JP5219040B2 - Carrier, reactant complex comprising this carrier, and method for producing carrier - Google Patents

Description

  The present invention relates to a carrier, a reactant complex including the carrier, and a method for producing the carrier.

  In recent years, the production of new nanoscale materials and the application of nanoscale materials have been actively performed. In particular, there are many attempts to fix the catalyst function and convenience by immobilizing a catalyst on a nanoscale material. For example, the production of an enzyme complex in which a protein enzyme is immobilized on a silica-based mesoporous material having uniform and regular nanopores made of silica as a raw material and using a surfactant as a template. Attempts have been made to apply the body to a reactor or the like (see, for example, Patent Document 1).

The membrane-like reactant complex (enzyme complex membrane) described in Patent Document 1 includes, for example, an anodized alumina membrane having a plurality of parallel through-holes (macropores) and the macro as shown in FIG. A silica-based mesoporous material formed in the pores, and a reactive substance (enzyme) fixed inside the pores of the silica-based mesoporous material. In this reactant composite, the penetration direction of the pores of the silica-based mesoporous material is the same as the penetration direction of the macropores of the anodized alumina film.
When such a membrane-like reactant complex is applied to a reactor or the like, a liquid or gas containing a specific substance (reaction substrate) is forced from one side of the reactant complex to the other. The specific method can be determined by a method of permeation or by immersing the reactant complex in an electrolytic solution, bringing a gas containing the specific material into contact with the electrolytic solution, and dissolving the specific material in the electrolytic solution. The substance is brought into contact with the reactive substance in the pores of the silica-based mesoporous material, and the specific substance is converted into a product. In this case, the specific substance diffuses in the region where the reactant is fixed in order to come into contact with the reactant and the product moves to the outside of the reactant complex. That is, in the conventional silica-based mesoporous material, the fixed region where the reactive substance is fixed and the diffusion region where the specific substance or product diffuses are not separated.

Here, examples of the shape of the silica-based mesoporous material include powder, granule, sheet, bulk, and membrane. In addition, the orientation of the pores may be random or controlled in one direction.
JP 2008-1993979 A

  However, in any shape and orientation, the size of the pores of the silica-based mesoporous material is on the order of nanometers, and the fixed region in which the reactant is fixed and the diffusion region in which the specific substance or product diffuses Therefore, if a reactive substance having a large molecular weight is fixed inside the pores of the silica-based mesoporous material, the diffusibility of the specific substance or product in the pores deteriorates. Therefore, there is a problem that the reaction cannot be carried out at a high speed particularly when the aspect ratio (pore depth / pore diameter) of the silica-based mesoporous material is high. In addition, in the case of a method for forcibly permeating a liquid or gas containing a specific substance, if a reactive substance having a large molecular weight is fixed inside the pores of the silica-based mesoporous material, the pressure loss increases. Cannot be transmitted at high speed, and the reaction cannot be carried out at high speed.

  An object of the present invention is to provide a carrier capable of realizing a reaction at a higher speed with a supported reactant, a reactant complex including the carrier, and a method for producing the carrier.

In order to solve the above-mentioned problem, the invention described in claim 1
In a carrier carrying a reactive substance that selectively reacts with a specific substance,
A substrate having a plurality of through holes parallel to each other;
A hollow fiber-like silica structure formed in the through hole along the inner wall of the through hole;
With
The silica structure has a plurality of holes in the order of nanometers on the inner wall surface,
The reactant is fixed in the hole.

The invention described in claim 2
The carrier according to claim 1,
The base material is an anodized alumina substrate obtained by anodizing a substrate containing aluminum,
The through hole is a hole formed by the anodic oxidation.

The invention according to claim 3
The carrier according to claim 1 or 2,
The reactant is a biocatalyst, and the size of the hole is 0.5 to 2.0 times the size of the biocatalyst.

The invention according to claim 4
In the reactant complex,
The carrier according to any one of claims 1 to 3,
The reactants supported on the carrier;
It is characterized by providing.

The invention described in claim 5
In the manufacturing method of the carrier according to any one of claims 1 to 3,
A silica layer forming step of forming a silica layer containing a predetermined surfactant on the inner wall of the through hole;
A silica structure forming step of removing the surfactant from the silica layer to form the silica structure;
It is characterized by providing.

The invention described in claim 6
In the manufacturing method of the support | carrier of Claim 5,
The silica layer forming step includes
A suction introduction step of sucking and introducing the silica source solution containing the surfactant into the through hole at a predetermined suction speed;
A suction drying step of sucking and drying the silica source solution introduced into the through hole at a predetermined suction speed;
With
The silica structure forming step is characterized by removing the surfactant from the silica layer by firing the silica layer.

According to the present invention, the carrier includes a base material having a plurality of through-holes parallel to each other, and a hollow fiber-like silica structure formed in the through-hole along the inner wall of the through-hole. The body has a plurality of holes in the order of nanometers on the inner wall surface, and the reactants are fixed inside the holes.
Therefore, the wall surface portion of the silica structure becomes a fixed region where the reactant is fixed, and the hollow portion of the silica structure becomes a diffusion region where the specific substance or product diffuses. That is, since the silica structure has a structure in which the fixed region and the diffusion region are separated, even when a reactant having a large molecular weight is fixed, the silica structure has a high aspect ratio. In addition, it is possible to provide a carrier capable of realizing a reaction at a higher speed by the supported reactant and a reactant complex including the carrier.

Further, according to the present invention, a silica layer forming step of forming a silica layer containing a predetermined surfactant on the inner wall of the through hole of the base material, and removing the surfactant from the silica layer, The silica structure forming step to be formed is used to manufacture the carrier.
That is, a carrier capable of realizing a reaction at a higher speed by the supported reactant can be produced by a simple method.

  Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings. The scope of the invention is not limited to the illustrated example.

  FIG. 1 is a schematic diagram for explaining the configuration of the carrier 10 of the present embodiment. FIG. 2 is a schematic diagram for explaining the configuration of the reactant complex 1 of the present embodiment, and FIG. 3 is a schematic cross-sectional view for explaining the main configuration of the reactant complex 1 of the present embodiment. It is.

<Carrier>
The carrier 10 is for supporting a reactive substance 20 that selectively reacts with a specific substance.
Specifically, the carrier 10 includes, for example, a base material 11 having a plurality of through-holes 11a parallel to each other, and a hollow fiber-like silica structure formed in the through-hole 11a along the inner wall 11a1 of the through-hole 11a. 12, and the reactant 20 is fixed inside the pores 12 a as the holes of the silica structure 12.

  The base material 11 is, for example, an anodized alumina substrate (anodized alumina film) obtained by anodizing a substrate containing aluminum (a substrate made of aluminum or an aluminum alloy).

The through hole 11a is, for example, a cylindrical hole that is formed by anodic oxidation and penetrates from one surface of the substrate 11 to the other surface.
The diameter of the through-hole 11a can be arbitrarily arbitrarily changed according to the type of the reactant 20 supported on the carrier 10, and specifically, for example, 10 nm to 10 μm.

  The base material 11 is not limited to an anodized alumina substrate, but a metal oxide having a plurality of parallel through holes 11a such as an anodized metal substrate obtained by anodizing a substrate containing a predetermined metal. Any substrate can be used.

The silica structure 12 has such a shape that a porous silica film (silica mesh body) having a plurality of pores 12a having a size on the order of nanometers is rounded and formed into a cylindrical shape. That is, the silica structure 12 is a hollow fiber-like silica-based mesoporous material having a plurality of pores 12a having a size of nanometer order on the wall surface.
The silica structure 12 is formed using the inner wall 11a1 of the through hole 11a of the substrate 11 as a mold. Specifically, for example, an organic-inorganic composite (silica layer containing a surfactant) is formed on the inner wall 11a1 of the through-hole 11a by self-assembly of a surfactant and silica, and then an organic-inorganic composite is formed. By removing the surfactant from the body by incineration or solvent extraction, a mesoporous porous material (silica structure 12) having a periodic structure is formed.

The pores 12a are holes that penetrate from the inner wall surface 12b to the outer wall surface 12c of the silica structure 12 and are formed using a surfactant micelle as a template. The penetration direction of the pores 12a is, for example, substantially perpendicular to the penetration direction of the penetration hole 11a included in the base material 11.
The size of the pores 12a (center pore diameter) can be arbitrarily arbitrarily changed according to the type of the reactant 20 supported on the carrier 10, and specifically, for example, 1 nm to 50 nm. Here, the size of the pores 12a can be controlled by changing the type of the surfactant and changing the diameter of the micelle of the surfactant. Also, the size of the pores 12a can be determined by, for example, adding a relatively hydrophobic molecule such as trimethylbenzene or tripropylbenzene together with a surfactant to swell the micelles and changing the micelle diameter. Can be controlled.
Here, the central pore diameter of the pores 12a is based on the assumption that the cross-sectional shape of the pores 12a is a perfect circle, and the pore volume (V) of the silica structure 12 is the diameter (D) of the pores 12a. Means the pore diameter at the maximum peak of a curve (pore diameter distribution curve) obtained by plotting the value (dV / dD) differentiated with respect to the diameter (D) of the pore 12a. Note that the cross-sectional shape of the pores 12a shown in FIGS. 1 and 2 is a regular hexagonal shape.

When the reactant 20 to be carried on the carrier 10 is a biocatalyst such as protein, for example, the size of the pores 12a of the silica structure 12 is about 0.5 to 2.0 times the size of the biocatalyst. It is preferable that it is about 0.7 to 1.4 times the size of the biocatalyst, and most preferably about the same as the size of the biocatalyst. If the size of the pores 12a is less than 0.5 times the size of the biocatalyst supported on the carrier 10, the biocatalyst tends to be insufficiently adsorbed into the pores 12a. If the length is larger than 2.0 times the size of the biocatalyst supported on the carrier 10, the three-dimensional structure of the biocatalyst tends not to be efficiently maintained.
That is, the size of the pores 12a of the silica structure 12 is about 0.5 to 2.0 times (more preferably about 0.7 to 1.4 times) the size of the biocatalyst supported on the carrier 10. (Preferably approximately the same), the fixation (adsorption) of the biocatalyst to the carrier 10 can be made more efficient, and the three-dimensional structure of the biocatalyst fixed to the carrier 10 can be easily maintained. It can be supported stably.
Specifically, for example, when formaldehyde dehydrogenase is supported on the carrier 10 as a biocatalyst, the diameter of the formaldehyde dehydrogenase is about 8 nm. Therefore, the size of the pores 12a of the silica structure 12 is as follows: About 4 nm to 16 nm is preferable.

When the reactant 20 to be carried on the carrier 10 is a protein and the protein forms a multimer, the size of the protein carried on the carrier 10 can be the size of the multimer. Here, the multimer means a compound in which two or more proteins are bonded directly or through a small molecule such as water, and the bond includes a covalent bond, an ionic bond, a hydrogen bond, and a coordinate bond. Is included. However, the type of these bonds is not particularly limited.
The size of the reactant 20 supported on the carrier 10 is the diameter of the reactant 20 when the reactant 20 has a spherical shape (for example, when there are a plurality of diameters such as an oval sphere) 1), in the case of a plate shape, the length of the long side of the reactant 20 can be set as such, but is not limited thereto, and is arbitrarily selected according to the shape and characteristics of the reactant 20 It is preferable to make a judgment.

  In addition, when the reactant 20 to be supported on the carrier 10 is a biocatalyst such as a protein, for example, the acid dissociation constant (pKa) of the silica structure 12 is from the viewpoint of suppressing denaturation of the supported biocatalyst. , PKa5-14 are preferred.

In addition, the depth of the pores 12a (that is, the thickness of the wall surface of the silica structure 12) can be arbitrarily arbitrarily changed according to the type of the reactant 20 to be supported on the carrier 10, and specifically, for example, 1 nm or more.
Here, as one of the factors that determine the thickness of the wall surface of the silica structure 12, the suction speed at the time of self-assembly of the surfactant and silica (that is, the suction speed at the time of suction introduction and suction drying) can be mentioned. . As the suction speed decreases, the thickness of the wall surface of the hollow fiber-like silica structure 12 formed in the through-hole 11a of the base material 11 increases, and when the suction speed falls below a predetermined threshold, the through-hole 11a enters the through-hole 11a. The silica-based mesoporous material (hollow fiber-like silica structure 12) having a structure in which the fixing region A1 and the diffusion region A2 are separated is not formed, and the fixing region A1 and the diffusion region A2 are not separated. A silica-based mesoporous material (for example, a conventional silica-based mesoporous material as shown in FIG. 11) is formed.

The silica structure 12 is preferably a silica-based mesoporous material having a pore volume of 0.1 to 1.5 mL / g, and is a silica-based mesoporous material having a specific surface area of 200 to 1500 m ^2. It is preferable. The silica structure 12 is a silica-based mesoporous material in which the ratio of the total volume of pores having a diameter within a range of ± 40% of the center pore diameter in the total pore volume is 60% or more. Is preferred.
Here, “the ratio of the total volume of pores having a diameter within the range of ± 40% of the center pore diameter in the total pore volume is 60% or more” means that the center pore diameter is 3. When it is 00 nm, it means that the total volume of pores in the range of ± 40% of 3.00 nm, that is, 1.80 to 4.20 nm occupies 60% or more of the total pore volume. To do.
A silica-based mesoporous material satisfying such conditions means that the pore diameter is very uniform. For example, the reactive mesoporous material having such a pore-arranged structure can be used as the reactant 20. When a biocatalyst such as protein is adsorbed, the stability of the biocatalyst and the adsorption amount (fixed amount) can be further improved. The pore volume is determined by, for example, a method (nitrogen adsorption method) in which the base material 11 is dissolved with a phosphoric acid solution or a nitric acid solution, the precipitated silica structure 12 is cooled to liquid nitrogen temperature, and nitrogen gas is introduced. Can be calculated.

The silica structure 12 is preferably a silica-based mesoporous material that exhibits an X-ray diffraction pattern having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more. When a peak appears in the X-ray diffraction pattern, it means that a periodic structure having a d value corresponding to the peak angle is present in the silica-based mesoporous material.
Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more means that the pores are regularly arranged at intervals of 1 nm or more. Thus, for example, when a biocatalyst such as protein is adsorbed as the reactant 20 on the silica-based mesoporous material having a very regular pore arrangement structure, the stability and the amount of adsorption of the biocatalyst are further improved. It becomes possible.

Note that the arrangement state (pore arrangement structure) of the pores 12a in the silica structure 12 is not particularly limited. Examples of the silica structure 12 include those having a hexagonal pore arrangement structure and those having a cubic or disorder pore arrangement structure.
Here, the silica structure 12 having a hexagonal pore arrangement structure means that the arrangement of the pores 12a of the silica structure 12 is a hexagonal structure. Examples of the hexagonal pore arrangement structure include two-dimensional hexagonal and three-dimensional hexagonal. A silica structure 12 having a two-dimensional hexagonal pore arrangement structure that can be suitably used in the present invention has a hexagonal column-like fine structure based on a two-dimensional hexagonal arrangement structure, for example, as shown in FIGS. The holes are regularly formed in parallel with each other.
The silica structure 12 having a cubic pore arrangement structure means that the arrangement of the pores 12a of the silica structure 12 is a cubic structure.
The silica structure 12 having a disordered pore arrangement structure means that the arrangement of the pores 12a of the silica structure 12 is irregular.

  In addition, when the silica structure 12 has a regular pore arrangement structure such as hexagonal or cubic, it is not necessary that all of the pores 12a have these regular pore arrangement structures. That is, the silica structure 12 can have both a regular pore arrangement structure such as hexagonal or cubic and a disordered irregular pore arrangement structure. However, 80% or more of all the pores 12a preferably have a regular pore arrangement structure such as hexagonal or cubic.

Examples of the silica structure 12 include a silica-based mesoporous material having an organic group and a silica-based mesoporous material having no organic group. In any silica-based mesoporous material, a metal element other than silicon (for example, Al, Zr, Ti) can be further included. In any silica mesoporous material, silanol groups (—SiOH groups) exist on the surface.
The silica-based mesoporous material having an organic group refers to a material in which an organic group is bonded to at least a part of silicon atoms constituting the silica-based mesoporous material by forming a carbon-silicon bond. Examples of the organic group include a hydrocarbon group, an amide group, an amino group, an imino group, a mercapto group, a sulfone group, and a carboxyl group that are generated by removing one or more hydrogens from hydrocarbons such as alkanes, alkenes, alkynes, benzenes, and cycloalkanes. Group, ether group, acyl group, vinyl group and the like.

<Reactive substances>
The reactive substance 20 is arbitrary as long as it is a substance that selectively reacts with a specific substance or its product. Specifically, for example, a molecular identification element derived from a living body (a biocatalyst such as a protein), palladium, Metal catalysts such as platinum, oxidation catalysts such as ruthenium oxide, manganese oxide, iron oxide and titanium oxide, other organic catalysts or inorganic catalysts, various polymers, polymer complexes, polyion complexes, light-absorbing substances, fluorescent substances, dyes and the like.
In addition, the kind of the reactant 20 supported on the carrier 10 may be one kind or plural kinds.

<Reactant complex>
For example, as illustrated in FIGS. 2 and 3, the reactant complex 1 includes a carrier 10 and a reactant 20 supported on the carrier 10. The reactant complex 1 can be suitably applied, for example, as a sensor for biochemical analysis or trace component analysis, or as a reactor in polymer synthesis or catalytic reaction.

Here, in the carrier 10, the inside of the through-hole 11 a of the base material 11, as shown in FIG. 3, for example, is a solid region A1 to which the reactant 20 is fixed, a specific substance (reactant), and a product (reaction). And a diffusion region A2 in which the product is diffused.
The fixing region A1 is a wall surface portion of the silica structure 12, and the reactant 20 is fixed inside the pores 12a formed in the wall surface portion.
Diffusion region A2 consists of a hole penetrating from one surface of reactant complex 1 to the other surface. That is, the diffusion region A2 is a hollow portion of the silica structure 12 and is a cavity that is not filled with anything.

Therefore, for example, when a liquid or gas containing a specific substance is forcibly permeated from one surface of the reactant complex 1 to the other surface, the liquid or gas passes through the diffusion region A2.
For example, in the case of the conventional reactant complex as shown in FIG. 11, the fixed region A1 and the diffusion region A2 are not separated (the specific substance or product diffuses in the region where the reactant 20 is immobilized). Therefore, the liquid or gas passes through the region where the reactant 20 is fixed. On the other hand, in the case of the reactant complex 1 of the present invention, the liquid or gas passes through the diffusion region A2 in a hollow state that is not filled with anything, as compared with the conventional reactant complex. Since the pressure loss is low and the liquid or gas can permeate at high speed, the reaction can be carried out at high speed.

Furthermore, when the liquid or gas passes through the diffusion region A2, the specific substance contained in the liquid or gas diffuses through the diffusion region A2 and moves to the reactant 20 fixed in the fixed region A1. In contact with the reactant 20. The product generated by the contact also diffuses in the diffusion region A2 and moves to the outside of the reactant complex 1.
For example, in the case of the conventional reactant complex as shown in FIG. 11, since the fixed region A1 and the diffusion region A2 are not separated, the specific substance or product is a region where the reactant 20 is fixed. Will spread. On the other hand, in the case of the reactant complex 1 of the present invention, the specific substance or product diffuses in the diffusion region A2 in a hollow state where nothing is filled, which is compared with the conventional reactant complex. In addition, since the diffusibility of the specific substance or product is increased, the reaction can be performed at high speed.

Further, for example, when the reactant complex 1 is immersed in an electrolytic solution, a gas containing the specific substance is brought into contact with the electrolytic solution, and the specific substance is dissolved in the electrolytic solution, the specific substance is Then, it diffuses outside the reactant complex 1 and moves to the inside (diffusion region A2), further diffuses through the diffusion region A2 and moves to the reactant 20 fixed to the fixed region A1, and the reactant 20 is contacted. The product generated by the contact also diffuses in the diffusion region A2 and moves to the outside of the reactant complex 1.
For example, in the case of the conventional reactant complex as shown in FIG. 11, since the fixed region A1 and the diffusion region A2 are not separated, the specific substance or product is a region where the reactant 20 is fixed. Will spread. On the other hand, in the case of the reactant complex 1 of the present invention, the specific substance or product diffuses in the diffusion region A2 in a hollow state where nothing is filled, which is compared with the conventional reactant complex. In addition, since the diffusibility of the specific substance or product is increased, the reaction can be performed at high speed.

<Method for producing reactant complex>
Next, a method for producing the reactant complex 1 will be described. The reactant complex 1 is produced by producing the carrier 10 and immobilizing the reactant 20 on the produced carrier 10.

(Manufacture of carrier)
First, a silica source solution containing a surfactant is prepared.
Here, the silica source solution is a solution containing a compound that becomes a silica source (for example, alkoxysilane such as tetraethyl orthosilicate (TEOS)).
The surfactant can be arbitrarily changed as appropriate according to the type of the reactant 20 to be supported on the carrier 10, and triblock copolymers CTAB, P123, F127, and the like can be preferably used.
Specifically, for example, CTAB, P123 and / or F127 are dissolved in a mixture of ethanol and hydrochloric acid, and stirred at about 30 ° C. to 60 ° C. for several hours using a refluxer.
Next, a silica source solution such as TEOS is added thereto, and the mixture is further stirred at about 30 ° C. to 60 ° C. for about 2 hours to about 20 hours using a refluxer, whereby a silica source solution containing a surfactant is obtained. Prepare.
In addition, the kind of surfactant contained in a silica source solution may be one kind, and plural kinds may be sufficient as it.

Next, a silica layer containing a surfactant is formed on the inner wall 11a1 of the through hole 11a of the base material 11 (silica layer forming step).
Specifically, for example, the prepared silica source solution containing the surfactant is dropped onto one surface of the base material 11 and dropped at a predetermined suction speed using a suction device such as a vacuum pump. A silica source solution containing a surfactant is sucked and introduced into the through-hole 11a (suction introduction step).
Next, for example, the silica source solution containing the surfactant introduced into the through hole 11a is sucked and dried at a predetermined suction speed using a suction device such as a vacuum pump (suction drying step), and the through hole is formed. A silica layer containing a surfactant is formed on the inner wall 11a1 of 11a.
Note that the suction speed at the time of suction introduction and the suction speed at the time of suction drying may be the same or different.

Next, the surfactant is removed from the silica layer formed on the inner wall 11a1 of the through hole 11a to form the silica structure 12 (silica structure forming step).
Specifically, for example, by firing the silica layer formed on the inner wall 11a1 of the through hole 11a and removing the surfactant from the silica layer, a hollow fiber-like shape is formed along the inner wall 11a1 of the through hole 11a. A silica structure 12 is formed.
The carrier 10 is manufactured as described above.

(Reaction substance fixation)
First, a reactant solution containing the reactant 20 is prepared.
Next, the produced carrier 10 is immersed in the prepared reactant solution, and the reactant 20 is adsorbed and fixed on the carrier 10.
Next, the reactant 10 in the diffusion region A2 is washed away by washing the carrier 10.
As described above, the reactant 20 is immobilized on the produced carrier 10 to produce the reactant complex 1.

  In addition, the manufacturing method of said support | carrier 10 and the manufacturing method of the reactant composite 1 are examples, and are not restricted to this.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

<Example 1>
In Example 1, a carrier was prepared and evaluated.

First, 1.0 g of surfactant (P123) was mixed with 20 mL of ethanol, 100 μL of concentrated hydrochloric acid and 2 mL of water, and refluxed at 60 ° C. for 1 hour with stirring.
Next, 2.13 g of TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.

  Next, a certain voltage is applied to the aluminum substrate in a phosphoric acid solution, and the aluminum substrate is anodized to produce an anodized alumina substrate (base material 11) having a through-hole diameter of 100 nm and a thickness of 60 μm. did.

Next, the prepared silica source solution containing the surfactant is dropped on one surface of the produced anodized alumina substrate, and the through hole of the anodized alumina substrate is used at a suction speed of 10 L / min using a suction device. Suction was introduced into the inside.
Next, the silica layer solution containing the surfactant sucked into the through-hole is sucked and dried at a suction speed of 10 L / min by using a suction device, whereby the silica layer containing the surfactant in the through-hole. Formed.

  Next, the anodized alumina substrate in which the silica layer containing the surfactant is formed in the through hole is dried overnight in a desiccator, and then baked at 500 ° C. for 6 hours. The carrier was prepared by removing

Next, the produced carrier was cut obliquely with respect to the through hole, and the cross section thereof was observed using an SEM (scanning electron microscope). The result is shown in FIG.
As shown in FIG. 4, as a result of SEM observation, it was confirmed that a hollow fiber-like structure was formed along the inner wall of the through hole of the anodized alumina substrate.

Further, the produced carrier was cut obliquely with respect to the through-hole, and the cross section was observed using a TEM (transmission electron microscope). The result is shown in FIG.
As shown in FIG. 5, as a result of TEM observation, it was confirmed that the hollow fiber-like structure formed along the inner wall of the through hole of the anodized alumina substrate had a mesh-like uniform three-dimensional structure. As a result of TEM observation, it was found that this hollow fiber-like structure had a wall thickness of about 8.0 nm. Furthermore, as a result of TEM observation, it was confirmed that the pores (pores 12a) of the hollow fiber-like structure have a substantially regular hexagonal cross-sectional shape and an average pore size of about 8.0 nm. . Here, the pore size is a distance between one side and another side facing the one side in the hexagon.

Further, the produced carrier was analyzed using EDX (energy dispersive X-ray spectroscopy).
As a result, it was confirmed that silica was distributed along the inner wall of the through hole of the anodized alumina substrate.

  From the results of the above SEM, TEM, and EDX, the hollow fiber shape formed along the inner wall 11a1 of the anodized alumina substrate (base material 11) and the through hole 11a of the base material 11 by the carrier manufacturing method of the present invention. It was confirmed that a carrier (carrier 10) having the structure (silica structure 12) can be produced.

<Example 2>
In Example 2, a support was prepared, and the amount of the surfactant and the amount of TEOS in the silica source solution containing the surfactant were evaluated.

First, surfactant (P123) was mixed with 20 mL of ethanol, 100 μL of concentrated hydrochloric acid and 2 mL of water, and refluxed at 60 ° C. for 1 hour with stirring.
Subsequently, TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.

  Next, a certain voltage is applied to the aluminum substrate in a phosphoric acid solution, and the aluminum substrate is anodized to produce an anodized alumina substrate (base material 11) having a through-hole diameter of 100 nm and a thickness of 60 μm. did.

Next, the prepared silica source solution containing the surfactant is dropped on one surface of the produced anodized alumina substrate, and the through hole of the anodized alumina substrate is used at a suction speed of 10 L / min using a suction device. Suction was introduced into the inside.
Next, the silica layer solution containing the surfactant sucked into the through-hole is sucked and dried at a suction speed of 10 L / min by using a suction device, whereby the silica layer containing the surfactant in the through-hole. Formed.

  Next, the anodized alumina substrate in which the silica layer containing the surfactant is formed in the through hole is dried overnight in a desiccator, and then baked at 500 ° C. for 6 hours. The carrier was prepared by removing

Here, three types of support | carriers were produced using each silica source solution (the amount of TEOS is 2.13g) whose amount of P123 is 0.6g, 1.0g, and 1.5g.
Three types of carriers were prepared using each silica source solution (the amount of P123 was 1.0 g) in which the amount of TEOS was 1.28 g, 2.13 g, and 3.2 g.

Next, each of the prepared six types of carriers was observed using a TEM.
As a result, when the amount of P123 was 0.6 g and 1.5 g, it was confirmed that the hollow fiber-like silica structure 12 was formed along the inner wall 11a1 of the through hole 11a of the base material 11, The fine pores 12a of the silica structure 12 were approximately hexagonal columnar shapes irregularly arranged on the inner wall 11a1 (inner wall surface) and distorted in shape.
On the other hand, when the amount of P123 is 1.0 g, for example, as shown in FIGS. 1 and 2, hollow fiber-like silica having regularly arranged regular hexagonal columnar pores 12a parallel to each other. It was confirmed that the structure 12 was formed along the inner wall 11a1 of the through-hole 11a which the base material 11 has.
Further, when the amount of TEOS was 1.28 g and 3.2 g, it was confirmed that the hollow fiber-like silica structure 12 was formed along the inner wall 11a1 of the through hole 11a of the base material 11, The fine pores 12a of the silica structure 12 were approximately hexagonal prisms irregularly arranged on the inner wall 11a1 (inner wall surface) and distorted in shape.
On the other hand, when the amount of TEOS is 2.13 g, for example, a hollow fiber-like silica having regular regular hexagonal columnar pores 12a arranged in parallel with each other as shown in FIGS. It was confirmed that the structure 12 was formed along the inner wall 11a1 of the through-hole 11a which the base material 11 has.
From the above results, when P124 is used as the surfactant, a silica source in which the amount of P123 is 1.0 g and the amount of TEOS is 2.13 g from the viewpoint of the shape of the pores 12 a of the silica structure 12. It has been found that it is preferable to make the carrier 10 using a solution.

Similarly, for the surfactant F127, a support was prepared, and the amount of the surfactant and the amount of TEOS in the silica source solution containing the surfactant were evaluated.
As a result, when F127 is used as the surfactant, from the viewpoint of the shape of the pores 12a of the silica structure 12, the silica source solution (0.92 g of F127 and 2.0 g of TEOS) ( It turned out that it is suitable to produce the support | carrier 10 using the specific composition (refer Example 4).

Similarly, for the surfactant CTAB, a carrier was prepared, and the amount of the surfactant and the amount of TEOS in the silica source solution containing the surfactant were evaluated.
As a result, when CTAB is used as the surfactant, a silica source solution having a CTAB amount of 1.52 g and a TEOS amount of 11.57 g from the viewpoint of the shape of the pores 12a of the silica structure 12 ( It turned out that it is suitable to produce the support | carrier 10 using the specific composition (refer Example 4).

<Example 3>
In Example 3, the carrier is prepared, and the silica containing the surfactant introduced into the through-hole 11a is sucked and introduced into the through-hole 11a when sucking and introducing the silica source solution containing the surfactant into the through-hole 11a. The suction speed when the source solution was dried by suction (at the time of suction drying) was evaluated.

First, 1.0 g of surfactant (P123) was mixed with 20 mL of ethanol, 100 μL of concentrated hydrochloric acid and 2 mL of water, and refluxed at 60 ° C. for 1 hour with stirring.
Next, 2.13 g of TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.

  Next, a certain voltage is applied to the aluminum substrate in a phosphoric acid solution, and the aluminum substrate is anodized to produce an anodized alumina substrate (base material 11) having a through-hole diameter of 100 nm and a thickness of 60 μm. did.

Next, the prepared silica source solution containing the surfactant was dropped onto one surface of the produced anodized alumina substrate, and sucked into the through hole of the anodized alumina substrate using a suction device.
Next, the silica source solution containing the surfactant sucked and introduced into the through hole is sucked and dried by using the suction device at the same suction speed as that when sucking is introduced, so that the surfactant is put into the through hole. A containing silica layer was formed.

  Next, the anodized alumina substrate in which the silica layer containing the surfactant is formed in the through hole is dried overnight in a desiccator, and then baked at 500 ° C. for 6 hours. The carrier was prepared by removing

  Here, the suction speed at the time of suction introduction and suction drying is 0.1 L / min, 0.5 L / min, 1 L / min, 2 L / min, 3 L / min, 5 L / min, 8 L / min, and 10 L / min. As a result, eight types of carriers were prepared.

Next, each of the produced eight types of carriers was observed using a TEM. The results are shown in Table 1.

As shown in Table 1, when the suction speed is 1 L / min or more as a result of TEM observation, the hollow fiber-like silica structure 12 is formed along the inner wall 11a1 of the through hole 11a of the base material 11. It was confirmed that That is, a silica-based mesoporous material (silica structure 12) is formed in which the penetration direction of the pores 12a is substantially orthogonal to the penetration direction of the penetration hole 11a and has a hollow portion (diffusion region A2). It was confirmed that
On the other hand, when the suction speed is 0.5 L / min or less, not the hollow fiber-like silica structure 12 but a conventional silica-based mesoporous material having pores having a pore size of about 8.0 nm (for example, 11) was formed in the through hole 11a of the base material 11. In other words, it was confirmed that a silica-based mesoporous material having a pore penetration direction substantially the same as the penetration direction of the through-hole 11a and having no hollow portion was formed.

  Moreover, as shown in Table 1, when the suction speed is 1 L / min or more as a result of TEM observation, the thickness of the wall surface of the hollow fiber-like silica structure 12 may become thinner as the suction speed increases. confirmed.

  From the above results, in order to form a hollow fiber-like silica structure 12 when a solution having the above composition (a solution containing a surfactant) is used and the base 11 having a diameter of the through hole 11a of 100 nm is used. It was found that it was necessary to introduce and suck and suck at a suction speed of 1 L / min or more. It was also found that the thickness of the wall surface of the hollow fiber-like silica structure 12 can be controlled by the suction speed.

<Example 4>
In Example 4, a support was prepared, and the relationship between the type of the surfactant in the silica source solution containing the surfactant and the size of the pores 12a of the hollow fiber silica structure 12 was evaluated.

First, 1.0 g of surfactant (P123) was mixed with 20 mL of ethanol, 100 μL of concentrated hydrochloric acid and 2 mL of water, and refluxed at 60 ° C. for 1 hour with stirring.
Next, 2.13 g of TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.

  Next, a certain voltage is applied to the aluminum substrate in a phosphoric acid solution, and the aluminum substrate is anodized to produce an anodized alumina substrate (base material 11) having a through-hole diameter of 100 nm and a thickness of 60 μm. did.

Next, the prepared silica source solution containing the surfactant is dropped on one surface of the produced anodized alumina substrate, and the through hole of the anodized alumina substrate is used at a suction speed of 10 L / min using a suction device. Suction was introduced into the inside.
Next, the silica layer solution containing the surfactant sucked into the through-hole is sucked and dried at a suction speed of 10 L / min by using a suction device, whereby the silica layer containing the surfactant in the through-hole. Formed.

  Next, the anodized alumina substrate in which the silica layer containing the surfactant is formed in the through hole is dried overnight in a desiccator, and then baked at 500 ° C. for 6 hours. The carrier was prepared by removing

Further, 0.92 g of a surfactant (F127) was mixed with 23.5 mL of ethanol, 200 μL of concentrated hydrochloric acid and 1.33 mL of water, and refluxed at 60 ° C. for 1 hour with stirring.
Next, 2.0 g of TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.
And the support | carrier was produced like the case of the silica source solution containing surfactant P123.

Further, 1.52 g of a surfactant (CTAB) was mixed with 15 g of ethanol and 4 mL of concentrated hydrochloric acid, and refluxed at 60 ° C. for 1 hour with stirring.
Next, 11.57 g of TEOS was added thereto, and the mixture was stirred at 60 ° C. for 12 hours using a refluxer to prepare a silica source solution containing a surfactant.
And the support | carrier was produced like the case of the silica source solution containing surfactant P123.

Next, each of the prepared three types of carriers was observed using a TEM. The results are shown in Table 2.

As shown in Table 2, as a result of TEM observation, it was confirmed that the size of the pores 12a of the hollow fiber silica structure 12 was different depending on the type of the surfactant.
From the above results, it was found that the size of the pores 12a of the silica structure 12 can be controlled depending on the type of surfactant contained in the silica source solution.

<Example 5>
In Example 5, a reactant complex 1 was prepared by immobilizing a biocatalyst (specifically, formaldehyde dehydrogenase) as the reactant 20 on the carrier 10, and the reactant complex 1 was evaluated.

First, the carrier 10 was produced in the same manner as in Example 1.
Next, formaldehyde dehydrogenase was dissolved in phosphate buffer (pH 7.4) to prepare an enzyme solution having a formaldehyde dehydrogenase concentration of 1.2 mg / mL.
Next, 2.5 mL of the prepared enzyme solution was dropped on one surface of the produced carrier 10 and allowed to stand overnight at 3 ° C.
Next, the carrier 10 to which the enzyme solution is dropped is washed three times with 5 mL of deionized water, and the enzyme in the diffusion region A2 in the surface of the anodized alumina substrate or the carrier 10 is washed away, whereby the reactant complex 1 was produced.

Next, the amount of enzyme immobilized in the produced reactant complex 1 was measured using TG-DTA (thermogravimetric differential thermal analyzer).
As a result, it was confirmed that 2.0 mg of formaldehyde dehydrogenase was immobilized on 1 g of the carrier 10.

<Example 6>
In Example 6, the reactant complex 1 produced in Example 5 was evaluated using a specific substance solution containing a specific substance (specifically, formaldehyde).
Specifically, a reaction for oxidizing formaldehyde to formic acid (HCHO + NAD ⁺ + 3H ₂ O − (formaldehyde dehydrogenase) → HCOO ⁻ + NADH + 2H ₃ O ⁺ ) (ie, NAD ⁺ (oxidation) Formaldehyde) provided in the reactant complex 1 produced in Example 5) by selecting a wavelength 340 nm characteristic of NADH (reduced type) generated by the reduction of the type) and determining the concentration of the produced NADH from the change in absorbance thereof. Dehydrogenase activity was measured.

First, 1.0 g of pulverized reactant complex 1 prepared in Example 5 was added to 3.0 mL of phosphate buffer (pH 7.4).
Next, 12 mg of coenzyme (nicotinamide adenine dinucleotide (NAD ⁺ )) and 300 μL of a formaldehyde aqueous solution having a formaldehyde concentration of 0.3% were added thereto, and the mixture was allowed to stand at 25 ° C.
Next, 600 μL of the supernatant of the specific substance solution added with the pulverized reactant complex 1 was collected and mixed with 400 μL of a phosphate buffer (pH 7.4) to obtain a sample (sample for Example 6). Was made.

  Next, the absorption at 340 nm of the produced sample for Example 6 was measured using an absorptiometer. The result is shown in FIG.

As Comparative Example 1, the same measurement was performed with a free enzyme.
Specifically, a sample (sample for Comparative Example 1) was prepared in the same manner as in Example 6 using 2.0 mg of formaldehyde dehydrogenase instead of 1.0 g of the pulverized reactant complex 1. Was made.
Next, the absorption at 340 nm of the prepared sample for Comparative Example 1 was measured using an absorptiometer. The result is also shown in FIG.

  In FIG. 6, the horizontal axis indicates the reaction time (that is, the elapsed time since the addition of the aqueous formaldehyde solution), and the vertical axis indicates the absorbance at 340 nm. Further, the circle plot (◯) shows the result of Example 6, and the triangle plot (Δ) shows the result of Comparative Example 1.

As shown in FIG. 6, as a result of the absorbance measurement, the immobilized enzyme of Example 6 (that is, the enzyme included in the reactant complex 1 prepared in Example 5) is immobilized in the silica structure 12 having a high aspect ratio. Nevertheless, it was found to have a reaction rate and enzyme activity equivalent to those of the free enzyme of Comparative Example 1.
From the above results, it was found that the carrier 10 of the present invention can realize a reaction at a reaction rate equivalent to that of the free enzyme by the supported reactant 20.

<Example 7>
In Example 7, the reactive substance complex 1 produced in Example 5 was evaluated using a specific substance gas containing a specific substance (specifically, formaldehyde).

First, the enzyme sensor S for gas detection shown in FIGS.
7 is a plan perspective view of the enzyme sensor S, FIG. 8 is a diagram schematically showing a cross section taken along line VIII-VIII in FIG. 7, and FIG. 9 is a cross section taken along line IX-IX in FIG. It is a figure shown typically.
The enzyme sensor S is a sensor that detects a specific substance in a gas sample (specific substance gas) by an electrochemical measurement method using the characteristics of the reactive substance 20 included in the reactive substance complex 1. Specifically, the enzyme sensor S includes, for example, a sensor head S1 and a reactant complex 1 as shown in FIGS.

The sensor head S1 includes a lower body portion S11, an upper body portion S12 disposed on the lower body portion S11, an electrode portion S13 disposed between the lower body portion S11 and the upper body portion S12, A liquid phase part S14 and a gas phase part S15 formed in the sensor head S1, a gas permeable film S16 separating the liquid phase part S14 and the gas phase part S15, and the like are provided.
The electrode part S13 includes a working electrode S13a, a counter electrode 13b, a reference electrode S13c, and the like.
The liquid phase part S14 includes a solution introduction port S14a for introducing the solution into the liquid phase part S14, a solution discharge port S14b for discharging the solution introduced into the liquid phase part S14, and the like. .
The gas phase section S15 includes a gas inlet S15a for introducing the specific substance gas into the gas phase section S15, a gas outlet S15b for discharging the specific substance gas introduced into the gas phase section S15, and the like. It has.

In the reactant complex 1, the penetration direction of the through hole 11 a of the base material 11 is substantially orthogonal to the upper surface of the electrode part S 13 between the electrode part S 13 and the gas permeable film S 16 in the liquid phase part S 14. Are arranged as follows.
Here, the specific substance in the specific substance gas introduced into the gas phase part S15 permeates the gas permeable membrane S16, moves to the liquid phase part S14, and is a reactant composite disposed in the liquid phase part S14. The diffusion region A2 in the body 1 is diffused to come into contact with the reactant 20 fixed in the fixed region A1 in the reactant complex 1. And the product produced | generated by the said contact diffuses the diffusion area | region A2 in the reactive substance complex 1, and transfers to the exterior (electrode part S13) of the reactive substance complex 1. FIG.
That is, the movement distance (diffusion distance) until the specific substance that has passed through the gas permeable membrane S16 comes into contact with the reactive substance 20 fixed in the fixing region A1, and the product generated by the contact are transferred to the electrode part S13. The reactant complex 1 was placed in the liquid phase part S14 so that the travel distance (diffusion distance) until it reached was shorter.

The enzyme sensor S applies a predetermined voltage (for example, a voltage of +600 mV) to the working electrode S13c with respect to the reference electrode S13a at room temperature (25 ° C.), for example, and measures the enzyme by measuring the current by amperometry By measuring the response current from the sensor S, the specific substance in the specific substance gas is detected.
For example, if a calibration curve indicating the relationship between the concentration and the response current is prepared in advance, the specific substance concentration of the specific substance gas can be measured based on the response current from the enzyme sensor S.

Next, 12 mg of NAD ⁺ was dissolved in 3 mL of phosphate buffer (pH 7.4) to prepare an electrolytic solution for filling the liquid phase part S14.
Next, the prepared electrolytic solution is introduced from the solution introduction port S14a into the liquid phase portion S14 and continued to be introduced until it leaks out from the solution discharge port S14b, whereby the liquid phase portion S14 in which the reactant complex 1 is disposed. The inside was filled with the electrolyte solution.

Next, measurement of the response current from the enzyme sensor S was started, and introduction of the specific substance gas into the gas phase S15 was started after about 6000 seconds had elapsed from the start of the measurement. As the specific substance gas, formaldehyde gas (HCHO gas) having a formaldehyde concentration of 100 ppb was used.
Next, the introduction of the specific substance gas was stopped after about 13,000 seconds from the start of the measurement, and the measurement was completed after about 16000 seconds from the start of the measurement. The measurement results are shown in FIG.

As Comparative Example 2, the same measurement was performed with a free enzyme.
Specifically, first, a product obtained by removing the reactant complex 1 from the enzyme sensor S (that is, the sensor head S1) was prepared.
Next, formaldehyde dehydrogenase is added to the electrolyte solution prepared in the same manner as in Example 7 (electrolyte solution for filling the liquid phase part S14) to prepare an enzyme solution having a formaldehyde dehydrogenase concentration of 12 mg / cc. did.
Next, the sensor (free enzyme sensor) of Comparative Example 2 was produced by filling the liquid phase portion S14 included in the sensor head S1 with the prepared enzyme solution.
Next, the response current from the free enzyme sensor when formaldehyde gas having a formaldehyde concentration of 100 ppb was introduced by the same method as in Example 7 was measured. The measurement results are also shown in FIG.

Further, as Comparative Example 3, the same measurement was performed with an FSM-immobilized enzyme immobilized on FSM, which is a conventional silica-based mesoporous material.
Here, since the FSM is a conventional silica-based mesoporous material, the fixed region A1 and the diffusion region A2 are not separated, for example, unlike the silica-based mesoporous material shown in FIG. Further, in the silica-based mesoporous material shown in FIG. 11, the orientation of the pores is controlled in one direction, but in the FSM, the orientation of the pores is random and the direction is not controlled.
Specifically, first, instead of the reactant complex 1, an FSM carrying formaldehyde dehydrogenase is disposed between the electrode part S13 of the sensor head S1 and the gas permeable membrane S16, so that the comparative example 3 Sensor (FSM immobilized enzyme sensor) was prepared.
Next, the inside of the liquid phase portion S14 included in the FSM-immobilized enzyme sensor was filled with an electrolytic solution prepared in the same manner as in Example 7 (electrolytic solution for filling the liquid phase portion S14).
Next, in the same manner as in Example 7, the response current from the FSM-immobilized enzyme sensor when formaldehyde gas having a formaldehyde concentration of 100 ppb was introduced was measured. The measurement results are also shown in FIG.

  In FIG. 10, the horizontal axis represents the elapsed time from the start of response current measurement, and the vertical axis represents the measured response current. The solid line shows the result of Example 7, the alternate long and short dash line shows the result of Comparative Example 2, and the broken line shows the result of Comparative Example 3.

As shown in FIG. 10, as a result of the response current measurement, in the enzyme sensor S of Example 7, the rise of the response was compared even though the enzyme was fixed in the silica structure 12 having a high aspect ratio. It was found to be equivalent to the free enzyme sensor of Example 2. That is, since the carrier 10 has the diffusion region A2 in the hollow state, it has been found that the diffusibility of the specific substance or product in the carrier 10 is as good as the diffusivity in the solution.
In the enzyme sensor S of Example 7, the enzyme included in the reactant complex 1 prepared in Example 5 is fixed to the carrier 10 at a high density, so that the saturation current is the free enzyme sensor of Comparative Example 2. It turned out to be bigger.
On the other hand, it was found that in the FSM-immobilized enzyme sensor of Comparative Example 3, the rise in response was slower than that of the free enzyme sensor of Comparative Example 2. This is presumably because the fixed region A1 and the diffusion region A2 are not separated and the enzyme is fixed to a carrier (FSM) with random pore orientation.
From the above results, it was found that the carrier 10 of the present invention can realize a reaction at a higher speed than the conventional carrier (conventional silica-based mesoporous material) by the supported reactant 20.

According to the carrier 10 of the present invention described above and the reactant complex 1 including the carrier 10, the carrier 10 includes a substrate 11 having a plurality of through-holes 11 a parallel to each other, and the through-hole 11 a in the through-hole 11 a. A hollow fiber-like silica structure 12 formed along the inner wall 11a1, and the silica structure 12 has a plurality of nanometer-order pores 12a on the wall surface. It is fixed inside the hole 12a.
Therefore, the wall surface portion of the silica structure 12 becomes the fixed region A1 where the reactant 20 is fixed, and the hollow portion of the silica structure 12 becomes the diffusion region A2 where the specific substance or product diffuses. That is, since the silica structure 12 has a structure in which the fixing region A1 and the diffusion region A2 are separated, even when the reactant 20 having a large molecular weight is fixed, the aspect ratio ( Even when the silica structure 12 (the length of the diffusion region A2) / the outer diameter of the silica structure 12) is high, the carrier 10 includes the diffusion region A2 in a hollow state. The diffusibility of the substance or product is as good as the diffusivity in the solution, and the reaction material 20 supported can realize a reaction at a higher speed.
Moreover, since the base material 11 has a plurality of through-holes 11a parallel to each other, the specific substance is fixed to the fixed region by arranging the reactant complex 1 as shown in Example 7, for example. The movement distance until the contact with the reactant 20 fixed on A1 and the movement distance until the product generated by the contact reaches the detection element (for example, the electrode part S13) are further shortened. Can do. Therefore, the reaction at a higher speed can be realized as compared with the case of using a base material in which the orientation of the through holes 11a is random.

Further, according to the carrier 10 of the present invention described above and the reactant composite 1 including the carrier 10, the base material 11 is an anodized alumina substrate obtained by anodizing a substrate containing aluminum, and the through hole 11a. Are holes formed by anodization.
Therefore, the base material 11 is suitable as a base material because a plurality of through holes 11a parallel to each other are easily and surely formed and the strength and stability are high.

Further, according to the carrier 10 of the present invention described above and the reactant composite 1 including the carrier 10, the reactant 20 is a biocatalyst, and the size of the pores 12a is 0.5 of the size of the biocatalyst. ~ 2.0 times.
That is, since a biocatalyst such as a protein can be firmly fixed inside the pores 12a of the silica structure 12, a change in the three-dimensional structure of the biocatalyst can be prevented. Further, by firmly fixing the biocatalyst inside the pores 12a of the silica structure 12, the biocatalyst is maintained in a moderately dispersed state, and thus the biocatalyst is aggregated and deactivated. Can be prevented. The silica structure 12 is porous and has a very large specific surface area. Therefore, when the silica structure 12 is used, the reactant 20 can be fixed at a higher concentration with a larger fixing amount than when a carrier having a specific surface area smaller than that of the silica structure 12 is used.
Therefore, the reactant complex 1 has a long lifetime and excellent stability, and the sensor and reactor to which the reactant complex 1 is applied have a long lifetime and excellent stability and sensitivity. This is suitable.

Moreover, according to the manufacturing method of the support | carrier 10 of this invention demonstrated above, the silica layer formation step which forms the silica layer containing a predetermined surfactant on the inner wall 11a1 of the through-hole 11a which the base material 11 has, and a silica layer And a silica structure forming step of forming a silica structure 12 by removing the surfactant. The silica layer forming step includes a suction introduction step of sucking and introducing a silica source solution containing a surfactant into the through-hole 11a at a predetermined suction speed, and a silica source containing the surfactant introduced into the through-hole 11a. A suction drying step of sucking and drying the solution at a predetermined suction speed. In the silica structure forming step, the silica layer is baked to remove the surfactant from the silica layer.
That is, the carrier 10 capable of realizing a faster and more sensitive reaction with the supported reactant 20 can be produced by a simple method.

  The present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the gist thereof.

The penetration direction of the pores 12a of the silica structure 12 is not limited to being substantially perpendicular to the penetration direction of the through holes 11a of the substrate 11, and the inner wall surface of the silica structure 12 having the hollow fiber shape of the pores 12a. It is optional as long as it penetrates from 12b to the outer wall surface 12c.
Moreover, the hole part which the silica structure 12 has is not restricted to the pore 12a which penetrates from the inner wall surface 12b of the silica structure 12 to the outer wall surface 12c, For example, it was formed in the inner wall surface 12b of the silica structure 12. A concave portion (that is, a hole opened on the inner wall surface 12b side and closed on the outer wall surface 12c side) may be used.

In the method for manufacturing the carrier 10, the silica layer forming step is not limited to the suction introducing step and the suction drying step, and a silica layer containing a predetermined surfactant is formed on the inner wall 11 a 1 of the through hole 11 a. It is optional if it can.
In the method for producing the carrier 10, the method for removing the surfactant is not limited to the firing method, and may be, for example, a solvent extraction method as long as the surfactant can be removed.

  In the method for producing the reactant complex 1, the produced carrier 10 is immersed in a reactant solution containing the reactant 20, and the reactant 20 is adsorbed and fixed on the carrier 10. Although the method of immobilizing the reactant 20 is not limited to the immersion method, for example, a predetermined functional group is introduced in advance on the surface of the silica structure 12 to chemically modify the reactant 20. Alternatively, a known immobilization method using a conductive polymer, glutaraldehyde, a photocrosslinkable resin, or the like may be used, or these immobilization methods may be used in combination.

In the method for producing the reactant complex 1, the produced carrier 10 is immersed in a reactant solution containing the reactant 20, and the reactant 20 is adsorbed and fixed on the carrier 10. However, the present invention is not limited to this, and any method for producing the carrier 10 and any method for producing the reactant complex 1 can be used as long as the reactant 20 can be carried on the carrier 10.
Specifically, when the reactant 20 is an oxidation catalyst, for example, the manufactured support 10 is immersed in a solution of metal alkoxide and hydrolyzed to apply a surface coating to the silica structure 12, and then fired. By doing so, oxidation of metal particles (generation of an oxidation catalyst) can be performed, and the reactant composite 1 can be manufactured. Alternatively, for example, a solution containing a surfactant, a silica source, and metal particles such as ruthenium, manganese, iron, and titanium is sucked and introduced into the through hole 11a of the substrate 11 at a predetermined suction speed. Then, after drying by suction, firing is performed to simultaneously remove the surfactant from the silica layer and oxidize the metal particles (generate an oxidation catalyst) to produce the reactant composite 1. May be.

The base material 11 is not limited to a metal oxide substrate such as an anodized alumina substrate, and may be any substrate as long as it has a plurality of through holes 11a parallel to each other.
Specifically, for example, a substrate 11 having a plurality of through-holes 11a parallel to each other is transferred by transferring to a thin film such as a polymer, metal, or ceramic using a periodic cylindrical structure at a nano level as a template. It can also be produced.

It is a schematic diagram for demonstrating the structure of the support | carrier of this invention. It is a schematic diagram for demonstrating the structure of the reaction material complex of this invention. It is a cross-sectional schematic diagram for demonstrating the principal part structure of the reactant composite of this invention. FIG. 4 is a diagram showing the results of SEM observation in Example 1. FIG. 4 is a diagram showing the results of TEM observation in Example 1. It is a figure which shows the result of the light absorbency measurement in Example 6. 10 is a plan perspective view of an enzyme sensor for gas detection produced in Example 7. FIG. It is a figure which shows typically the cross section in the VIII-VIII line in FIG. It is a figure which shows typically the cross section in the IX-IX line in FIG. It is a figure which shows the result of the response current measurement in Example 7. It is a schematic diagram for demonstrating the structure of the conventional support | carrier.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reactive material complex 11 Base material 11a Through-hole 11a1 Inner wall 12 Silica structure 12a Pore (hole)
12b inner wall surface 10 carrier 20 reactant

Claims (6)

In a carrier carrying a reactive substance that selectively reacts with a specific substance,
A substrate having a plurality of through holes parallel to each other;
A hollow fiber-like silica structure formed in the through hole along the inner wall of the through hole;
With
The silica structure has a plurality of holes in the order of nanometers on the inner wall surface,
The carrier, wherein the reactant is fixed inside the hole. The carrier according to claim 1,
The base material is an anodized alumina substrate obtained by anodizing a substrate containing aluminum,
The carrier, wherein the through hole is a hole formed by the anodic oxidation. The carrier according to claim 1 or 2,
The reaction material is a biocatalyst, and the size of the hole is 0.5 to 2.0 times the size of the biocatalyst. The carrier according to any one of claims 1 to 3,
The reactants supported on the carrier;
A reactant complex comprising: In the manufacturing method of the carrier according to any one of claims 1 to 3,
A silica layer forming step of forming a silica layer containing a predetermined surfactant on the inner wall of the through hole;
A silica structure forming step of removing the surfactant from the silica layer to form the silica structure;
A method for producing a carrier comprising the steps of: In the manufacturing method of the support | carrier of Claim 5,
The silica layer forming step includes
A suction introduction step of sucking and introducing the silica source solution containing the surfactant into the through hole at a predetermined suction speed;
A suction drying step of sucking and drying the silica source solution introduced into the through hole at a predetermined suction speed;
With
The silica structure forming step includes removing the surfactant from the silica layer by firing the silica layer.