KR101796634B1 - Apparatus for sterilizing microorganism using photoenergy and Sterilizing method using the same - Google Patents

Abstract

The present invention relates to an apparatus for disinfecting food microorganisms, comprising at least one of a container (10), a photofunctional bead (20), a light source device (30), a conduit (40) and a circulation motor The disinfecting device and the disinfecting method can remove the microorganisms in the food safely without deteriorating the quality of the food and remaining the chemical quality, and the disinfection method is simple.

Description

TECHNICAL FIELD The present invention relates to a microorganism disinfection apparatus using photo-energy and a method of sterilizing microorganisms using photoinergy and sterilizing method using the same.

The present invention relates to an apparatus for disinfecting microorganisms using light energy, and a method of disinfecting agricultural products using the same.

In recent years of well-being, the consumption of fresh vegetables and fruits including sprouts vegetables, baby vegetables, etc. has been rapidly increasing worldwide. However, with the growth of the fresh vegetable market, the number of people suffering from food poisoning has increased sharply. Therefore, there is a need for an excellent sterilization technology for food poisoning prevention.

In general, there are physical and chemical methods of disinfection of food. Physical methods are methods such as heating and freezing, and chemical methods are sterilization methods through chemical synthesis agents such as preservatives and bactericides. However, conventional heat treatment methods have disadvantages such as deterioration of freshness of food, deterioration of quality and nutrition loss, and refrigeration and freezing methods proposed as a method to compensate them have disadvantages such as enormous cost input due to low temperature maintenance and quality deterioration at thawing . Sterilization methods using chemical synthetic agents can prevent high sterilization efficiency and food quality deterioration, but they are not used due to the negative effects on the human body due to the resistance of microorganisms, resistance to drugs, residual risks of drugs and environmental problems. Therefore, development of a sterilization technology for food that complements the above disadvantages is urgently required.

Journal of Agricultural Science, Vol. 15, No. 2, 2011 Korean Journal of Food Preservation and Distribution Volume 20, Issue 3, 2013

The present invention relates to an apparatus for disinfecting harmful microorganisms in foods and a method of sterilizing food by using the apparatus for sterilizing harmful microorganisms of foods, comprising at least one of a container (10), a photofunctional bead (20), a light source device (30), a conduit (40) Disclosed is a disinfection apparatus for disinfecting harmful microorganisms in food without any loss of food freshness, quality deterioration, nutritional loss, resistance to microorganisms, and the risk of chemical residues.

According to the present invention,

A container for receiving water;

A photofunctional bead contained in water and comprising a photosensitizer; And

A disinfecting device including a light source device for irradiating light is provided.

Also,

Placing a disinfecting object in the water of the device according to the present invention; And

And a step of irradiating light.

The disinfecting device and the disinfecting method according to the present invention can safely remove microorganisms in food without deteriorating the quality of food and remaining chemical, and the disinfection method is simple.

1 is a schematic diagram showing a configuration of a disinfecting apparatus according to the present invention.
2 is a graph showing the disinfection efficacy of photo-functional beads according to the conditions of Table 1 of Example 1. Fig.
Fig. 3 is a graph showing the disinfecting effect of the photo-functional bead according to the conditions of Table 2 of Example 1. Fig.
4 is a graph showing disinfection efficacy of photo-functional beads according to Table 3 conditions of Example 1. Fig.
FIG. 5 is a graph showing the disinfecting effect of the photo-functional beads according to the conditions of Table 4 of Example 1. FIG.
6 is a graph showing the disinfection efficacy of photo-functional beads according to the conditions of Table 5 of Example 1. Fig.
7 is a graph showing the disinfecting effect of the photo-functional container containing the photo-functional film according to the conditions of Table 6 of Example 2. Fig.
FIG. 8 is a graph showing the disinfecting effect of the photo-functional container containing the photo-functional film according to the conditions of Table 7 of Example 2. FIG.
9 is a graph showing the disinfecting effect of the photo-functional container including the photo-functional alloy film according to the conditions of Table 8 of Example 3. Fig.
10 is a graph showing the light absorption rate of the photo-functional bead prepared in Production Example 1 of Experimental Example 1-1 and the photo-functional bead containing TDCPP prepared in Production Example 2 according to the wavelength.
11 is a graph showing the light absorption rate of the photo-functional material including the photo-sensitizer hematoporphyrin (HP) solution of Experimental Example 1-2 and the photo-functional film containing the hematoporphyrin (HP) prepared in Production Example 3 according to the wavelength.
12 is a graph showing the concentration change of 4-chlorophenol according to the wavelength in Experimental Example 2-1.
13 is a graph showing the absorbance of 4-chlorophenol according to wavelengths in Experimental Example 2-2 at measurement time.
14 is a graph showing the decay of phosphorescence due to the relaxation of monooxygen from the photofunctional film containing TDCPP prepared in Production Example 2. Fig.
15 is a graph showing the absorbance of 1,3-phenylisobenzofuran (DPBF) according to the wavelength of light irradiated to the photo-functional alloy film produced in Production Example 3 of Experimental Example 2-4.
FIG. 16 is a graph showing X-ray photoelectron spectroscopy (XPS) of each kind of film: (a) pure stainless steel, (b) stainless steel containing hydroxyl group, (c) To a photo-functional alloy film.

The disinfection apparatus according to one embodiment of the present invention includes:

A container for receiving water;

A photofunctional bead contained in water and comprising a photosensitizer; And

A disinfecting device including a light source device for irradiating light is provided.

According to another embodiment of the present invention,

A conduit connecting at least two points of the vessel to allow water to circulate; And

And a circulation motor installed in the conduit to circulate the water.

The disinfection apparatus according to the present invention comprises a container 10, a photo-functional bead 20, a light source device 30, a conduit 40, and a circulation motor (not shown) 50). ≪ / RTI >

The container 10 may have a structure in which a photosensitive region is dispersed in a certain region or more of the inner surfaces. The container 10 is not particularly limited as long as it is a material exhibiting light transmittance. The container 10 may comprise, for example, a photofunctional film or a photosensitizer alloy film. The photo-functional film may mean a film in which a photo-sensitizer and a photo-curable polymer resin are mixed. The photocurable polymer resin may include at least one selected from the group consisting of silicon, latex, polyurethane, and polyethylene terephthalate. By using the photo-curable polymer resin, the resin 10 and the photo-sensitizer can be mixed to produce the photo-functional film to produce the container 10.

The meaning of "certain area" of the inner surface of the container may be inclusive of the bottom surface and / or side surface of the container, and in some cases both bottom surface and / or side surface, As shown in FIG. For example, the structure includes a structure in which a region where the photosensitive material is dispersed and a region where the photosensitive material is not dispersed are alternately repeated.

On the other hand, the photo-sensitizer alloy film may mean a film having a photo-sensitizer ester-bonded to a metal surface. The metal may include at least one selected from the group consisting of stainless steel, aluminum, magnesium, tin, titanium, tungsten, and nickel.

The container 10 may serve to receive the disinfecting object 60 contaminated with water and harmful microorganisms. The size and the volume of the container 10 are not particularly limited and can be appropriately set.

A container (10) comprising a photofunctional film or a photosensitizer alloy film generates active oxygen in oxygen using the light energy of the light source during light irradiation, and sterilizes the harmful microorganisms in the water contained in the container with the active oxygen can do.

The disinfecting object 60 contaminated with the harmful microorganisms is not particularly limited and may include at least one of vegetable and fruit. Foods containing harmful microorganisms may be used. The harmful microorganisms may include, for example, bacteria, food poisoning bacteria, and the like. Specifically, the harmful microorganism may include any one or more selected from the group consisting of Escherichia coli, Staphylococcus aureus, cholera, and Salmonella.

The photofunctional bead 20 may be a polymer bead carrying a photosensitizer through a swelling method in which the solution of the photosensitizer is absorbed by the polymer beads. The photo-functional beads 30 may be beads having bactericidal action by the active oxygen generated through light energy induction by the polymer beads into which the photosensitizer is introduced. The polymer beads may be at least one selected from the group consisting of polyurethane, polyurethane acrylate, and polyethylene phthalate. Preferably, polypropylene can be used.

The diameter of the photofunctional bead 20 may be 0.1 to 40 mm. Specifically, the diameter of the beads 20 may be 0.1 to 35 mm, 0.1 to 30 mm, 0.5 to 30 mm, 1.0 to 30 mm, 0.5 to 25 mm, 1.0 to 25 mm, 1.5 to 25 mm, and 0.1 to 20 mm. The photofunctional bead 20 having a diameter in the above range is effective for sterilizing the disinfection target body 60 without tangling in water.

The light source device 30 is capable of irradiating light to at least one of a side surface, a lower surface, and an upper surface of the container 10, and irradiates light to induce photodynamic inactivation (PDI). As the light source device 30, for example, a light emitting diode (LED), a laser Xenon lamp, or the like can be used, and preferably a green LED can be used. The output of the light source device 50 may be, for example, 1 mW / cm ^{2 or} more. Specifically, the output of the light source device 50 is from 1 to 20 mW / cm ^2, 1 to 15 mW / cm ^2, 1 to 13 mW / cm ^2, 1 to 10 mW / cm ^2, from 1 to 8 mW / cm ² , 0.1 to 8 mW / cm ^2, and 0.1 to 5 mW / cm ² .

In addition, the wavelength of the light source device 30 may be 400 to 700 nm. Specifically, the wavelength of the light source device 30 is 405 to 700 nm, 405 to 680 nm, 410 to 680 nm, 410 to 660 nm, 415 to 650 nm, 420 to 650 nm, 420 to 620 nm and 460 to 600 nm Lt; / RTI > The light source device 30 in the wavelength range can be used to measure the wavelength of the light emitted from the light emitting device 30 in the container 10, the bead 20, or the conduit 40, because the absorption rate is high when the wavelength of the photosensitizer used in the present invention is 400 to 700 nm. The efficacy of the disinfection of harmful microorganisms can be enhanced.

The inner surface of the conduit 40 may be ester-bonded with a photosensitizer. The conduit may include at least one selected from the group consisting of stainless steel, aluminum, magnesium, tin, titanium, tungsten, and nickel. The conduit 40 can connect more than two points of the vessel 10 to circulate the water. Because it includes the conduit 40, it is easy to inject and discharge the water, and the circulation of the optical functional beads 20 included in the water is facilitated, so that further prevention of pollution, recovery and reusability are easy. Also, it is possible to control the photo-energy induced active oxygen for the destruction of harmful microorganisms.

The water circulation motor 50 is not particularly limited as long as it is a motor that smoothly flows the water in the container. The water circulation motor 50 may be located in the middle of the conduit 40. The water circulation motor 50 facilitates the circulation of the photofunctional beads 20 in the container 10, thereby facilitating further prevention of contamination, recovery, and reusability. Also, it is possible to control the photo-energy induced active oxygen for the destruction of harmful microorganisms.

In the present invention, the photosensitizer is a compound selected from the group consisting of a porphyrin compound and its substituent, a phthalocyanine compound, a substituent thereof, and a dye selected from the group consisting of a porphyrin compound and its substituent, Or more.

Specifically, the photosensitizer is selected from the group consisting of hemato porphyrin (HP), tris (1,3-dichloroisopropyl) phosphate (TDCPP), tetraphenyl porphyrin ₂ TPP), 5,10,15-triphenyl-20- (4-carboxyphenyl) -porphyrin platinum (PtCP), 5,15 Bisphenyl-10,20-bis (4-methoxycarbonylphenyl) -porphyrin platinum, t-PtCP), protoporphyrin proto porphyrin, PP), indocyanine green (ICG) and meso-tetrakis (psulfonatophenyl) porphyrin (TSPP). .

The concentration of the photosensitizer may be 1 × 10 ^-8 to 30 × 10 ^-7 mol per 1 g of the polymer resin. Excellent dispersibility can be obtained at such a concentration range. This concentration range is a range in which the introduced photosensitizer does not cause entanglement and also expresses active oxygen depending on the concentration of the introduced photosensitizer. The photosensitizer is included in the polymer bead body to impart bactericidal properties. Specifically, the photosensitizer absorbs light energy in an absorption wavelength region of 400 nm to 700 nm, and generates active oxygen by induced light energy Thereby exhibiting bactericidal action.

In addition, the present invention, in one embodiment,

Placing a disinfecting object in the water of the disinfecting apparatus according to the present invention; And

And irradiating light.

Firstly, the step of inserting the disinfection object 60 into the water is a step of inserting at least one of vegetables and fruits into the disinfecting apparatus according to the present invention. The object to be sterilized is not particularly limited, and it can be used if it is food that is washed in water. Specifically, it may be an agricultural product such as vegetables and fruits contaminated with harmful microorganisms.

Also, in the step of irradiating the light, a light source having a wavelength of 400 to 700 nm may be irradiated to one or more of the side surface, the lower surface, and the upper surface of the container 10. Upon irradiation of the light source, the photosensitizer contained in at least one of the vessel 10, the bead 20, and the conduit 40 may react with oxygen to produce active oxygen. The active oxygen may sterilize the harmful microorganisms in the disinfection target body 60.

In the step of irradiating light, the light irradiation output may have a light irradiation time of 30 minutes or more. Specifically, it may be 30 to 200 minutes, 30 to 190 minutes, 35 to 180 minutes, 40 to 170 minutes, 45 to 160 minutes, 50 to 150 minutes, 55 to 140 minutes, and 60 to 140 minutes. The step of irradiating light can sufficiently sterilize the disinfection target object 60 by irradiating at least one of the container 10, the photo-functional bead 20, and the conduit 40 with sufficient light for 30 minutes or more.

Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the scope of the present invention is not limited by the following Examples.

The invention may be better understood by reference to the following examples, which are intended to be illustrative of the invention and are not intended to limit the scope of protection which is defined by the appended claims.

Manufacturing example  One

The photosensitizer solution is prepared by dissolving the photosensitizer tetraphenyl porphyrin (H ₂ TPP) in dichloromethane as a solvent. Polyfunctional beads were prepared by immersing the polypropylene beads in the photosensitizer solution at 60 占 폚 for 24 hours.

Production Example 2

A mixed solution is prepared by dissolving photo-curable polymer resin polyurethane acrylate and photo-sensitizer tris (1,3-dichloroisopropyl) phosphate (TDCPP) in a dichloromethane solvent. The mixed solution is poured into a rectangular frame, and ultraviolet rays are irradiated to cure the polymer resin mixed solution to prepare a photo-functional film.

Production Example 3

The stainless steel sheet is placed in a mixture of nitric acid and ethanol to oxidize the steel sheet to bind a hydroxyl group (OH group) on the surface of the steel sheet. An alloy film or alloy conduit is prepared by bonding a photosensitizer, hematoporphyrin (HP), to the steel sheet to which the hydroxyl group is bonded.

Example  One

The disinfection efficacy of the photo-functional beads was evaluated by using the apparatus and method of the specifications and conditions as shown in Tables 1 to 5, respectively. Specifically, the apparatus according to the present invention was used to disinfect vegetables and fruiting bodies contaminated with microorganisms with photo-functional beads, and the results are shown in FIGS. 2 to 6.

Sample H ₂ TPP polymer beads (B310) Bacteria E. coli (ATCC 25922) Bacteria Resuspended Turbidity
(Bacteria resuspension turbidity) 0.5 (1.5 x 10 ⁸ CFU / ml) x 1/100 Pollution method 100 μL of microbial solution and 1 tangerine tablet vortexing
(300 rpm / 1 min)
→ incubation 1 hour (37 ℃, Dark) Subject One piece of orange peel Experiment environment 25 ° C, Air Light source Green LED Light quantity 4 mW / cm ² (per side) Investigation time 0, 10, 20, 30 minutes Analysis method Colony count method
(Colony count method, 100 [mu] L)

Referring to FIG. 2, it can be seen that the number of E. coli decreases over time in the contaminated citrus peel under the conditions of Table 1 of Example 1. FIG. Especially, when 30 minutes passed, the number of E. coli decreased to 10 ^0.5 CFU / ml or less. Also, as in Comparative Example 1-1 and Comparative Example 1-2, when irradiated with visible light in a dark place or not at a specific wavelength, a decrease in the number of E. coli is not apparent. Therefore, it means that the photo-functional bead containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED area to generate active oxygen to sterilize harmful microorganisms.

Sample H ₂ TPP polymer beads (B310) Bacteria E. coli (ATCC 25922) Bacteria Resuspended Turbidity
(Bacteria resuspension turbidity) 0.5 (1.5 x 10 ⁸ CFU / ml) x 1/100 Pollution method Using a syringe, randomly injected into 10 tomato surfaces (100 μL of microbial solution)
→ incubation 1 hour (37 ℃, Dark) Subject 1 drop tomato Experiment environment 25 ° C, Air Light source Green LED Light quantity 4 mW / cm ² (per side) Investigation time 0, 20, 40, 60 minutes Analysis method How to Count Colonies After Mashed Tomatoes
(Colony count method, 100 [mu] L)

Referring to FIG. 3, it can be seen that the number of E. coli decreases with time in the contaminated drop tomato of the condition of Table 2 of Example 1. [ Especially, when 60 minutes passed, the number of E. coli decreased to 10 ^1.5 CFU / ml or less. Also, as in Comparative Example 1-1 and Comparative Example 1-2, when irradiated with visible light in a dark place or not at a specific wavelength, a decrease in the number of E. coli is not apparent. Therefore, it means that the photo-functional bead containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize the harmful microorganism.

Sample H ₂ TPP polymer beads (B310) Bacteria E. coli (ATCC 25922) Bacteria Resuspended Turbidity
(Bacteria resuspension turbidity) 0.5 (1.5 x 10 ⁸ CFU / ml) x 1/100 Pollution method 100 μl of microbial solution and 1 g of sprout vegetable vortexing
(300 rpm / 1 min)
→ incubation 1 hour (37 ℃, Dark) Subject 1 g sprout vegetables Experiment environment 25 ° C, Air Light source Green LED Light quantity 4 mW / cm ² (Per side) Investigation time 0, 20, 40, 60, 90 minutes Analysis method Colony count method
(Colony count method, 100 [mu] L)

Referring to FIG. 4, it can be seen that the number of E. coli in the contaminated sprouts vegetables under the conditions of Table 3 of Example 1 decreases over time. Especially, when 90 minutes passed, the number of E. coli decreased to 10 ^0.5 CFU / ml or less. Also, as in Comparative Example 1-1 and Comparative Example 1-2, when irradiated with visible light in a dark place or not at a specific wavelength, a decrease in the number of E. coli is not apparent. Therefore, it means that the photo-functional bead containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize the harmful microorganism.

Sample H ₂ TPP polymer beads (B310) Bacteria E. coli (ATCC 25922) Bacteria Resuspended Turbidity
(Bacteria resuspension turbidity) 0.5 (1.5 x 10 ⁸ CFU / ml) x 1/100 Pollution method 100 μL of microbial solution and 2.5 g of broccoli vortexing
(300 rpm / 1 min)
→ incubation 1 hour (37 ℃, Dark) Subject Broccoli 2.5 g Experiment environment 25 ° C, Air Light source Green LED Light quantity 4 mW / cm ² (Per side) Investigation time 0, 10, 20, 30 minutes Analysis method Colony count method
(Colony count method, 100 [mu] L)

Referring to FIG. 5, it can be seen that the number of E. coli decreases over time in the contaminated broccoli under the conditions in Table 4 of Example 1. FIG. Especially, when 30 minutes passed, the number of E. coli decreased to 10 ^0.5 CFU / ml or less. Also, as in Comparative Example 1-1 and Comparative Example 1-2, when irradiated with visible light in a dark place or not at a specific wavelength, a decrease in the number of E. coli is not apparent. Therefore, it means that the photo-functional bead containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize the harmful microorganism.

Sample H ₂ TPP polymer beads (B310) Bacteria E. coli (ATCC 25922) Bacteria Resuspended Turbidity
(Bacteria resuspension turbidity) 0.5 (1.5 x 10 ⁸ CFU / ml) x 1/100 Pollution method 100 μL of microbial solution and 2.5 g of broccoli vortexing
(300 rpm / 1 min)
→ incubation 1 hour (37 ℃, Dark) Subject Red cabbage 2.5 g Experiment environment 25 ° C, Air Light source Green LED Light quantity 4 mW / cm ² (Per side) Investigation time 0, 10, 20, 30 minutes Analysis method Colony count method
(Colony count method, 100 [mu] L)

Referring to FIG. 6, it can be seen that the number of E. coli in the contaminated drop cabbage under the conditions of Table 5 of Example 1 decreases over time. Especially, when 30 minutes passed, the number of E. coli decreased to 0.5 CFU / ml or less. Also, as in Comparative Example 1-1 and Comparative Example 1-2, when irradiated with visible light in a dark place or not at a specific wavelength, a decrease in the number of E. coli is not apparent. Therefore, it means that the photo-functional bead containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize the harmful microorganism.

Example 2

The disinfection efficiency of the photo-functional beads was evaluated by using the apparatuses and methods with the specifications and conditions as shown in Tables 6 to 7, respectively. Specifically, the apparatus according to the present invention was used to disinfect vegetables and fruits contaminated with microorganisms in a container 10 composed of a highly branched film, and the results are shown in FIGS. 7 and 8. FIG.

Sample TDCPP @ polyurethane film Bacteria S. aureus (ATCC 25923) Light source Green LED (3.5 mW / cm ² ) Investigation time 60 minutes Temperature At room temperature (25 ° C)

7, it can be seen that the number of Staphylococcus aureus decreases with time in the solution of Staphylococcus aureus under the conditions of Table 6 in Example 2. [ In particular, when 40 minutes have elapsed, the survival rate approaches zero. Further, when the experiment was conducted in a dark place as in Comparative Example 2, the decrease in the number of Staphylococcus aureus did not appear clearly. Therefore, it means that the photo-functional film containing TDCPP absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize the harmful microorganism.

Sample H ₂ TPP @ Silicone polymer Bacteria S. aureus (ATCC 25923)
E. coli (ATCC 25922) Light source Green LED (3.5 mW / cm ² ) Investigation time 2 hours Pre-incubation time & temperature 24 hours, 37 ℃

Referring to FIG. 8, it can be seen that the number of Staphylococcus aureus and E. coli decreases with time in the solution of Staphylococcus aureus and the solution of E. coli under the conditions of Table 7 of Example 2. In particular, S. aureus, a Gram-positive bacterium, shows a decrease in the number of S. aureus to less than 10 ³ CFU / ml after a lapse of 120 minutes. In E. coli, a gram-negative organism, the number of E. coli was reduced to less than 10 ⁴ CFU / ml after a lapse of 120 hours. Further, when the experiment was conducted in a dark place as in Comparative Example 2, the decrease in the number of Staphylococcus aureus was not apparent. Therefore, it means that the photo-functional film containing tetraphenylporphyrin (H ₂ TPP) absorbs the light source of the wavelength of the green LED region to generate active oxygen to sterilize harmful microorganisms. In addition, it can be seen that the photo-functional film containing tetraphenylporphyrin (H ₂ TPP) is more excellent in sterilizing power in Gram-positive Staphylococcus aureus. Further, it can be confirmed that the sterilizing power of the photo-functional bead is superior to that of the photo-functional film.

Example 3

The disinfection efficacy of photo-functionalities was evaluated by using the apparatus and method of the specifications and condition as shown in Table 8, respectively. Specifically, the apparatus according to the present invention was used to disinfect vegetables and fruits contaminated with microorganisms in a container 10 made of a photo-functional alloy film, and the results are shown in FIG.

Sample HP @ 215LSS Bacteria S. aureus (ATCC 25923)
E. coli (ATCC 25922) Light source Green LED (3.5 mW / cm ² ) Investigation time 2 hours Pre-incubation time & temperature 24 hours, 37 ℃

9, it can be seen that the number of Staphylococcus aureus and E. coli decreases with time in the Staphylococcus aureus solution and E. coli solution under the condition of Table 8 of Example 3. [ In particular, S. aureus, a Gram-positive bacterium, had a number of S. aureus of 10 CFU / ml. ≪ / RTI > In addition, it can be confirmed that the number of E. coli decreased to below 10 ⁵ CFU / ml when the time passed from 120 grams of E. coli. Also, when the experiment was conducted in a dark place as in Comparative Example 3, the number of Staphylococcus aureus did not decrease. Therefore, it means that the photo-functional alloy film containing hematoporphyrin (HP) absorbs the light source of the wavelength of the green LED area to generate active oxygen to sterilize harmful microorganisms. In addition, the photo-functional alloy film containing hematoporphyrin (HP) has superior sterilizing power in Staphylococcus aureus, which is a Gram-positive bacterium.

Comparative Example 1-1

Experiments were carried out in the same manner as in Tables 1 to 5 except that the experiment was conducted in a dark condition without a light source, and the results are shown in FIG. 2 to FIG.

Comparative Example 1-2

Experiments were carried out in the same manner as in Tables 1 to 5 except that the experiment was performed in the space where the article ray was present, and the results are shown in FIG. 2 to FIG.

Comparative Example 2

Experiments were carried out in the same manner as in Tables 6 and 7 except that the experiment was conducted in a dark condition without a light source, and the results are shown in FIG. 7 and FIG.

Comparative Example 3

Experiments were carried out in the same manner as in Table 8 except that the experiment was performed in a dark condition without a light source, and the results are shown in FIG.

Experimental Example 1-1

The absorption spectrum of the photo-functional film comprising the photo-sensitizer TDCPP prepared in Preparation Example 2 and the photo-functional bead prepared in Production Example 1 was measured. Referring to FIG. 10, it can be seen that the photo-functional bead (TDCPP in dichloromethane) and the photo-functional film (TDCPP polymer film) absorb light having a wavelength of 400 to 700 nm. Specifically, it can be confirmed that the photo-functional beads absorb most light having a wavelength of 380 to 550 nm, and the photo-functional film absorbs most of light having a wavelength of 300 to 600 nm. The reason why the light source device 50 having a wavelength of 400 to 700 nm is used in the present invention is that the absorption is the most at the above wavelength.

Experimental Example 1-2

The absorption spectrum of the photo-functional alloy film prepared in Production Example 3 including a hematoporphyrin (HP) solution and hematoporphyrin (HP) was measured. 11, it is confirmed that the hematoporphyrin (HP) solution and the photo-functional alloy film (HP-bonded 316L Stainless steel) absorb light having a wavelength of 400 to 700 nm. Specifically, it can be confirmed that the hematoporphyrin (HP) solution absorbs the light of the wavelength of 300 to 600 nm most and the photo-functional alloy film absorbs the light of the wavelength of 350 to 700 nm the most. The reason why the light source device 50 having a wavelength of 400 to 700 nm is used in the present invention is that the absorption is the most at the above wavelength.

Experimental Example 2-1

In order to evaluate the active oxygen (singlet oxygen) emission efficiency of the photo-functional film (TDCPP polymer film) prepared in Production Example 2, polyurethane acrylate resin and the photo-functional film prepared in Production Example 2 were treated with 4-chloro- Phenol was added and the light was irradiated at a power of 3.5 mW / cm ² of green LED to measure the concentration of 4-chlorophenol with time, and the results are shown in FIG. Referring to FIG. 12, the concentration of 4-chlorophenol was constant even after 100 minutes in general polymer resin. On the other hand, the photo-functional film shows that the concentration of 4-chlorophenol is reduced by about 25% of the initial concentration over time. This means that the photosensitizer TDCPP contained in the photo-functional film produced active oxygen, and 4-chlorophenol reacted with the generated active oxygen to decrease the concentration of 4-chlorophenol.

Experiment 2-2

4-chlorophenol, which is used as a quencher, was added to the photo-functional film prepared in Preparation Example 2, and the light absorption rate of 4-chlorophenol was measured at the output of 3.5 mW / cm ² of green LED, The results are shown in Fig. 13, the absorption rate was the highest at a wavelength of 270 to 325 nm, and the absorption rate decreased at a wavelength of 270 to 325 nm as time elapses. This means that as the time for irradiating the light source is prolonged, active oxygen is generated and the concentration of 4-chlorophenol reacts with active oxygen to decrease the concentration.

Experimental Example 2-3

The emission of singlet oxygen from the TDCPP of the photo-functional film prepared in Preparation Example 2 was confirmed by directly detecting the phosphorescence emitted from the TDCPP of the photo-functional film prepared in Production Example 2.

The quantum yield of the singlet oxygen (φΔ (O ₂ )) and its lifetime were measured by detecting near-infrared phosphorescent emission peaks at 1270 nm. The phosphorescence signal was collected using a germanium photodiode (EG & G, Judson) at a vertical angle to the excitation beam (<1000 nm, CVI) passing through the cut-off and the interference filter (1270 nm, spectrogon). Nd-YAG pumped OPO laser (BM Industries, OP901-355, 5 ns FWHM pulse) was used as the excitation source. The signals collected by the 500 MHz digital oscilloscope were passed for data analysis. A single anti-oxygen phosphorescent signal per hour is shown in FIG.

As shown in Fig. 14, the lifetime of the singlet oxygen of the photofunctional film containing TDCPP was ~ 500 mu s.

Experimental Example 2-4

In order to evaluate the emission efficiency of singlet oxygen of the photo-functional alloy film produced in Production Example 3, the decomposition method of 1,3-diphenylisobenzofuran (DPBF) was used, Respectively. As a specific singlet oxygen quencher, 1,3-phenylisobenzofuran (DPBF) gradually undergoes a 1,4-ring addition reaction with monooxygen to form endo-peroxide. And then decomposed into irreversible products of 1,2-dibenzoylbenzene.

The alloy film prepared in Preparation Example 3 was injected into a 1 cm quartz cell in a dark state. The above experiment was conducted by irradiating a sample with a light source having a power of 7.5 mW / cm ² using a green LED.

Referring to FIG. 15, it can be seen that the absorption rate is the highest at a wavelength of 350 to 450 nm, and the absorption rate decreases at a wavelength of 350 to 450 nm over time. This means that as the time for irradiating the light source increases, active oxygen is generated and the concentration of 1,3-phenylisobenzofurane (DPBF) reacts with active oxygen to decrease the concentration.

Experimental Example 3

X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy) of a pure stainless steel plate, a stainless steel plate containing a hydroxyl group on its surface, and an alloy film prepared in Preparation Example 3 were used to confirm the binding properties between the components constituting the alloy film produced in Production Example 3, ray photoelectron spectroscopy (XPS) were measured. The results are shown in Fig.

16 (a) is a graph showing the components of a pure stainless steel plate.

FIG. 16 (b) is a graph showing the composition of stainless steel obtained by oxidizing stainless steel using nitric acid and ethanol as a solvent in a pure stainless steel sheet in Production Example 3 and binding a hydroxyl group to the surface. FIG. (b), it can be seen that O ^{2 -} and OH ^- exist at binding energies of about 530 ± 0.5 eV and about 532.8 ± 0.5 eV in the O1s graph. Further, in the Ni2P and Cr2p graphs, NiO, Cr (OH) ₃ and NiO were found at binding energies of about 853 ± 0.5 eV, about 577 ± 0.5 eV, and about 530.8 ± 0.5 eV, And the presence of Cr ₂ O ₃ can be confirmed. That is, in Production Example 3, stainless steel obtained by oxidizing stainless steel by using nitric acid and ethanol as a solvent in a pure stainless steel sheet and having hydroxyl groups bonded to its surface shows that hydroxyl groups are bonded to the surface.

16 (c) is a graph showing the composition of the alloy film produced in Production Example 3. Fig. (c), it can be seen that the ester bond is present at the binding energy of about 533 ± 0.5 eV in the O1s graph. That is, the alloy film prepared in Preparation Example 3 shows that the ester bond binds to the photosensitizer hematoprofilin.

10: container
20: Optical functional bead
30: Light source device
40: conduit
50: Circular motor
60: disinfection object

Claims (12)

A container for receiving water;
A photofunctional bead contained in water and comprising a photosensitizer;
A light source device for irradiating light;
A conduit connecting at least two points of the vessel to allow water to circulate; And
And a circulation motor installed in the conduit for circulating the water,
The container has a structure in which a photosensitive region is dispersed in a certain region or more among the inner surfaces,
The diameter of the photo-functional bead is 0.1 to 40 mm,
The photo-functional beads are prepared by supporting a photo-sensitizer on a polymer bead through a swelling method of absorbing a photo-sensitizer solution into polymer beads,
Wherein the light source device has a wavelength of 460 to 600 nm.
delete delete The method according to claim 1,
Wherein the inner surface of the conduit is ester-bonded with the photosensitizer.
5. The method of claim 4,
Wherein the conduit comprises at least one selected from the group consisting of stainless steel, aluminum, magnesium, tin, titanium, tungsten and nickel.
5. The method according to any one of claims 1 to 4,
Each of the photosensitizers is independently selected from the group consisting of tris (1,3-dichloroisopropyl) phosphate (TDCPP), hemato porphyrin (HP), 5,10,15-triphenyl Bisphenyl-10,20-bis (4-carboxyphenyl) -porphyrin platinum, PtCP), 5,15- Bis (4-methoxycarbonylphenyl) -porphyrin platinum, t-PtCP), tetraphenyl porphyrin (H ₂ TPP), protoporphyrin proto porphyrin, PP), indocyanine green (ICG) and meso-tetrakis (psulfonatophenyl) porphyrin (TSPP). Containing disinfection device.
delete The method according to claim 1,
Wherein the polymeric bead comprises at least one selected from the group consisting of polyurethane, polyurethane acrylate, and polyethylene phthalate.
delete A step of preparing a photo-functional bead for producing a bead having bactericidal action by the active oxygen generated through light energy induction by immersing in a photosensitizer solution;
Placing a disinfection object in a container containing the manufactured photofunctional bead and water; And
And irradiating light using a light source device,
Wherein the light source device has a wavelength of 460 to 600 nm.
11. The method of claim 10,
The disinfection subject is at least one of vegetable and fruit.
11. The method of claim 10,
Wherein the light irradiation is performed at an output of 1 mW / cm ² or more for 30 minutes or more.

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