9. The use of an oxime sulfonate photosensitizer with both acid-producing and reactive oxygen-producing functions as described in any one of claims 1 to 5 in the construction of an antibacterial coating.

10. The application according to claim 9, characterized in that, The method for constructing the antibacterial coating includes: mixing an oxime sulfonate photosensitizer with a polymerizable monomer, coating it onto the surface of a substrate, and curing it under light to obtain an antibacterial polymer coating.

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