JP2003128502A - Treating material for harmful substance and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating material for harmful substances capable of efficiently inactivating these harmful substances by a titanium dioxide film. SOLUTION: The titanium dioxide 5 inactivates harmful substances 2 such as Escherichia coli and HIV which are in danger of being mixed in a material to be treated such as blood plasma with a photocatalyst function. A retaining substance 8 having a specificity retaining only specific harmful substance 2 is crosslinked on the surface of the titanium dioxide 5 in parallel by a monomolecular crosslinking molecule 7. As a result, since the film thickness of the crosslinking molecule 7 becomes thicker, the crosslinking molecule 7 scarcely inhibits inactivation of the harmful substance which the retaining substance 8 retains by photocatalyst function of the titanium dioxide film 5. The treating material can efficiently inactivate the harmful substance 2 which the retaining substance 8 retains by the photocatalyst function of the titanium dioxide film 5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to viruses and bacteria,
The present invention relates to a treatment material for harmful substances that inactivates specific harmful substances such as toxins and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, as a treatment material for this kind of harmful substance, the one described in Japanese Patent Application No. 2000-321552 has been proposed.

The treatment material described in Japanese Patent Application No. 2000-321552 is a biological hazard contained in blood, plasma, blood products, body fluids, etc. on the surface of a titanium dioxide film as a transition metal oxide having a photocatalytic action. Antibodies such as receptors as retention substances that selectively adsorb organisms such as viruses and pathogenic bacteria and toxins as potential harmful substances, and 3-aminopropyltrisilane that is an aminoalkylethoxysilane as a silane coupling agent. Ethoxysilane (AminoPr
It is cross-linked through a cross-linking molecule composed of opylTriEthoxySilane (APTES) and glutaraldehyde.

The organisms such as viruses and pathogenic bacteria and toxins adsorbed by the antibody of the treatment material are inactivated by the high oxidizing power of the titanium dioxide film.

[0005]

However, in the treatment material described in the above-mentioned Japanese Patent Application No. 2000-321552, when APTES is introduced into the surface of the titanium dioxide film, the film structure of this APTES is not controlled. Therefore, this APTES exists in the form of a film on the surface of the titanium dioxide film. Further, when glutaraldehyde, which is a cross-linking molecule, is introduced into APTES introduced on the surface of the titanium dioxide film, the glutaraldehyde also excessively contains AP.
Combines with TES.

As a result, the film-like APTES and glutaraldehyde introduced on the surface of the titanium dioxide film hinders the photocatalytic action of the titanium dioxide film on harmful substances such as HIV. There is a problem that inactivation of a substance cannot be performed efficiently.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a treatment material for a harmful substance which can efficiently inactivate a harmful substance with a transition metal oxide, and a method for producing the same. .

[0008]

The treatment material for harmful substances according to claim 1 is a specific harmful substance which may or may be mixed in an object to be treated in at least one of a liquid phase and a gas phase. A holding substance having a specificity of holding only, a transition metal oxide which inactivates the harmful substance held by the holding substance by a photocatalytic function, and the transition metal oxide formed in parallel on the surface of the transition metal oxide. A monomolecular cross-linking molecule that cross-links the holding substance to the transition metal oxide.

The surface of the transition metal oxide, which inactivates harmful substances by photocatalytic function, which may or may not be mixed in the object to be treated in the form of at least one of liquid phase and gas phase, is provided on the surface of the transition metal oxide. A holding substance having a specificity of holding only a harmful substance is cross-linked in parallel by a single molecule of cross-linking molecule. As a result, since the film thickness of the cross-linking molecule becomes thinner, the cross-linking molecule is less likely to inhibit the deactivation of the harmful substance held by the holding substance by the photocatalytic function of the transition metal oxide. Therefore, the photocatalytic function of the transition metal oxide allows the harmful substance held by the holding substance to be efficiently inactivated.

The treatment material for harmful substances according to claim 2 is the treatment material for harmful substances according to claim 1, in which the cross-linking molecules are formed on the surface of the transition metal oxide by an inorganic bond. is there.

By forming a cross-linking molecule by an inorganic bond on the surface of the transition metal oxide, the effect of the photocatalytic action of the transition metal oxide on the cross-linking molecule is reduced, and at the same time, the transition metal oxide It is possible to prevent the retention substance and the cross-linking molecules from being detached from the surface.

The treatment material for a harmful substance according to claim 3 is the treatment material for a harmful substance according to claim 1 or 2, wherein the cross-linking molecules are along the normal direction to the surface of the transition metal oxide. .

Then, a cross-linking molecule is formed on the surface of the transition metal oxide along the direction of the normal to the surface of the transition metal oxide so that the surface of the transition metal oxide is retained by a single molecule of the cross-linking molecule. Can be crosslinked more than once. Therefore, the retention of the specific harmful substance by the retention substance becomes more efficient, and the inactivation of the harmful substance by the photocatalytic function of the transition metal oxide becomes more efficient.

In the method for producing a treatment material for harmful substances according to the fourth aspect of the present invention, the photocatalytic function prevents harmful substances from being mixed or likely to be mixed in the object to be treated in at least one of the liquid phase and the gas phase. A single molecule cross-linking molecule is formed in parallel on the surface of the transition metal oxide to be activated, and a holding substance having the specificity of holding only the specific harmful substance through the cross-linking molecule is added to the transition metal oxide. It is to be crosslinked.

Then, a cross-linking molecule is formed on the surface of the transition metal oxide which inactivates a harmful substance which is mixed or may be mixed into the object to be treated in the form of at least one of the liquid phase and the gas phase by the photocatalytic function. A retention substance having a specificity of forming only a single molecule and retaining only a specific harmful substance through this cross-linking molecule is cross-linked to the transition metal oxide. As a result, since the film thickness of the cross-linking molecule becomes thinner, the cross-linking molecule is less likely to inhibit the deactivation of the harmful substance held by the holding substance by the photocatalytic function of the transition metal oxide. Therefore, the photocatalytic function of the transition metal oxide allows the harmful substance held by the holding substance to be efficiently inactivated.

The method for producing a treatment material for harmful substances according to claim 5 is the method for producing a treatment material for harmful substances according to claim 4, wherein cross-linking molecules are formed on the surface of the transition metal oxide by an inorganic bond. To do.

By forming a cross-linking molecule by an inorganic bond on the surface of the transition metal oxide, the effect of the photocatalytic action of the transition metal oxide on the cross-linking molecule is reduced, and at the same time, the transition metal oxide It is possible to prevent the retention substance and the cross-linking molecules from being detached from the surface.

The method for producing a treatment material for a harmful substance according to claim 6 is the method for producing a treatment material for a harmful substance according to claim 4 or 5, wherein a cross-linking molecule provided with a silane coupling agent is reacted with a silane coupling reaction. Thus, only a single molecule is formed on the surface of the transition metal oxide.

When a single molecule of the cross-linking molecule provided with the silane coupling agent is formed on the surface of the transition metal oxide by the silane coupling reaction, the single molecule of the cross-linking molecule is formed on the surface of the transition metal oxide. Will be easier.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The configuration of a harmful substance treating apparatus according to an embodiment of the present invention will be described below with reference to the drawings.

In FIG. 2, reference numeral 1 denotes a processing apparatus main body. The processing apparatus main body 1 is provided with a harmful substance 2 having a constituent protein showing a particularly specific binding property or an antigenicity, for example, for viruses, bacteria, toxins and the like. There is a risk of contamination or contamination,
It is provided with a plurality of processing chambers 3 into which an object to be processed having at least one of a liquid phase and a gas phase is introduced.

As shown in Table 1, there are mainly three types of sites showing strong antigenicity in bacterial cells, and the antigenicity differs depending on the bacterial species. For example, the bacterium E. coli O-157
Indicates the 157th position of the O antigen. Any bacteria exhibiting these specific antigenicity is targeted. Further, as the virus, for example, as shown in Table 2, any virus having a protein having strong binding property among constituent proteins is a target. Furthermore, as the toxin, for example, in addition to the toxins produced by various bacteria shown in Table 3, blowfish poison (tetrodotoxin), snake venom,
Any toxin with a specific antigenicity, such as venom of insects such as scorpions, bees, and spiders, is targeted.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

On both sides of each processing chamber 3 of the processing apparatus main body 1, rectangular flat plate-shaped processing materials 4 whose surface directions are separated from each other in parallel are provided. These treatment materials 4
Is a titanium dioxide (TiO ₂ ) film 5 which is a transition metal oxide as a photocatalytic material having a photocatalytic function, that is, the surface of a rectangular flat plate-shaped substrate 6 coated with a crosslinking molecule 7 as a crosslinking part. The holding substance 8 which is a selective receptor having specificity of binding only to the specific harmful substance 2 is bound via the. Here, each base material 6 transmits ultraviolet rays,
Silicon dioxide (S that guides light from a light source not shown)
iO ₂₎ is a sheet-shaped glass molded at. Further, the titanium dioxide film 5 is formed on the surface of the base material 6 by the atmospheric pressure CVD (C
The film is formed by a chemical vapor deposition (chemical vapor deposition) method.

Further, as shown in FIG. 1, the bond of the holding substance 8 is, for example, 3-aminopropyltriethoxysilane which is aminoalkylethoxysilane as a silane coupling agent for the hydroxyl group bonded to the surface of the titanium dioxide film 5. (AminoPropylTriEthoxySilane: APTES) 11 only a single molecule is bound, only a single molecule of glutaraldehyde 12 is bound to the amino group of the bound APTES11, and a retaining substance that is a protein to the terminal aldehyde group of the bound glutaraldehyde 12 8 amino group is bound to reduce the Schiff base, that is, after binding the retention substance 8, AP
The double bond of the bond between TES 11 and glutaraldehyde 12 and the bond between glutaraldehyde 12 and the holding substance 8 is reduced and bonded.

The holding substance 8 is a specific antibody against the specific antigenicity of bacteria shown in Table 1, a receptor (receptor) for the constituent protein showing a strong specific binding of the virus shown in Table 2, Those that specifically retain the harmful substance 2, such as those having an amino group having specificity that binds only to the harmful substance 2 such as antibodies of the toxins shown in Table 3 and proteins that have specificity, are used. Here, the retention of the harmful substance 2 refers to any form in which the harmful substance 2 is retained, such as a physical bond such as adsorption or a chemical bond such as a chemical bond.

Further, the processing apparatus main body 1 is provided with a light source (not shown) for irradiating the processing material 4 in the processing chamber 3 with light.
This light source is, for example, a fluorescent lamp that illuminates visible light having a peak wavelength of about 600 nm, or a wavelength of 300 nm or more 420
Black light with peak below nm, approximately 185n
An ultraviolet lamp that emits ultraviolet rays such as a low-pressure mercury lamp that has a peak even at m and can generate ozone is used.

It should be noted that the titanium dioxide film 5 is no longer excited by light having a long wavelength from visible light to infrared light or more, so that the photocatalytic function cannot be obtained, and when the wavelength is too short, the light is a constituent component or treatment of the object to be treated. Since the material 4 may be damaged, it is in the range of visible light to ultraviolet light of approximately 150 nm.
A light source having a peak wavelength of about 600 nm or less is used.

Next, a method of manufacturing the treatment material of the above-described one embodiment will be described.

First, as shown in FIG. 3A, a base material 6 (10 cm long × 10 cm wide) formed of SiO ₂ glass.
The titanium dioxide film 5 is coated only on one surface (thickness 0.5 mm) by the atmospheric pressure CVD method. At this time, the titanium dioxide film 5 does not denature plasma components and the like in the object to be treated, can absorb the ultraviolet rays necessary for photocatalytic activity, and has a sufficient antibacterial property.
The film thickness of the titanium dioxide film 5 is controlled so that it has an optimum film thickness that does not peel off.

After that, as shown in FIG. 3 (b), the substrate 6 on which the titanium dioxide film 5 was formed was treated with the vapor phase of a dehydrated toluene solution containing APTES11 forming a part of the cross-linking molecule 7. It is installed inside, and APTES 11 is immobilized on the surface of the titanium dioxide film 5 by a chemical bond by a silane coupling reaction.

Then, the base material 6 having the APTES 11 immobilized on its surface is treated with dehydrated ethanol, dehydrated toluene, 1 m.
After washing several times with an aqueous solution of M NaOH and an aqueous solution of 1 mM HNO ₃ , it is finally washed with ultrapure water and dried using nitrogen gas.

Here, when the film thickness of APTES 11 fixed on the surface of the titanium dioxide film 5 of the base material 6 was measured by spectroscopic ellipsometry, it was found to be 1.1 ± 0.1 nm. This value is the length dimension of APTES11 single molecule 1.1n.
Since it corresponds to m, it can be inferred that only the APTES11 single molecules are regularly arranged on the surface of the titanium dioxide film 5 in the direction normal to the surface of the titanium dioxide film 5.

Next, as shown in FIG. 3 (c), APTES1
A single molecule is immobilized on the surface of the titanium dioxide film 5 on the substrate 6, and the concentration is 3.0% with 0.1M potassium phosphate buffer.
Add the glutaraldehyde 12 solution adjusted to, and mix thoroughly with stirring at room temperature.

Further, as shown in FIG. 3 (d), after thoroughly stirring and washing with a 0.1 M potassium phosphate buffer (pH 7.5), a retention substance 8 which is a protein, for example, HIV (Human I) was used.
mmunodeficiency Virus: Human immunodeficiency virus) CD4, a protein component on the surface of T cells as a receptor that binds
([Cys (Bzl)] ⁸⁴ -Fragment 81-92, manufactured by Sigma-Aldrich) is added, and the mixture is stirred at 4 ° C for 24 hours. At this time, the amino group of this CD4 is bonded to the aldehyde group of the cross-linking molecule 7 so that the base material 6 holds the CD4.

After this, glutaraldehyde 12 was converted to APTE.
After dehydrating the substrate 6 bonded to S11, the substrate 6 is
It is suspended in M Tris HCl buffer (pH 7.5) and reacted at room temperature for 1 hour to inactivate the aldehyde group of glutaraldehyde 12.

Further, as shown in FIG. 3 (e), NaBH ₄ is added to this base material 6 to reduce and stabilize the Schiff base of glutaraldehyde 12 of this base material 6 for biomedical science. The processing material 4 which is a reactor is prepared.

Next, the processing operation of the object to be processed according to the above embodiment will be described.

First, a treatment having a retaining substance 8 for the specific antigenicity of the harmful substance 2 to be removed from the object to be treated, which is a liquid such as blood, blood components, blood products, or gas such as air. The material 4 is provided on the surface of the base material 6. The base material 6 is installed in each processing chamber 3 of the processing apparatus main body 1.

Thereafter, the object to be processed is caused to flow into each of the processing chambers 3 at a predetermined flow rate and the light source is illuminated.

At this time, due to the inflow of the object to be processed, the harmful substance 2 mixed in the object to be processed is the holding substance 8 of the processing material 4.
The toxic substance 2 is inactivated by being bound and retained by the adsorbent and the like, and the harmful substance 2 is removed from the object to be treated.

Further, the harmful substance 2 held by the holding substance 8 and inactivated is decomposed by the strong oxidizing power of the photocatalytic function of the titanium dioxide film 5 irradiated with light from the light source.

That is, when water (H ₂ O) adhering to the surface of the titanium dioxide film 5 irradiated with light from the light source or water in the air collides with the titanium dioxide film 5, hydroxy radicals (.OH) are generated. with resulting oxidation reaction to produce superoxide anion by oxygen collide (· O ₂ ^-) is occurs photocatalytic action of the reducing reaction occurs to produce.

By this photocatalytic action, the object to be treated is purified and, for example, disease caused by the harmful substance 2 is surely prevented.

Next, the operation of the processing material of the above-mentioned one embodiment will be described with reference to an experimental example.

(Experimental Example 1) First, anti-HIV by the treating material 4
An experiment was conducted on the evaluation.

With the titanium dioxide film 5 of the base material 6 manufactured by the above-described method for manufacturing a treatment material facing upward, the base material 6 is placed in a well plate (24 wells) not shown, and H
500 μl of IV solution was added.

At this time, the HIV solution was prepared by adding HI in a culture solution (RPMI-1640 MEDIUM, SIGMA CHEMICAL CO.).
V (HIV-1) was added, and the p24 protein concentration was 10
Adjust to 0 μg / ml.

After that, the well plate having the base material 6 installed therein is placed in a shake incubator (not shown), and the wavelength of 30 is applied while shaking the well plate in the shake incubator.
UV light from 0 to 400 nm (using black light) 15,
Irradiation was performed for 30 and 60 minutes, respectively. At this time, the intensity of the ultraviolet light irradiated on the titanium dioxide film 5 of the base material 6 is set to 350 ± 2.
It was set to 0 μW / cm ² (ultraviolet ray measuring instrument UM-360 manufactured by Minolta Co., Ltd.).

Furthermore, after irradiating with ultraviolet rays for a predetermined time, the HIV solution was taken out from the well plate, mixed with H9 cells as host cells, and cultured in an incubator at 37 ° C. and 5% CO ₂ for 14 days. The amount of p24 antigen in the culture supernatant that was mass-produced was measured, and the amount of residual infectious virus after the treatment was indirectly measured.

[0053]

[Table 4]

As a result, as shown in Table 4 and FIG.
The treatment material 4 in which only a single molecule of the crosslinking molecule 7 is immobilized on the titanium dioxide film 5 is a treatment material in which the titanium dioxide film 5 is formed on the surface of the base material 6, and a plurality of crosslinking molecules on the surface of the titanium dioxide film 5. In comparison with each of the treatment materials 4 in which 7 is fixed in series, the H by the titanium dioxide film 5 with respect to the ultraviolet irradiation time is increased.
It was confirmed that the IV inactivation efficiency was improved.

(Experimental Example 2) Next, an anti-HIV evaluation was conducted by using the treatment material 4 in which the titanium dioxide film 5, the cross-linking molecule 7 and the retaining substance 8 were introduced into the inner surface of the cylindrical base material 6.

Inner diameter 2 mmφ, thickness 0.5 mm, length 20
A commercially available TiO ₂ coating liquid (ST-K01 manufactured by Ishihara Sangyo Co., Ltd.) was applied to the inner surface of a quartz glass tube as a 0 mm base material 6, and a titanium dioxide film was formed under the conditions of 500 ° C. for 30 minutes in the atmosphere. Burned 5

Then, a vapor phase of a dehydrated toluene solution of APTES11 was prepared, and this vapor phase was fed into the inside of this quartz glass tube from a tube previously connected to the quartz glass tube, and was burned into the inside of this quartz glass tube. A monolayer of APTES11 was formed on the surface of the titanium film 5.

Furthermore, after the completion of feeding the vapor phase of the dehydrated toluene solution of APTES11 into the quartz glass tube,
After being washed several times with dehydrated ethanol, dehydrated toluene, 1 mM NaOH aqueous solution, and 1 mM HNO ₃ aqueous solution, it is finally washed with ultrapure water and dried using nitrogen gas.

Here, in order to inspect that APTES11 is a monomolecular film, the film thickness of APTES11 was measured by spectroscopic ellipsometry on the inner surface of the quartz glass tube and found to be 1.1 ± 0.2 nm. I was able to confirm that there is.
Since this value corresponds to the length dimension of 1.1 nm of APTES11 single molecule, AP formed inside this quartz glass tube
It was confirmed that TES11 was a monomolecular film.

After this, glutaraldehyde 12 was chemically bonded to APTES 11 formed inside the quartz glass tube, and then CD4 was bonded to this glutaraldehyde 12.

Then, a sterilized disposable tube (not shown) is attached to one end of a sample, which is a quartz glass tube having CD4 immobilized on the titanium dioxide film 5 baked inside by a cross-linking molecule 7, and is attached to an infusion pump (not shown). The HIV solution was sent at a rate of 200 ml / hr.

However, in the quartz glass tube as the sample,
The culture medium (RPMI-1640 MEDIUM, SIGMA CHEMICAL CO.) Was filled in advance, and the titanium dioxide film 5 in this quartz glass tube was filled.
And CD4 is always moistened, and a sterilized collection container (not shown) is installed on the outflow side of this quartz glass.

Further, simultaneously with the operation of the infusion pump, the quartz glass tube was irradiated with ultraviolet rays having a wavelength of 300 nm to 400 nm at an intensity of 350 ± 20 μW / cm ² (ultraviolet ray measuring instrument UM-360 manufactured by Minolta Co., Ltd.).

Then, after 30 minutes from the start of the test, 500 μl each of 10 μl was collected from the liquid accumulated in the sampling container.
Samples were sampled, H9 cells as host cells were mixed with each of these 10 samples, and the cells were cultured in an incubator at 37 ° C. and 5% CO ₂ for 14 days, and then the amount of p24 antigen in the culture supernatant mass-produced from the infected cells. The amount of infectious virus remaining after the treatment was indirectly measured.

As a result, in all 10 specimens, HI
It was found that V was inactivated.

(Experimental Example 3) Next, the photocatalytic action of the titanium dioxide film 5 depending on the film thickness of the cross-linking molecule 7 was tested.

Plate-shaped (vertical 10 mm × horizontal 10
mm × thickness 0.5 mm) on one surface of the base material 6 formed into
A treatment material 4 in which a titanium dioxide film 5 is formed by an atmospheric pressure CVD method, a plurality of cross-linking molecules 7 are serially connected to the surface of the titanium dioxide film 5, and CD4 is immobilized on these cross-linking molecules 7.
And an ultraviolet ray having a wavelength of 300 nm to 400 nm is applied to each of the processing material 4 produced by the above-described method for producing the processing material 4 at an intensity of 2000 μW / cm ² and a condition of 500 μm for 120 minutes.
Irradiation was carried out in 1 l of ultrapure water.

Thereafter, each of the treatment materials 4 taken out from the ultrapure water was immersed in a Coomassie Brilliant Blue (CBB) solution which is a protein stain.

As a result, the treatment material 4 in which a plurality of cross-linking molecules 7 were immobilized in series on the surface of the titanium dioxide film 5 was CB.
Liquid B was not stained, whereas monomolecular cross-linking molecule 7
Treated material 4 in which titanium dioxide is immobilized in parallel on the surface of titanium dioxide film 5
Was confirmed to be stained by the CBB solution.

That is, the treatment material 4 in which the monomolecular cross-linking molecules 7 are immobilized in parallel on the surface of the titanium dioxide film 5 is treated with the titanium dioxide film of the treatment material 4 even if it is irradiated with the relatively strong ultraviolet rays under the above conditions. 5, suggesting that CD4 does not shed from the surface of 5.

As shown in FIG. 1, this is because a monomolecular film of APTES11 is formed on the surface of the titanium dioxide film 5,
The interface between the APTES 11 and the titanium dioxide film 5 is Si-
Since they are linked by an O bond, that is, an inorganic bond, the influence of the photocatalytic action of the titanium dioxide film 5 on the cross-linking molecule 7 is reduced, and the cross-linking molecule 7 and CD4 are separated from the titanium dioxide film 5. It can be inferred that it was not.

As described above, according to the above-described embodiment, a part of the cross-linking molecule 7 is formed on the surface of the titanium dioxide film 5 of the processing material 4 shown in the AFM (Atomic Force Microscope) image of FIG. When APTES11 is simply introduced, as shown in the AFM image shown in FIG. 6, this APTES11 obviously becomes a multimolecular film and is immobilized on the surface of the titanium dioxide film 5.

Further, as shown in the AFM image shown in FIG. 7, AP introduced as a polymolecular film on the surface of the titanium dioxide film 5.
When glutaraldehyde 12 forming a part of the cross-linking molecule 7 is chemically bonded to the surface of the TES 11, the thickness of the glutaraldehyde 12 itself causes the thickness of the cross-linking molecule 7 immobilized on the surface of the titanium dioxide film 5. It will be further increased.

Therefore, on the surface of the titanium dioxide film 5, APTES 11 and glutaraldehyde in the form of a multi-molecular film are formed.
After the introduction of 12, as shown in the AFM image shown in FIG. 8, when glutaraldehyde 12 was bound to CD4 as the retention substance 8, APTES 11 and glutaraldehyde were introduced.
At the thickness of 12 itself, it becomes difficult for ultraviolet rays to pass through the titanium dioxide film 5, so that H as the harmful substance 2 held by the CD 4
The bactericidal action against viruses such as IV, that is, the photocatalytic activity of the titanium dioxide film 5 is reduced.

Then, after a single molecule of APTES11 is introduced in parallel to the surface of the titanium dioxide film 5 in a state along the normal line direction on the surface of the titanium dioxide film 5 to immobilize them, the single molecule structure A single molecule of glutaraldehyde 12 is chemically bonded to each of APTES11, and CD4 is bonded to each of glutaraldehyde 12 of each of these single molecule structures, and CD4 is crosslinked to the surface of titanium dioxide film 5 by these APTES11 and glutaraldehyde12. Let

Then, since the thickness of the cross-linking molecule 7 by APTES 11 and glutaraldehyde 12 becomes as thin as possible, the transmission of ultraviolet rays to the titanium dioxide film 5 is prevented.
Of the titanium dioxide film 5 and the CD
Since the space between the titanium dioxide film 5 and the titanium dioxide film 4 is narrowed, the efficiency of deactivating and detoxifying the HIV retained in the CD4 by the photocatalytic action of the titanium dioxide film 5 can be improved. Further, since excessive binding of glutaraldehyde 12 to APTES 11 can be suppressed, the film thickness of the cross-linking molecule 7 by these APTES 11 and glutaraldehyde 12 can be made uniform.

Further, as shown in FIG. 1, since APTES11 is bonded to the surface of the titanium dioxide film 5 by an inorganic bond, the bonding interface between the titanium dioxide film 5 and APTES11 is made inorganic. As a result, this APTES
Since the influence of the photocatalytic action of the titanium dioxide film 5 on 11 is reduced and the deterioration of APTES11 due to the photocatalytic action of the titanium dioxide film 5 can be suppressed, APTES11, glutaraldehyde 12, CD4, etc. from the surface of the titanium dioxide film 5 Can be prevented from coming off.

Further, by introducing APTES11, which is a silane coupling agent, into the surface of the titanium dioxide film 5 of the treating material 4 by a chemical bond by a silane coupling reaction, only a single molecule of APTES11 of the titanium dioxide film 5 is formed. Since it is introduced to the surface, it is possible to easily introduce APTES11 having a monomolecular structure to the surface of the titanium dioxide film 5.

In the above embodiment, the harmful substance 2
As a result, I conducted an experiment targeting the virus HIV.
As shown in Table 2, viruses have specific receptor-binding or antigenicity, there are specific receptors or antibodies against them, and the retention of proteins showing such specific binding Any virus in which substance 8 is present can be targeted.

Further, as shown in Tables 1 and 3, bacteria and toxins have specific antigenicity, and there are specific antibodies against this antigenicity. Any of the bacteria having a protein retention substance 8
You can target toxins.

That is, such viruses, bacteria, and toxins can be easily bound to the titanium dioxide film 5 having a photocatalytic function by binding a predetermined holding substance 8 through the cross-linking molecule 7. The photocatalytic function of the titanium dioxide film 5 of the treatment material 4 that is retained can be imparted with the selective retention function of the specific harmful substance 2.

The holding substance 8 is not limited to protein, and any holding substance 8 having an amino group bonded to the aldehyde group at the terminal of the cross-linking molecule 7 can be applied. In addition,
Since a protein has an amino group, a virus having a constituent protein having specific binding or antigenicity,
For bacteria and toxins, the receptor or antibody that selectively retains this constituent protein is also a protein, and the retention substance 8 can be relatively easily prepared.

Further, a single molecular cross-linking molecule 7 was introduced into the surface of the titanium dioxide film 5 of the treating material 4 by chemical bonding by a silane coupling reaction using APTES11 as a silane coupling agent. If a single molecule of cross-linking molecule 7 can be introduced in parallel to APTES11
A silane coupling agent other than the above, or a cross-linking molecule 7 having any constitution may be used.

Although titanium dioxide was used as the transition metal oxide having a photocatalytic function, any transition metal oxide exhibiting a strong oxidizing power by light irradiation can be used. Note that, as described above, titanium dioxide has a photocatalytic function with an extremely strong oxidizing power and high stability, and further has a hydroxyl group for bonding the cross-linking molecule 7 to the surface in the presence of air at room temperature. Of the transition metal oxides of When another transition metal oxide is used or titanium dioxide having few hydroxyl groups on the surface is used, for example, treatment with an acid is performed to form hydroxyl groups on the surface, and then the cross-linking molecule 7 is bonded.

Further, as the cross-linking molecule 7, APTES
11 and glutaraldehyde 12, not limited to,
Any structure that allows the holding substance 8 to be bonded to the surface of the titanium dioxide film 5 may be used.

When there are a plurality of harmful substances 2 mixed in the object to be processed, for example, the holding substances 8 corresponding to the respective substances are held on the base material 6 or they correspond to different specific harmful substances 2. The treatment material 4 holding the holding substance 8 may be used for the treatment.

Furthermore, the object to be treated is not limited to the continuous treatment in which the harmful substance 2 held by irradiating light with the object to be treated is brought into contact with the object to be treated 4 and the object to be treated 4 is not irradiated with light. The harmful substance 2 is held in the holding substance 8 by contacting with the treatment target material, and after the contact of the object to be treated with the processing material 4 is terminated, light is irradiated to inactivate the harmful substance 2 which is held and captured in advance. It can also be performed intermittently. In addition, in this intermittent treatment, it is possible to reliably prevent the constituent components of the object to be treated from being denatured due to the photocatalytic action, and some of the decomposed harmful substance 2 constituent components may be peeled off and mixed into the object to be treated again. Can be reliably prevented.

Then, the holding substance 8 was bonded to the titanium dioxide film 5. For example, the titanium dioxide film 5 was provided on the surface of glass beads (not shown), and the holding substance 8 was bonded to the surface of the titanium dioxide film 5. Good.

Further, so that the constituent components of the object to be processed are in a dense state where they cannot contact the titanium dioxide film 5 of the processing material 4,
The titanium dioxide film 5 of the treatment material 4 may be provided with cross-linking molecules 7 or a holding substance 8 to cover the titanium dioxide film 5. As a result, the constituents of the object to be processed do not come into contact with the titanium dioxide film 5, so that the constituents of the object to be processed can be reliably prevented from being denatured.

Further, as in Experimental Example 2, when the treatment material 4 is bonded to the inner surface of the tubular quartz glass tube, the quartz glass tube itself becomes the treatment material 4, so that the manufacturability is easy and the weight is small. It can be easily realized and the versatility can be improved.

[0091]

EFFECT OF THE INVENTION According to the treatment material for harmful substances according to claim 1, when the holding substance is crosslinked in parallel with the surface of the transition metal oxide by a single molecule of crosslinking molecule, the film thickness of the crosslinking molecule is increased. Since it becomes thinner, the deactivation of the transition metal oxide of the harmful substance retained by the retention substance due to the photocatalytic function is less likely to be inhibited by the cross-linking molecule. The substance can be efficiently inactivated.

According to the treatment material for harmful substances described in claim 2, in addition to the effect of the treatment material for harmful substances described in claim 1, a cross-linking molecule is formed on the surface of the transition metal oxide by an inorganic bond. In this case, the effect of the photocatalytic action of the transition metal oxide on the cross-linking molecule is reduced, and the retention substance and the cross-linking molecule can be prevented from being detached from the surface of the transition metal oxide.

According to the treatment material for harmful substances described in claim 3, in addition to the effect of the treatment material for harmful substances described in claim 1 or 2, crosslinking molecules are formed along the normal direction on the surface of the transition metal oxide. If formed on the surface of this transition metal oxide, more than one retention substance can be crosslinked on the surface of this transition metal oxide by a single cross-linking molecule. Therefore, retention of a specific harmful substance by this retention substance and transition metal oxidation The inactivation of harmful substances by the photocatalytic function of substances can be performed more efficiently.

According to the method for producing a treatment material for harmful substances according to claim 4, only a single molecule of the cross-linking molecule is formed on the surface of the transition metal oxide, and the retaining substance is changed to the transition metal oxide through the cross-linking molecule. When the cross-linking is carried out, the film thickness of the cross-linking molecule becomes thinner. Therefore, the cross-linking molecule hardly inhibits the inactivation of the transition metal oxide of the harmful substance held by the holding substance by the photocatalytic function. Due to the photocatalytic function, the harmful substance held by the holding substance can be efficiently inactivated.

According to the method for producing a treatment material for a harmful substance according to claim 5, in addition to the effect of the method for producing a treatment material for a harmful substance according to claim 4, an inorganic bond is formed on the surface of the transition metal oxide. By forming the cross-linking molecule by this, the influence of the photocatalytic action of the transition metal oxide on the cross-linking molecule is reduced, and the retention substance and the cross-linking molecule can be prevented from being detached from the surface of the transition metal oxide.

According to the method for producing a treatment material for a harmful substance according to claim 6, in addition to the effect of the method for producing a treatment material for a hazardous substance according to claim 4 or 5, a crosslinking molecule provided with a silane coupling agent is added. If only a single molecule is formed on the surface of the transition metal oxide by the silane coupling reaction, it is possible to easily form a single molecule of the crosslinked molecule on the surface of the transition metal oxide.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an embodiment of a treatment material of the present invention.

FIG. 2 is a perspective view showing an embodiment of a processing apparatus using the same processing material.

FIG. 3 is a structural diagram showing a manufacturing process of the treated material. (a) An explanatory diagram of introducing a silane coupling agent into a transition metal oxide (b) An explanatory diagram of introducing glutaraldehyde into a silane coupling agent introduced into a transition metal oxide (c) Glutar introduced into a transition metal oxide Illustration of introducing a retention substance into aldehyde (d) Illustration of reducing a cross-linking molecule introduced into a transition metal oxide (e) Illustration of introducing a retention substance into a transition metal oxide via a cross-linking molecule

FIG. 4 is a graph showing the relationship between the HIV inactivation efficiency by the treated material and the UV irradiation time.

FIG. 5A shows the surface of a titanium dioxide film of a conventional treated material.
It is an FM image.

FIG. 6 is an AFM image showing a state in which 3-aminopropyltriethoxysilane is introduced into the titanium dioxide film of the above-mentioned treated material.

FIG. 7: AF showing a state in which glutaraldehyde is introduced into 3-aminopropyltriethoxysilane which is the same as the above treatment material.
It is an M image.

FIG. 8 is an AFM image showing a state in which CD4 is introduced into glutaraldehyde as a treatment material of the above.

[Explanation of symbols]

2 Hazardous substance 4 Treatment material for hazardous substance 2 Titanium dioxide film as transition metal oxide 7 Cross-linking molecule 8 Retaining substance 11 3-Aminopropyltriethoxysilane APTES as silane coupling agent

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61L 2/16 A61L 2/16 Z A61M 1/36 535 A61M 1/36 535 B01J 35/02 B01J 35/02 J (72) Shinji Kato, No. 1-36, Noritake Shinmachi, Nishi-ku, Nagoya, Aichi Prefecture Noritake Co., Ltd. Limited (72) Inventor, Hirokazu 3-36, Noritake Shinmachi, Nishi-ku, Nagoya, Aichi Prefecture Noritake Company Limited within (72) Inventor Kurutoku Kurobe Aichi Prefecture Noritake Shinmachi 3-chome, Nishi-ku, Nagoya No. 1-36 Noritake Company Limited Inside (72) Inventor Kondo Yoichi City Aichi Prefecture Nagoya City Nishi-ku Noritake Shincho 3-chome 1-36 Issue Noritake Company Limited Limited (72) Inventor Misao Iwata Noritake Company Limited 1-36-36 Noritake Shinmachi, Nishi-ku, Aichi Prefecture (72) Inventor Akira Yamaguchi 1-14-16 Honmachi, Koganei-shi, Tokyo F-term (reference) 4C058 AA28 AA30 BB06 BB07 BB09 CC04 EE15 EE16 EE23 JJ04 JJ05 JJ27 JJ30 KK01 KK02 KK27 KK46 4C077 AA07 AA30 BB10 CC07 CC09 EE01 KK09 NN14 NN15 PP16 PP24 4G069 AA02 BA04A BA04B BA14ABB22A11 BB21A01 BB11A01 BA01 A01 BA01 CA01 CA01 CA11 CA01 CA11 CA01 CA11 CA01 CA11 CA11 CA01 CA11

Claims (6)

[Claims] 1. At least one of a liquid phase and a gas phase
Retaining substance with specificity to retain only specific harmful substances that may be mixed or may be mixed into the object to be treated in one of the two forms, and the harmful substance retained by this retaining substance is inactivated by the photocatalytic function. Treatment of harmful substances, comprising a transition metal oxide and a monomolecular cross-linking molecule that is formed in parallel on the surface of the transition metal oxide and cross-links the retention substance with the transition metal oxide. Material. 2. The treatment material for harmful substances according to claim 1, wherein the cross-linking molecule is formed on the surface of the transition metal oxide by an inorganic bond. 3. The treatment material for harmful substances according to claim 1, wherein the cross-linking molecule is along the direction of a normal line on the surface of the transition metal oxide. 4. At least one of a liquid phase and a gas phase
One type of cross-linking molecule is formed in parallel on the surface of the transition metal oxide that inactivates harmful substances that may be mixed or may be mixed into the object to be treated by the photocatalytic function, and specified through this cross-linking molecule. 2. A method for producing a treatment material for harmful substances, which comprises cross-linking a holding substance having specificity of holding only the harmful substance with the transition metal oxide. 5. The method for producing a harmful substance treating material according to claim 4, wherein a cross-linking molecule is formed on the surface of the transition metal oxide by an inorganic bond. 6. The treatment material for harmful substances according to claim 4, wherein a single molecule of a cross-linking molecule provided with a silane coupling agent is formed on the surface of the transition metal oxide by a silane coupling reaction. Manufacturing method.