TW202241586A - Anti-bacterial and anti-viral photocatalytic compositions and methods for manufacturing an article comprising the same - Google Patents

Abstract

Provided is a photocatalytic composition having anti-bacterial and anti-viral activities under visible light irradiation. The photocatalytic composition includes a photocatalyst material, a silver nanoparticle, and a quantum dot. Also provided is an anti-bacterial and anti-viral agent including the photocatalytic composition and a method of manufacturing an article having anti-bacterial and anti-viral activities by using the anti-bacterial and anti-viral agent.

Description

Antibacterial and antiviral photocatalytic composition and method for manufacturing substrate comprising same

The present disclosure relates to photocatalytic compositions comprising photocatalyst materials, in particular to photocatalytic compositions that enhance antibacterial and antiviral activities.

Photocatalysts are semiconductor materials, and the most common photocatalyst semiconductor materials can be made of titanium dioxide (TiO ₂ ). When the photocatalyst is irradiated with light, the energy of the photon can be absorbed by TiO ₂ , and the electron will be excited from its ground state to a higher energy level, thereby promoting an electron in the covalent band (valence band) to the conduction band (conduction band) ), thereby generating a pair of free electrons and holes. The holes can generate oxygen molecules or OH ^- radicals (free radicals), so they have a strong oxidation ability, while the electrons can generate hydrogen peroxide (H ₂ O ₂ ) or superoxide molecules (super oxygen, O ^2- ), also has strong oxidation ability. Therefore, photocatalyst has a strong oxidation ability and is regarded as one of the materials with antibacterial and bactericidal prospects.

However, photocatalysts must be irradiated with ultraviolet rays to have antibacterial activity, but the indoor environment does not necessarily have ultraviolet _rays . Therefore, _{photocatalysts} with _visible light have also been developed one after another. (CGS), Cu ₂ ZnSnS ₄ (CZTS), Ag ₂ S and other nano-ionic materials are paired with each other and mixed in porous carrier materials to make powders, which can produce photocatalyst sterilization effect through visible light irradiation .

Even so, since the semiconductor materials or metal ions used in visible light photocatalysts can only absorb light of a specific wavelength, but there is not necessarily strong light of this specific wavelength in the environment, therefore, compared with direct irradiation of ultraviolet rays on photocatalysts, The bactericidal effect of visible light photocatalyst is usually poor. In view of this, it is still necessary to provide a photocatalyst material that can also have ideal antibacterial, bactericidal, and even antiviral activities under the irradiation of visible light.

The present disclosure provides a photocatalytic composition with adjustable light wavelength and its application in antibacterial and antiviral applications. The photocatalytic composition disclosed in this disclosure is composed of quantum dots and photocatalysts that can adjust the wavelength of light. enhanced antibacterial and antiviral activity.

In at least one embodiment of the present disclosure, the photocatalytic composition of the present disclosure includes photocatalyst materials, silver nanoparticles and quantum dots, which have photocatalytic activity in the spectrum of visible light. In some embodiments of the present disclosure, the photocatalyst material includes titanium dioxide (TiO ₂ ). In some embodiments of the present disclosure, the photocatalyst material further includes CuBiS ₂ , CuGaS ₂ , Cu ₂ ZnSnS ₄ , Ag ₂ S or any combination thereof.

In at least one embodiment of the present disclosure, the quantum dots include CdS, CdSe, Cd/ZnS, ZnS, CdSe/ZnS, perovskite quantum dots or any combination thereof. In some embodiments of the present disclosure, the quantum dots are CdS quantum dots, CdSe/ZnS quantum dots or perovskite quantum dots. In some embodiments of the present disclosure, the quantum dots are blue light quantum dots, for example, the quantum dots absorb light with a wavelength of 360 nm to 780 nm and emit light with a wavelength of 435 nm to 480 nm.

In some specific embodiments of the present disclosure, the present disclosure further provides an antimicrobial agent, such as an antibacterial agent, an antiviral agent or both, which comprises the above-mentioned photocatalytic composition and is formulated into a spray, a coating agent or a film .

In some specific embodiments of the present disclosure, the present disclosure also provides a method for manufacturing a substrate having antibacterial and antiviral activity, comprising applying the above-mentioned antibacterial and antiviral agents to the substrate, and exposing the substrate to UV or visible light to make substrates with antibacterial and antiviral activity. In some embodiments of the present disclosure, the substrate is exposed to the ultraviolet light or the visible light for less than 1 hour, for example, less than 50 minutes, less than 45 minutes, less than 30 minutes, less than 20 minutes, less than 15 minutes, less than 10 minutes minutes, less than 5 minutes, less than 3 minutes, less than 1 minute, less than 30 seconds, less than 10 seconds, or less than 5 seconds.

The photocatalytic composition provided by this disclosure has a high photocatalytic effect under the irradiation of sunlight, fluorescent lamp, visible light or ultraviolet light, therefore, it can also exhibit excellent antibacterial and antiviral activities in an environment with only visible light, and It can be formulated as a spray, coating or film without skin irritation or allergies, and is suitable for application to various substrate surfaces, such as the outer layer of masks, face masks, gloves, filters and other protective covers , or can be sprayed onto the surface of the target to inactivate bacteria and viruses by exposure to ambient light.

The following specific implementations are used to illustrate the technical content of the present disclosure. After reading the disclosure of this specification, those skilled in the art can easily understand its advantages and effects. Furthermore, all ranges and values herein are inclusive and combinable. Any numerical value or point, such as any integer, falling within a range stated herein can be used as a minimum or maximum value to derive the underlying range.

As used in this disclosure and the appended claims, the singular forms "a" and "the" include pluralities, and the term "or" includes "and/or" unless otherwise indicated herein.

The photocatalytic composition of the present disclosure includes photocatalyst material, nano silver particles and quantum dots. By combining quantum dots that can adjust the wavelength of light, photocatalysts, and silver nanoparticles with antibacterial and antiviral activities, the photocatalytic composition of the present disclosure can exhibit excellent antibacterial and antiviral activities under visible light. The viruses mentioned include DNA viruses and RNA viruses, such as influenza virus, enterovirus and coronavirus, such as SARS-CoV-2, etc., and are not limited thereto.

In at least one embodiment of the present disclosure, the photocatalyst material includes TiO 2 such as rutile TiO ₂ and anatase TiO ₂ , such as nanometer _{TiO 2 ,} and may further include other materials. For example, the _{photocatalyst} material can include _TiO2 as the N layer, and other materials such as _CuBiS2 , _CuGaS2 , _Cu2ZnSnS4 , _Ag2S , _etc. /or visible light photocatalyst complex.

In at least one specific embodiment of the present disclosure, the photocatalyst material can be a visible light photocatalyst complex formed by adding nano-iron, nano-silver, nano-gold and/or nano-platinum to the nano-TiO ₂ photocatalyst. For example, the photocatalyst material may include nano-silver, nano-gold and nano-platinum in the nano-TiO ₂ photocatalyst. As shown in Figure 1 and Figure 2, they respectively show the light absorption produced by adding different contents of Fe and Ag in the nano- _TiO2 photocatalyst, and it is found that there is a red shift phenomenon moving to the visible light absorption region.

In at least one specific embodiment of the present disclosure, the quantum dots in the photocatalytic composition of the present disclosure can be irradiated by a light source of a specific wavelength by adjusting the size of the quantum dots to form the wavelength required for the photocatalyst photocatalytic effect For example, quantum dots with different particle sizes can emit light of different wavelengths under the illumination of different light sources. In some embodiments of the present disclosure, the quantum dots in the photocatalytic composition of the present disclosure are blue light quantum dots, which can absorb visible light of different wavelengths and emit blue light.

In at least one embodiment of the present disclosure, the quantum dots may be single-component quantum dots, such as CdS quantum dots. In some specific embodiments of the present disclosure, the quantum dots may also be quantum dots with a multilayer nano-core-shell structure, such as comprising quantum dots selected from CdS, CdSe, Cd/ZnS, ZnS, CdSe/ZnS, and perovskite quantum dots. A multilayer structure composed of components or any combination thereof. In some embodiments of the present disclosure, the quantum dots can also be a mixture of multiple multi-wavelength quantum dots made of different nanometer sizes. As shown in FIG. 3 , it shows that CdSe/CdS/ZnS multilayer structure quantum dots with different particle sizes in some embodiments of the present disclosure emit fluorescence of different wavelengths under the illumination of a light source. Also as shown in FIG. 4 , it shows the absorption spectrum and emission spectrum of quantum dots with a dominant wavelength of 620 nanometers (nm) in some embodiments of the present disclosure.

In at least one embodiment of the present disclosure, the photocatalytic composition of the present disclosure may further include phosphor. In some embodiments of the present disclosure, the phosphor can be a single-wavelength phosphor, such as SrS:Eu ²⁺ phosphor that emits red wavelength after being irradiated by a blue light source. In some specific embodiments of the present disclosure, the fluorescent powder can also be a multi-wavelength fluorescent powder, such as YAG: Ce ³⁺ fluorescent powder (YAG, yttrium aluminum garnet (yttrium aluminum garnet)). In some specific embodiments of the present disclosure, the photocatalytic composition of the present disclosure may also include the above two phosphors.

In at least one embodiment of the present disclosure, the photocatalytic composition of the present disclosure may further include a matrix, such as a soluble polymer or an insoluble polymer. In some specific embodiments of the present disclosure, examples of the soluble polymer include, but are not limited to, polymethyl methacrylate (poly (methyl methacrylate), PMMA), polystyrene (polystyrene, PS), poly Vinyl (polyethylene, PE) and polycarbonate (polycarbonate, PC). In some embodiments of the present disclosure, examples of the insoluble polymer include, but are not limited to, silica gel.

In at least one specific embodiment of the present disclosure, the photocatalytic composition of the present disclosure can be formulated into an antibacterial agent or an antiviral agent, and its use form is not particularly limited, such as spray, coating agent or film, wherein, the present disclosure The film can be single-layer or multi-layer film. For example, the antibacterial agent or antiviral agent of the present disclosure comprises a spray of the above-mentioned photocatalytic composition, which is arranged in a container equipped with a nozzle, and the spray can be sprayed on such as a mask, a face mask, etc. through the nozzle of the container during use. , gloves, protective clothing, filters, or other daily necessities, utensils, clothing, housing facilities, car air conditioning filters, medical equipment, plastic surfaces, glass surfaces, metal surfaces, vehicles (such as airplanes, Ships, cars, public transport), cell phone panels or kiosks, or skin surfaces, making the sprayed target antibacterial and antiviral. In at least one specific embodiment of the present disclosure, the nozzle of the container containing the antibacterial and antiviral spray of the present disclosure can be further equipped with a light source of ultraviolet light or visible light, so that the contained photocatalytic composition can be sprayed during the spraying process. Direct exposure to ultraviolet or visible light can stimulate its photocatalytic antibacterial and antiviral activities.

FIG. 5 is a schematic diagram of a photocatalyst film formed from a photocatalytic composition according to at least one embodiment of the present disclosure. The photocatalyst film 1 includes quantum dots 11 , photocatalyst complex 12 , phosphor powder 13 and matrix 14 . In some specific embodiments of the present disclosure, the quantum dot 11 includes a single-component quantum dot 111, a multilayer nano-core-shell quantum dot 112 or a combination thereof, wherein the multilayer nano-core-shell quantum dot 112 can be composed of a CdSe layer 1121, The CdS layer 1122 , the Cd/ZnS layer 1123 and the ZnS layer 1124 are composed, but not limited thereto. In some specific embodiments of the present disclosure, the average particle size of the quantum dots 11 is 25±2 nm, the emission wavelength is 460 nm, and the full width at half maximum (FWHM) is 28 nm. In some specific embodiments of the present disclosure, the photocatalyst complex 12 can be made of TiO ₂ as the N-type semiconductor powder 121, and other materials (such as CdS, CdSe, Cd/ZnS, ZnS, CdSe/ZnS, perovskite quantum dots, etc.) as a composite formed by the P-type semiconductor powder 122 . In some specific embodiments of the present disclosure, the photocatalyst complex 12 of the present disclosure may also contain nano-iron 123 , nano-silver 124 or both added therein. In some embodiments of the present disclosure, the phosphor 13 includes SrS:Eu ²⁺ phosphor 131 , YAG:Ce ³⁺ phosphor 132 or a combination thereof, but not limited thereto.

The present disclosure also provides a method for manufacturing a substrate with antibacterial and antiviral activity, comprising applying the antibacterial and antiviral agent of the present disclosure to the substrate, and exposing the substrate to ultraviolet light or visible light to form a substrate with antibacterial and antiviral activity. Substrates for antiviral activity. In some specific embodiments of the present disclosure, examples of the substrate include, but are not limited to, a single substrate composed of general components such as fibers, metals, ceramics, and glass, and a substrate composed of two or more of the above components. composite substrates.

The places where the antibacterial and antiviral agents of the present disclosure are used are not particularly limited. For example, the antibacterial and antiviral agents of the present disclosure can also be used in dark places except in the presence of arbitrary light, because the antibacterial and antiviral agents of the present disclosure can still have excellent antibacterial properties in dark places after being irradiated with light. And antiviral activity, which can continuously inactivate bacteria or viruses. For example, the antibacterial and antiviral agents of the present disclosure can be applied on walls, floors, ceilings, etc., and can also be applied in dark places such as inside machinery, storage rooms of refrigerators, hospital facilities that become dark places at night or when not in use Antibacterial and antiviral agents of the present disclosure.

The features and functions of the present disclosure are further illustrated by specific specific examples below, but are not intended to limit the scope of the present disclosure. Example Example 1: Cell Culture

Huh7 human hepatoma cells were cultured in Dulbecco's Modified Eagle Medium (DMEM; Gibco) containing 10% fetal bovine serum (FBS; Gibco) and placed in 5% CO ₂ cultured in a 37°C incubator. When the cells were subcultured, the cells were washed twice with phosphate buffered saline (PBS), and then an appropriate amount of 2.5% trypsin-ethylenediaminetetraacetic acid (EDTA) was added to treat the cells. After the cells fell off the surface of the culture dish, fresh 10% FBS DMEM medium was added, the cells were broken up and evenly distributed in the culture dish, and then cultured in a 37°C incubator containing 5% CO ₂ . Example 2: Virus Culture

Coronavirus 229E was cultured in Huh7 cells. Specifically, the cells were cultured in DMEM medium containing 10% FBS, and when they grew to about 90% full, they were washed with PBS, and then the cells were infected with a virus amount of about 0.01 at a multiplicity of infection (MOI) , and added to DMEM medium containing 10% FBS, and then placed in a 35°C incubator containing 5% CO ₂ for about 48 hours. When 50% of the cells have cytopathic effect (CPE), collect all the culture medium containing virus and CPE cells, centrifuge at 2,000 rpm for 10 minutes, remove all supernatants and store in -80°C . Embodiment 3: the preparation of photocatalyst film

The photocatalyst stock solution is composed of matrix, CdS single-component quantum dots, nano silver and visible light photocatalyst. The matrix is a matrix of insoluble polymers, such as silica gel made of silicon dioxide (SiO ₂ ), but not This is the limit. In other specific embodiments of the present disclosure, the matrix can also be a matrix of soluble polymers, such as polymethyl methacrylate (PMMA), polystyrene (PS), polyethylene (PE) and polycarbonate (PC). When the matrix is an insoluble polymer matrix, quantum dots, nano-silver and visible light photocatalysts can be directly mixed with silica gel to form a silica gel mixture. When the matrix is a matrix of soluble polymers, organic solvents (such as chloroform and toluene) can be used to stir and dissolve the polymers first, and then mix with quantum dots, nano silver and visible light photocatalysts to form polymers polymer mixture.

In at least one specific embodiment of the present disclosure, the photocatalyst stock solution comprises about 2.0% TiO ₂ photocatalyst, about 0.0005% to about 0.001% nano-silver, about 0.001% CdS quantum dots and about 2.0% SiO mixed in water ₂ . In some specific embodiments of the present disclosure, the content of _TiO in the photocatalyst stock solution can be about 0.1%, about 0.2%, about 0.5%, about 0.8%, about 1%, about 1.2%, about 1.5%, about 1.8% %, about 2%, about 2.5%, about 3%, about 4%, or about 5%, without limitation. In some specific embodiments of the present disclosure, the content of quantum dots in the photocatalyst stock solution can be about 0.0005%, about 0.001%, about 0.0015%, about 0.002%, about 0.0025%, about 0.003%, about 0.004%, about 0.005% %, about 0.01%, about 0.02%, or about 0.05%, without limitation. In some specific embodiments of the present disclosure, the content of nano-silver in the photocatalyst stock solution can be about 0.0005%, about 0.0006%, about 0.0007%, about 0.0008%, about 0.0009%, about 0.001%, about 0.005%, about 0.008%, about 0.01%, about 0.02%, about 0.03%, about 0.04% or about 0.05%; 0.002%, or not greater than 0.0025%, or not greater than 0.055%.

In some embodiments of the present disclosure, the photocatalyst film can be made from the mixed solution containing the photocatalyst through physical precipitation method, electrochemical reaction method, ultraviolet curing method or thermocatalytic curing method.

In one of the specific embodiments of the present disclosure, the physical sedimentation method is to use ultrasonic waves to first remove the air bubbles in the polymer mixture, and then pour it into the forming mold. After the organic solvent in it is completely volatilized, it can be Obtain photocatalyst film.

In one of the specific embodiments of the present disclosure, the ultraviolet curing method is to add the polymer mixed liquid or the silicone rubber mixed liquid first into the ultraviolet curable adhesive, and then draw it into a thin film after being fully mixed, and irradiate it with ultraviolet light to make it undergo Cures into a thin film.

In one of the specific embodiments of the present disclosure, the thermal catalytic curing method is to place the silicone rubber mixture in a vacuum box first, then remove the air and organic solvent, and then heat and cure in a curing furnace to obtain Photocatalytic film. Embodiment 4: antiviral test

In order to test the antiviral activity of the photocatalyst film, the virus liquid prepared by 0.5 mL of embodiment 2 and the photocatalyst film prepared by embodiment 3 acted under specific experimental conditions, and the virus liquid was sucked back after completion to carry out the following the test described.

First, after the cells were collected by trypsin-EDTA solution, the cell concentration was adjusted to ⁶ × 105 cells/mL with DMEM medium containing 10% FBS, and then 1 mL of it was inoculated into a 6-well plate and placed in Incubate for 18 to 24 hours in a 37°C incubator with 5% CO ₂ .

Next, the reacted virus solution was serially diluted 10 times to 1×10 ⁸ , then added to the 6-well plate containing the cultured cells, and then put back into the incubator for 64 hours of cultivation. Finally, cells were fixed with 10% formalin (Riedel-de Haen) for 1 hour, and then stained with 0.1% crystal violet (JT Baker) for 5 minutes. Count the number of virus plaques (plaque) compared with the blank group to know the anti-virus ability of the photocatalyst film. The experimental conditions and results of the test examples 1 to 3 are further described below.

test case 1

Experimental conditions: The virus liquid was reacted with the photocatalyst film containing nano-silver and without nano-silver, and UV irradiation was carried out for 5 minutes at a distance of 5 cm from the light source. The results are shown in Table 1 below: Table 1 group Titer of coronavirus 229E Inhibition rate control group 5×10 ⁵ PFU/mL ^* 0% TA 2.4×10 ⁵ PFU/mL 52% TA+UV 0.84×10 ⁵ PFU/mL 83.2% TH+UV 2×10 ⁵ PFU/mL 60% ^* PFU: virus plaque forming unit (plaque forming unit) TA: photocatalyst + nano silver TH: photocatalyst

test case 2

Experimental conditions: The virus solution (the virus concentration is 5 × 10 ⁶ PFU/mL) and the photocatalyst film were mixed with different concentrations of quantum dots, and UV irradiation was performed for 15 minutes at a distance of 7 cm from the light source. The results are shown in Table 2 Shown: Table 2 group Quantum Dot Concentration* 229E coronavirus suppression rate control group none >99.99% 2T0P Low >99.99% 2T1P middle >99.99% 2T2P high >99.99% *0P: No addition; 1P: 0.5%; 2P: 1%

Test case 3

Experimental conditions: The virus liquid (the virus concentration is 5 × 10 ⁶ PFU/mL) and the photocatalyst film are reacted under the condition that the quantum dot concentration is 2P, and UV irradiation is carried out for 5 minutes or 10 minutes at a distance of 7 cm from the light source. As shown in Table 3 below: Table 3 group UV irradiation Action time Photocatalyst film 229E coronavirus suppression rate 1 none 5 minutes have 0% 2 have none 83% 3 have have >99.99% 4 none 10 minutes have 0% 5 have none 93% 6 have have >99.99%

Test case 4

According to the experimental conditions of the above-mentioned test examples 1 to 3, only UV irradiation was changed to visible light irradiation, and it was found that the photocatalyst film irradiated with visible light had an antiviral effect equivalent to that of only UV irradiation. Embodiment 5: photocatalyst antibacterial ability test

In order to test the antibacterial ability of the photocatalyst film prepared in Example 3, the photocatalyst film (containing 1% quantum dot material) and the bacteria were acted on under specific treatment conditions. After the completion, the bacterial solution in the petri dish was serially diluted with PBS. After smearing and culturing for 24 hours, count the number of colonies to calculate the bacteriostatic rate of the photocatalyst film.

The results found that, as shown in Figure 6A, without UV irradiation and without photocatalyst film treatment, the bacteriostatic rate ( E. coli ATCC25922) was 0% (in Figure 6A, from left to right is 100, 10, 1 times dilution The culture medium after the bacteria solution was coated); and Figure 6B shows that after 15 minutes of UV irradiation and photocatalyst film treatment, there are no visible colonies on the culture medium (in Figure 6B, from bottom to top, from left to right are the following 100,000, 10,000, 1,000, 100, 10-fold diluted culture medium after plating).

In addition, after 10 minutes of UV irradiation, the antibacterial rates of photocatalyst film against S. aureus BAA977 and E. coli ATCC25922 can reach 99.99% and 100%, respectively; after 1 minute and 5 minutes of UV irradiation, the inhibition rate of S. aureus BAA977 The bacterial rate is still 99.97%, while the bacteriostatic rate of E. coli ATCC25922 is about 99.92% to 99.95%.

For carbapenem-resistant Acinetobacter baumannii (CR-AB), after 10 minutes of UV irradiation, the bacteriostatic rate of the photocatalyst film can reach 99.99%; and for Pseudomonas aeruginosa , the antibacterial rate of the photocatalyst film irradiated by UV for 10 minutes can reach 100%.

Further, after only 10 seconds, 20 seconds, 30 seconds and 40 seconds of UV irradiation, the antibacterial rate of photocatalyst film to S. The antibacterial rate of . coli ATCC25922 can reach 99.964%, 99.995%, 99.973% and 99.988% respectively.

Under the condition of irradiating with visible light, after the photocatalyst film was irradiated with visible light for 10 minutes, the bacteriostatic rate of E. coli ATCC25922 was 99.999%, which was equivalent to the bacteriostatic effect when only irradiated with UV; and after 20 minutes of irradiating with visible light, S The antibacterial rates of aureus BAA977 and E. coli ATCC25922 can reach 99.9379% and 100%, respectively. For CR-AB and Pseudomonas aeruginosa, it was also found that the photocatalyst film irradiated with visible light had an antibacterial effect equivalent to that only irradiated with UV. Embodiment 6: skin irritation test

In order to test the skin irritation of the photocatalyst stock solution, the following animal experiments were carried out, wherein the photocatalyst stock solution used for the test contained CdSe/ZnS quantum dots, perovskite quantum dots, titanium zeolite, rutile titanium dioxide mixed in pure water , Anatase Titanium Dioxide, Silicon Dioxide, Nano Gold, Nano Platinum and Nano Silver. In some embodiments of the present disclosure, titanium zeolites can be used to prevent precipitation. In some specific embodiments of the present disclosure, the _TiO2 content in the photocatalyst stock solution is about 0.1% to 5% (such as 0.1% to 1.1%, 0.2% to 3.5% and 0.3% to 2%), and the quantum dot content is about 0.0005% to 0.05% (such as 0.001% to 0.05%, 0.005% to 0.02% and 0.008% to 0.01%), nano silver content is about 0.0005% to 0.05% (such as 0.0008% to 0.03%, 0.001% to 0.011% % and 0.003% to 0.008%), the silicon dioxide content is about 0.01% to 1% (such as 0.05% to 1%, 0.1% to 0.8% and 0.3% to 0.5%).

Experimental animals: New Zealand white rabbits (male, purchased from Banqiao Weixin), weighing about 2.4 kg to 3.5 kg. One per cage, the temperature of the feeding environment is 20 ± 3°C, the humidity is 50 ± 20%, the daily lighting time is 12 hours, and the feed and reverse osmosis pure water can be freely ingested.

Test procedure: Before the test, use the electric shaver for animals to push in one direction to shave the upper back hair of the animal, and check whether the skin surface is complete. If the skin surface has scratches or skin diseases, the test will not be carried out. Continue to divide the depilated skin part of the back into upper and lower back areas.

Then, 0.5 mL of the photocatalyst stock solution was applied to gauze with a size of 2.5 cm × 2.5 cm, and then covered on the upper back fur-removed surface, while the lower back skin was not injected with any substance, as a control area. This delivery method is in accordance with the OECD 404 guidelines published by the Organization for Economic Cooperation and Development.

Then the body of the animal was fixed with an elastic air-permeable bandage, and the elastic air-permeable bandage and gauze were removed 4 hours after the administration, and the skin surface was washed with sterilized water for skin irritation evaluation.

Irritation evaluation: at the first ± 0.1 hour, 24 ± 2 hours, 48 ± 2 hours, 72 ± 2 hours after removing the photocatalyst stock solution gauze, observe and record according to the skin reaction judgment standard table (OECD 404) (Table 4) The skin reactions at the injection site and the control site were calculated based on the scores of erythema and edema (primary cutaneous irritation index, PCI), and the irritation of the photocatalyst stock solution was judged according to the single skin irritation evaluation standard table (Table 5) sex. If the skin irritation reaction is observed for more than 72 hours, it is necessary to continue to observe and record the skin irritation reaction until the 14th day to evaluate whether the skin damage is reversible or irreversible. Table 4. Skin reaction judgment standard table (OECD 404) Level of reaction score Erythema and crust formation ． no erythema 0 ． very mild erythema 1 ． obvious erythema 2 ． moderate to high erythema 3 ． Highly erythematous, dark red and crusted 4 edema formation ． no puffiness 0 ． very mild edema 1 ． Mild puffiness (highness identifiable with well-defined borders) 2 ． Moderate edema (approximately 1 mm bump) 3 ． Severe edema (more than 1 mm raised) 4 Table 5. Single skin irritation evaluation benchmark table Principal Skin Irritation Coefficient (PCI) Irritation judgment PCI ≤ 0.5 Non-irritant 0.5 < PCI ≤ 3.0 Slight irritant 3.0 < PCI ≤ 5.0 Moderate irritant 5.0 < PCI ≤ 8.0 Severe irritant

實施例7：皮膚敏感性試驗 The test results are shown in Table 6 below. During the test period, no skin-related reactions were observed caused by the photocatalyst stock solution, and its primary skin irritation coefficient (PCI) was 0. It can be seen that the photocatalytic composition provided by the present disclosure has no skin irritation. Table 6. Skin reaction score group control group test group number of animals 3 3 test substance none Photocatalyst stock solution test site lower back upper back PCI ^# 0 0 ^# PCI=

Embodiment 7: skin sensitivity test

In order to test whether the photocatalyst stock solution will produce a delayed sensitive reaction to the skin, the photocatalyst stock solution described in Example 6 was used to carry out the following animal experiments.

Test animals: guinea pigs (female, Hartley strain, purchased from Banqiao Weixin Co., Ltd.), weighing about 315 grams to 427 grams. One per cage, the temperature of the feeding environment is 20 ± 3°C, the humidity is 50 ± 20%, the daily lighting time is 12 hours, and the feed and reverse osmosis pure water can be freely ingested.

Test procedure: The experimental animals were divided into three groups, namely (1) the negative control group, which was given sterilized water; (2) the positive control group, which was given hexyl cinnamic aldehyde (HCA), which was dissolved in cottonseed oil; and ( 3) The test group was given photocatalyst stock solution. Before the test, the electric shaver for animals was pushed forward in one direction to shave the back hair of the animals. The depilated skin on the back was divided into left and right back, with a total size of about 2 cm × 4 cm.

The test is divided into sensitive evoked response phase and sensitive attack response phase. The sensitivity-induced reaction stage is during the sensitive induction period of intradermal injection. The photocatalyst stock solution is mixed with an adjuvant and injected into the intradermal site on the upper back. During the local injection induction period, the photocatalyst stock solution is directly attached to the injected site. In the sensitive attack reaction stage, the photocatalyst stock solution is directly coated on the lower back. This delivery method follows the OECD 406 guidelines published by the Organization for Economic Cooperation and Development.

On the day of intradermal injection sensitive induction period test, symmetrically inject 0.1 mL each of the following three substances into the left and right upper back respectively: Position (A): Emulsion (E-FCA) of control solvent mixed with Freund’s complete adjuvant (FCA) at a volume ratio of 1:1. The test group and the negative control group used the E-FCA of the negative control group, and the positive control group used the E-FCA of the positive control group; Position (B): The photocatalyst stock solution (undiluted) was directly administered to the animals in the test group, the negative control group was administered with sterilized water, and the positive control group was administered with HCA; Position (C): Photocatalyst stock solution (undiluted) and E-FCA were mixed at a ratio of 1:1 to form an emulsion, which was directly administered to the animals in the test group. The control solvent was mixed with E-FCA to form an emulsion and administered to the negative control group and the positive group. control group.

One week later, the local administration induction period was carried out, and 0.5 mL of 10% sodium dodecyl sulfate (sodium dodecyl sulfate, SDS) solution was applied to the site of the previous intradermal injection, and 24 hours later, it was covered with 0.2 mL of photocatalyst stock solution or control solvent The dressing was placed on the same site and removed after 48 hours.

The sensitive challenge reaction period was two weeks after the induced administration, and the dressing (2 cm × 2 cm) containing 0.1 mL of the photocatalyst stock solution was covered on the lower back of the animals and removed after 24 hours.

Sensitivity assessment: at 24 ± 2 hours and 48 ± 2 hours after the treatment of the sensitive attack reaction test, scores are given according to the skin reaction judgment standard table (OECD 406) (Table 7). If the score of the control group is less than 1 and the score of the test group is not less than 1, or the score of the control group is not less than 1 and the score of the test group is greater than the score of the control group, it is judged that the test substance is sensitive to the skin. Table 7. Skin reaction judgment standard table (OECD 406) Level of reaction score No significant change 0 Diffuse or macular erythema 1 moderate confluent erythema 2 Severe erythema and edema 3

The test results are shown in Table 8 and Table 9 below. At 24 ± 2 and 48 ± 2 hours after the sensitive attack reaction test, the photocatalyst stock solution and the negative control group had no obvious skin reaction, while 60% of the positive control group had The test animals have a positive reaction, meeting the OECD 406 requirement of at least 30%. It can be seen that the photocatalytic composition provided by the present disclosure will not cause delayed sensitive reaction to animal skin. Table 8. Score results of skin reaction symptoms of individual animals group animal number Sensitive challenge reaction 24 ± 2 hours after treatment Sensitive challenge reaction 48 ± 2 hours after treatment Negative control group (sterilized water) 212722201 0 0 212722202 0 0 212722203 0 0 212722204 0 0 212722205 0 0 positive control group (HCA) 212722206 1 1 212722207 1 1 212722208 0 0 212722209 0 0 212722210 1 1 Test group (photocatalyst stock solution) 212722211 0 0 212722212 0 0 212722213 0 0 212722214 0 0 212722215 0 0 212722216 0 0 212722217 0 0 212722218 0 0 212722219 0 0 212722220 0 0 Table 9. Incidence of skin reaction symptoms group negative control group positive control group test group number of animals 5 5 10 test substance Sterilized water HCA Photocatalyst stock solution erythema 0/5 ^* 3/5 0/10 edema 0/5 0/5 0/10 ^* n/n: number of animals with erythema or edema/number of animals in each group Example 8: oral acute toxicity test

In order to test the acute toxicity changes that may be caused by the photocatalyst stock solution after oral administration, the photocatalyst stock solution described in Example 6 was used to carry out the following animal experiments.

Experimental animals: 8-week-old SD rats (female, purchased from Lesco Biotechnology Co., Ltd.). During the test period, one cage was used, the temperature of the breeding environment was 22 ± 3°C, the humidity was 50 ± 20%, the daily lighting time was 12 hours, and the feed and reverse osmosis pure water could be freely ingested.

Test procedure: The photocatalyst stock solution was prepared into 60 mg/mL and 400 mg/mL operating solutions with sterilized water (the injection volume was 5 mL/kg). The test animals were fasted the night before the administration, and the formulated photocatalyst stock solution was orally administered once on the day of the administration. The test was conducted using step-wise administration (see Table 10 below), using three test animals per step, with 300 mg/kg for steps 1 and 2, followed by 2,000 mg/kg for steps 3 and 2,000 mg/kg 4 doses. This delivery method is in accordance with the OECD 423 guidelines published by the Organization for Economic Cooperation and Development. Table 10. Step-by-step test administration process step Administration dose (mg/kg) Administration concentration (mg/mL) Administration volume (mL/kg) number of animals 1 300 60 5 3 2 300 60 5 3 3 2,000 400 5 3 4 2,000 400 5 3

Observation of clinical symptoms and pathological examination: Observe the health status and abnormal clinical symptoms of the animals before administration on the test day, 0.5, 4 ± 0.5 hours after administration, and every day during the observation period of the experiment. The observation period of the experiment is 14 days. Observations include skin, hair, eyes, and mucous membranes, as well as respiratory, circulatory, autonomic, central nervous, motor nervous system, and behavioral patterns. Animals that died during the experiment were required to undergo necropsy. At the end of the experiment, all surviving animals were euthanized by carbon dioxide and sacrificed for necropsy. The appearance, oral cavity, cranial cavity, and all tissues and organs in the chest and abdominal cavity were inspected with the naked eye, and records were made.

The results of the test found that during the test, all the test animals did not die, did not have any abnormal clinical symptoms, had no abnormal changes in body weight, and could eat normally. observed lesions. It can be seen that the oral half-lethal dose (LD ₅₀ ) of the photocatalytic composition provided in this disclosure to SD rats is greater than 2,000 mg/kg, according to the globally harmonized system of classification and labeling of chemicals (globally harmonized system of classification and labeling of chemicals, GHS) can be classified as level 5, that is, the lowest acute toxicity hazard level. Example 9: In Vitro Cytotoxicity Test

In order to test whether the photocatalyst stock solution has cytotoxicity, the photocatalyst stock solution described in Example 6 was used to carry out the following in vitro cytotoxicity agar diffusion evaluation test, and this test was based on the specification of the International Organization for Standardization (ISO 10993-5).

Test procedure: the mouse lung fibroblast cell line (NCTC Clone 929, BCRC No.: RM 60091, from the Bioresource Conservation and Research Center of the Food Industry Development Institute of the Foundation) was cultured in the minimum essential medium (MEM) Medium (containing 10% fetal bovine serum, 2 mM L-glutamine, 2.2 g/L sodium bicarbonate, 0.11 g/L sodium pyruvate and 100 U penicillin/100 μg/mL streptomycin), placed at 37 ℃, 5% _CO2 incubator. Subculture was carried out when the cells grew to 7 or 8 minutes under microscope. After 2 or 3 passages, the cells were quantified as 1 × 106 cells per well and cultured in ⁶ -well cell plates, placed in 37°C, 5% Incubate in a CO ₂ incubator for 24 hours.

3% Noble agar (from BD Biosciences) was sterilized at 121°C for 30 minutes under high temperature and high pressure, mixed with the same volume of 2×MEM medium, and cooled to about 39°C. After the cells were cultured, suck off the old medium and then add 2 mL of agar medium, and let stand at room temperature to solidify the agar layer.

About 0.1 mL of the photocatalyst stock solution was evenly spread on a 1 cm × 1 cm filter paper, and then the filter paper was placed on the agar layer, so that the photocatalyst stock solution was in direct contact with the agar layer, and left for 24 hours. High density polyethylene film (high density polyethylene film, HDPE, from Hatano Research Institute) and zinc diethyldithiocarbamate polyurethane film (from Hatano Research Institute) were used as negative control and positive control, respectively Group substances were cut into 1 cm × 1 cm size and placed on the agar layer for 24 hours. Each test sample was tested in triplicate.

Next, trace the outline of the test sample from the bottom of the cell plate, add 2 mL of neutral red (neutral red) solution, continue to incubate for 1 hour, suck off the neutral red solution, and check the growth of cells under and around the test sample under a microscope situation.

Cytotoxicity assessment: Scores were given based on the area formed by cells that were not stained with neutral red solution (Table 11). When the scoring result is greater than 2, it is judged that the test sample causes a cytotoxic reaction. If a cytotoxic reaction is observed in the negative control group, or no cytotoxic reaction is observed in the positive control group, the test is invalid. Table 11. Agar Diffusion Test Cytotoxicity Grade Scoring Criteria grade reactivity illustrate 0 non-cytotoxic No observable area formed under or around the test specimen 1 mild cytotoxicity Some cells below the test sample showed abnormal patterns 2 mild cytotoxicity Confined to the formation of an observable area beneath the test sample 3 moderate cytotoxicity An observable area formed below the test sample extending outward to a range of 1.0 cm 4 severe cytotoxicity Formation of an observable area extending outward beyond 1.0 cm below the test sample

The test results are shown in Table 12 and Figure 7. The negative control group has a score of 0, indicating that the substance in the negative control group has no cytotoxicity, while the positive control group exhibits moderate cytotoxicity (the score is 3), indicating that the test is Valid test. Under this test condition, the cytotoxicity score of the photocatalyst stock solution is 0; in other words, the cytotoxicity level caused by the photocatalyst composition provided in this disclosure is not greater than 2, which meets the requirements of ISO 10993-5 in vitro cytotoxicity test specification. Table 12. Cytotoxic reaction grade group Reaction Rating (0 to 4) ^# Cytotoxicity 1 2 3 average value Blank group (only cells) 0 0 0 0 none Photocatalyst stock solution 0 0 0 0 none negative control group 0 0 0 0 none positive control group 3 3 3 3 Moderate ^#Carry out scoring according to the standard of table 11 Example 10: environment clearing test

In this example, the photocatalyst stock solution described in Example 6 was used as an environmental cleaning agent and sprayed on the surface of environmental objects susceptible to pathogen contamination to evaluate the antibacterial and antiviral long-lasting effects of the photocatalyst stock solution applied to the environment.

test case 1

Application area: equipment frequently touched by passengers in Taoyuan Airport MRT Station A18 and A17

Application method: On the day of disinfection (D), use the photocatalyst stock solution to disinfect the test equipment, and wipe it with clean water or disinfect according to the original disinfection method of the station during the rest of the test period.

Inspection method:

1. Using the adenosine triphosphate (ATP) biological luminescence reaction method, using a hand-held ATP microbial luminescence instrument (Kikkoman), the same person and the same method were used for sampling.

2. Fix the sampling point and area, and frame it with a paper frame. The minimum sampling area is 5 × 5 cm ² , and the maximum is 10 × 10 cm ² . The principle is to sample 10 × 10 cm ² at large-area sampling points, and completely sample at sampling points less than 5 × 5 cm ² .

3. Before sampling, wipe the surface of the application area with clean water before sampling, and avoid sampling in over-humidity or water droplets, so as to avoid the inability to completely obtain ATP of a fixed area.

4. Confirm whether the ATP sampling and testing swab is kept in a wet state. The sampling and testing method is first to wipe horizontally in a Z-shape and then vertically up and down. The sampling and testing swab touches the sampling surface at 360 degrees.

5. After the sampling is completed, put the sampling swab back into the test tube, and make an interpretation within 4 hours.

6. When reading, press the test swab vertically to the bottom to mix with the reagent under the test tube to activate, shake it left and right for 5 seconds, knock out the air bubbles, and put it into a photometer to read its relative light unit (RLU) value. Read within 30 seconds of activation.

Before cleaning the original solution of photocatalyst, spray and disinfect the application area with quaternary ammonium, and carry out ATP sampling after 1 hour as the original bacterial value. After the photocatalyst stock solution is cleared, it will be tested immediately, and then re-tested 3 to 24 days later. The test results are shown in Table 13 and Table 14 below: Table 13 station equipment Raw bacteria count (RLU value) Inspection date Test observation conditions On the day of disinfection (D) D+3 D+10 D+16 D+24 A18 Add-in machine panel No. 1 1,326 411 985 51 394 232 Wipe with clean water during the test No. 2 value-added machine panel 1,810 868 486 149 354 210 Normal disinfection during testing Table 14 station equipment Raw bacteria count (RLU value) Inspection date Test observation conditions On the day of disinfection (D) D+4 D+10 D+18 A17 No. 1 ticket vending machine panel 9,341 1,217 195 293 437 Wipe with clean water during the test No. 2 value-added machine panel 5,633 1,361 395 497 394 Normal disinfection during testing Add-in machine panel No. 3 5,092 2,084 555 270 306 Normal disinfection during testing

test case 2

Work area: Taoyuan Aviation Service Co., Ltd.

Application method: ATP sampling was carried out before and after the photocatalyst stock solution was used to disinfect the sampling point (the sampling method is the same as the above), and the sample was collected again 14 days after disinfection to evaluate the long-term disinfection effect of the photocatalyst stock solution.

The test results are shown in Table 15 below: Table 15 Check point Sampling RLU value before spraying Sampling RLU value after spraying Sample RLU value after 14 days Sustained effect after 14 days Medium Bus Seat Armrest 5,096 679 146 97.1% Toilet cleaning truck hose connector 6,807 964 203 97.1% wheelchair armrest 7,526 1,829 337 95.5% Patient car compartment wall 85 49 53 37.6%

The above results show that the photocatalytic composition provided in the present disclosure can form a coating film on the surface after being sprayed, and the continuous disinfection effect after 14 days is above 95%. According to the commonly used RLU management benchmark value recommended by the original instrument factory, the RLU value of medical institutions and central kitchens should be 200 to 500. Therefore, after cleaning with the photocatalytic composition provided in this disclosure, the RLU value of the environment meets the requirements of medical institutions. The management benchmark of the Institute, and the effect can last for more than 24 days.

It can be seen from the above that the photocatalytic composition provided by this disclosure has a high photocatalytic effect under the irradiation of sunlight, fluorescent lamp, visible light or ultraviolet light, so it can also exhibit excellent antibacterial and antibacterial properties in an environment with only visible light. Viral activity; in addition, compared with common products such as alcohol, hypochlorous acid water, quaternary ammonium, and chlorine dioxide, the effect lasts only for 1 hour at most. The photocatalytic composition disclosed in this disclosure has stable and Long-term anti-pathogenic effect, and can reduce the amount of silver ions, that is, the photocatalytic composition of the present disclosure contains silver ions in an amount lower than the human body's silver ion tolerance (0.0025%), which can achieve effective Antibacterial and antiviral effects. Therefore, the photocatalytic composition of the present disclosure provides a safe antibacterial and antiviral method that is convenient to use and has low impact on the human body.

The above-mentioned embodiments are used to illustrate the principles and functions of the present disclosure, but not to limit the present disclosure. Anyone skilled in the art can modify the above embodiments without departing from the scope of this disclosure. Therefore, the scope of protection of the present disclosure should be listed in the scope of the patent application described later.

1: Photocatalyst film 11: Quantum dots 111: Single-component quantum dots 112: Multilayer nano-core-shell quantum dots 1121: CdSe layer 1122: CdS layer 1123: Cd/ZnS layer 1124: ZnS layer 12: Photocatalyst complex 121: N Type semiconductor powder 122: P-type semiconductor powder 123: nano-iron 124: nano-silver 13: phosphor powder 131: SrS: Eu ²⁺ phosphor powder 132: YAG: Ce ³⁺ phosphor powder 14: matrix

Fig. 1 is the absorption spectrum diagram of Fe/TiO ₂ photocatalyst powder made by doping TiO ₂ photocatalyst with different proportions of nano-iron. Abs: Absorbance.

Figure 2 is the absorption spectrum diagram of Ag/ _TiO2 photocatalyst powder made by mixing nano-silver into _TiO2 photocatalyst in different proportions. Abs: Absorbance.

FIG. 3 shows that CdSe/CdS/ZnS quantum dots with different particle sizes emit fluorescence of different wavelengths under the illumination of a light source.

Figure 4 shows the absorption and emission spectra of quantum dots with a dominant wavelength of 620 nm.

FIG. 5 is a schematic diagram of a photocatalyst film formed from a photocatalytic composition according to one embodiment of the present disclosure.

Figure 6A and Figure 6B show the antibacterial effect of untreated photocatalyst film treatment and UV irradiation for 15 minutes, respectively.

FIG. 7 shows the results of a cytotoxic reaction test of a photocatalytic composition according to one embodiment of the present disclosure. Blank group: no treatment; negative control group: high density polyethylene film (HDPE); positive control group: zinc diethyldithiocarbamate (ZDEC) polyurethane film; test substance group: The photocatalytic composition of the present disclosure. The magnification is 100×, stained with neutral red (neutral red).

1: Photocatalyst film

11: Quantum dots

111: Single Component Quantum Dots

112: Multilayer nano-core-shell quantum dots

1121: CdSe layer

1122:CdS layer

1123: Cd/ZnS layer

1124: ZnS layer

12: Photocatalyst complex

121: N-type semiconductor powder

122: P-type semiconductor powder

123: Nanoiron

124: nano silver

13: Phosphor powder

131:SrS: Eu ²⁺ phosphor

132:YAG: Ce ³⁺ phosphor

14: Matrix

Claims (19)

A photocatalytic composition, including photocatalyst material, nanometer silver particles and quantum dots. The photocatalytic composition according to claim 1, wherein the photocatalyst material comprises titanium dioxide. The photocatalytic composition according to claim 2, wherein the photocatalyst material further comprises CuBiS ₂ , CuGaS ₂ , Cu ₂ ZnSnS ₄ , Ag ₂ S or any combination thereof. The photocatalytic composition according to claim 1, wherein the quantum dots comprise CdS, CdSe, Cd/ZnS, ZnS, CdSe/ZnS, perovskite quantum dots or any combination thereof. The photocatalytic composition according to claim 1, wherein the quantum dots are blue light quantum dots. The photocatalytic composition according to claim 1, wherein the quantum dots are CdS quantum dots. The photocatalytic composition according to claim 6, wherein the quantum dots absorb light with a wavelength of 360 nm to 780 nm and emit light with a wavelength of 435 nm to 480 nm. The photocatalytic composition as described in Claim 1, further comprising nano-gold, nano-platinum or a combination thereof. The photocatalytic composition according to claim 1, further comprising fluorescent powder. The photocatalytic composition according to claim 9, wherein the phosphor is single-wavelength phosphor, multi-wavelength phosphor or a combination thereof. The photocatalytic composition according to claim 10, wherein the phosphor is SrS:Eu ²⁺ phosphor, YAG:Ce ³⁺ phosphor or a combination thereof. The photocatalytic composition according to claim 1, further comprising a matrix selected from the group consisting of polymethyl methacrylate, polystyrene, polyethylene, polycarbonate and silica gel. The photocatalytic composition according to claim 1, which has photocatalytic activity under the irradiation of visible light spectrum. An antimicrobial agent, comprising the photocatalytic composition as described in any one of claims 1 to 13. The antimicrobial agent according to claim 14, which is an antibacterial agent or an antiviral agent. The antimicrobial agent according to claim 14, which is formulated as a spray, coating or film. A method of manufacturing a substrate with antibacterial and antiviral activity, comprising applying the antimicrobial agent as described in any one of claims 14 to 16 on the substrate, and exposing the substrate to ultraviolet light or visible light, To make substrates with antibacterial and antiviral activities. The method as described in claim 17, wherein the base material is a mask, face mask, gloves, protective clothing, filter screen, clothing, house facilities, vehicle interior, medical equipment, plastic surface, glass surface, metal surface, mobile phone panel or a kiosk. The method according to claim 17, wherein the substrate is exposed to the ultraviolet light or the visible light for less than 1 hour.

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