JP5199759B2 - Sensor system - Google Patents

Description

The present invention relates to a sensor system .

Conventionally, a matrix sensor in which a plurality of sensor units are arranged in a two-dimensional matrix is known (see, for example, Patent Documents 1 and 2).
Specifically, the sensor unit included in the matrix sensors described in Patent Documents 1 and 2 includes a detection element (electrode) and a reactive substance fixed on the detection element or on the upper surface of a porous film disposed on the detection element. (Biological substance), and the detection element detects an interaction between the reactive substance and a substance that reacts specifically with the reactive substance.
JP 2004-020238 A JP 2003-043009 A

However, in Patent Documents 1 and 2, since the reactive substance is fixed on the detection element or on the upper surface of the porous film disposed on the detection element, the size of the sensor unit is reduced in order to reduce the size of the matrix sensor. Then, the area of the region for fixing the reactant (the upper surface of the detection element) is also reduced. Therefore, when the matrix sensor is reduced in size, the amount of the reactive substance in the sensor unit is reduced, so that the sensitivity of the sensor unit is lowered.
In addition, nano-sized proteins and organic / inorganic substances such as enzymes and metal catalysts tend to aggregate with each other, so that sufficient performance cannot be obtained as they are. Even if dispersed in a porous material, the diffusibility of the substrate or product is poor as it is, and the sensor sensitivity cannot be improved.

An object of the present invention is to provide a sensor system comprising a matrix sensor which can suppress the decrease in sensitivity of the sensor unit be miniaturized.

In order to solve the above-mentioned problem, the invention described in claim 1
In the sensor system,
A matrix sensor having a substrate, a plurality of sensor units arranged in a two-dimensional or three-dimensional matrix on the substrate, and a partition unit arranged on the substrate and separating the sensor units;
A calculation unit that performs predetermined statistical processing using detection data from each of the plurality of sensor units having the same detection concentration range, and calculates the concentration of the detection target substance based on a result of the predetermined statistical processing;
With
The sensor unit includes a detection element disposed on the substrate, a porous body disposed on the detection element and having at least a pore penetrating in a direction substantially perpendicular to the substrate, and a pore of the porous body And a reactive substance that selectively reacts with a substance to be detected , and detects a predetermined change accompanying the reaction by the detection element ,
The porous body is a membranous silica-based mesoporous body formed independently of the detection element .

The invention described in claim 2
The sensor system according to claim 1 ,
Of the previous SL plurality of sensor units, and designating means for designating a predetermined sensor portion,
Obtaining means for obtaining detection data by the sensor unit designated by the designation means;
With
The detection element is an electrode;
The reactive substance is a biological substance .

According to the present invention, the matrix sensor includes a substrate, a plurality of sensor units arranged in a two-dimensional or three-dimensional matrix on the substrate, and a partition unit arranged on the substrate and separating the sensor units. The sensor unit includes a detection element disposed on the substrate, a porous body disposed on the detection element and having pores penetrating at least substantially perpendicular to the substrate, and inside the pores of the porous body. And a reaction substance that selectively reacts with the detection target substance, and a predetermined change accompanying the reaction is detected by the detection element.
That is, since the reactive substance that selectively reacts with the detection target substance is fixed to the porous body, the amount of the reactive substance provided in the sensor unit is larger than when the reactive substance is fixed on the detection element, Even if the matrix sensor is downsized, it is possible to suppress a decrease in sensitivity of the sensor unit.
Therefore, it is preferable because a smaller matrix sensor can be provided as compared with the case where the reactive substance is immobilized on the detection element.

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.
In this embodiment, a sensor system including a matrix sensor having a sensor unit that functions as an enzyme sensor will be described as an example.

[First Embodiment]
First, the sensor system 1 and the matrix sensor 10 included in the sensor system 1 according to the first embodiment will be described.

<Sensor system>
FIG. 1 is a block diagram showing a functional configuration of the sensor system 1 of the first embodiment, and FIG. 2 is a diagram schematically showing the sensor system 1 of the first embodiment.

The sensor system 1 is a system that detects a detection target substance using, for example, the matrix sensor 10 and measures the concentration of the detection target substance.
Specifically, the sensor system 1 includes, for example, a matrix sensor 10, a seal removal unit 30, a detection data acquisition unit 40, a control unit 50, a memory unit 60, an operation unit 70, and a display unit 80. , And so on.
In the sensor system 1, the matrix sensor 10 and the seal removal unit 30, the detection data acquisition unit 40, the control unit 50, the memory unit 60, and the like may be configured separately, or the seal removal unit 30 or The detection data acquisition unit 40, the control unit 50, the memory unit 60, and the like may be formed on the same substrate 11 as the matrix sensor 10 and integrated (single chip). In the case of a one-chip configuration, the matrix sensor 10 and a substrate on which the seal removal unit 30, the detection data acquisition unit 40, the control unit 50, the memory unit 60, and the like are stacked are stacked to form a multilayer type. Also good.

<Matrix sensor>
3 is a plan perspective view of the matrix sensor 10, FIG. 4 is an exploded view of the matrix sensor 10, FIG. 5 is a cross-sectional view taken along line V-V in FIG. 3, and FIG. 6 is a plan view of the substrate 11 on which the electrodes 12 are formed. FIG. 7 is a diagram for explaining a specific method of the sensor unit 20.

  For example, as shown in FIG. 3, the matrix sensor 10 includes 25 sensor units 20 arranged in a 5 × 5 two-dimensional matrix. The sensor unit 20 is, for example, an enzyme sensor that detects a detection target substance in a gas sample or a liquid sample by using an electrochemical measurement method using the characteristics of the enzyme E.

Here, the substrate 11 side of the matrix sensor 10 is the lower side, the cover member 18 side is the upper side, the row direction of the matrix sensor 10 is the left-right direction, and the column direction is the front-back direction.
Further, for example, as shown in FIG. 7, numbers “1” to “5” are assigned to each row (X) in order from the top, and “1” to “5” are assigned to each column (Y) in order from the left. When the sensor unit 20 is specified by assigning the number, the sensor unit (X, Y) is referred to.

Specifically, for example, as illustrated in FIG. 5, the sensor unit 20 includes a detection layer 21 disposed on the substrate 11, a transmission layer 22 disposed on the detection layer 21, and a transmission layer 22. And the supply layer 23 formed.
The detection layer 21 is filled with an electrolytic solution. The electrode 12 as a detection element is disposed on the detection layer 21, and the enzyme E as a reactive substance (biological substance) that selectively reacts with the detection target substance is supported (fixed) on the porous body 13. It is contained in the detection layer 21. The surface of the supply layer 23 that faces the transmission layer 22 (that is, the surface of the sensor unit 20 that faces the substrate 11) is sealed with a removable sealing member 17.
That is, the sensor unit 20 is blocked from the outside by the sealing member 17 in a state where the detection layer 21 contains the electrolytic solution and the enzyme E.

In the sensor unit 20, when the sealing member 17 is removed and the sample is supplied to the supply layer 23, the detection target substance in the sample passes through the transmission layer 22 and moves to the detection layer 21. Reacts with enzyme E. Then, the sensor unit 20 detects a predetermined change accompanying the reaction (specifically, a change in the amount of current flowing between the working electrode 121 and the counter electrode 123) by the electrode 12, thereby detecting the detection target substance. It comes to detect.
That is, for example, when the detection target substance is formaldehyde (HCHO) and the enzyme E is formaldehyde dehydrogenase, the reaction in which formaldehyde dehydrogenase oxidizes formaldehyde in the presence of a coenzyme (NAD ⁺ ) (HCHO + NAD ⁺ + 3H ₂ O − (enzyme E) ) → HCOO ⁻ + NADH + 2H ₃ O ⁺ ), a change in the amount of the reduced enzyme produced by the electrode 12 is detected as a change in the amount of current flowing between the working electrode 121 and the counter electrode 123. Is supposed to be detected. Specifically, as the oxidized formaldehyde dehydrogenase oxidizes formaldehyde, the oxidized formaldehyde dehydrogenase (oxidized enzyme) becomes a reduced formaldehyde dehydrogenase (reduced enzyme), and the reduced enzyme directly Indirectly or indirectly through an electron carrier, electrons (e ⁻ ) are transferred to the working electrode 121 to return to the oxidized enzyme. At this time, the detection target substance is detected by detecting the amount of current for reoxidizing the reducing enzyme or the reducing electron carrier flowing between the working electrode 121 and the counter electrode 123 at the electrode 12. ing.
Further, for example, when the detection target substance (substrate) is glucose and the enzyme E is glucose oxidase, hydrogen peroxide and consumption generated by the enzyme reaction (substrate + O ₂ − (enzyme E) → product + H ₂ O ₂ ) The detection target substance is detected by detecting the change in the amount of the electrode active substance such as oxygen that is detected by the electrode 12 as the change in the amount of current flowing between the working electrode 121 and the counter electrode 123. .

  For example, as shown in FIG. 5, the matrix sensor 10 includes a substrate 11 having a hydrophobic insulating film 112 formed on the upper surface, and an electrode 12 (working electrode 121, reference electrode) disposed in the analysis unit 111 on the upper surface of the substrate 11. 122 and the counter electrode 123), the porous body 13 disposed on the electrode 12, the enzyme E carried inside the pores 13 a of the porous body 13, the partition wall portion 14 disposed on the substrate 11, and the partition wall A permeable membrane 15 disposed on the portion 14, a spacer 16 disposed on the permeable membrane 15, a sealing member 17 disposed on the spacer 16, and a cover member 18 disposed on the sealing member 17. , And so on.

(substrate)
The substrate 11 is formed, for example, in a substantially rectangular shape in plan view. The substrate 11 has, for example, an analysis unit 111 having a substantially circular shape in plan view arranged in a 5 × 5 two-dimensional matrix on the upper surface of the substrate 11. For example, a region corresponding to the analysis unit 111 on the upper surface of the substrate 11. A hydrophobic insulating film 112 such as a SiO thin film is formed in a region other than.

As the substrate 11, for example, a semiconductor substrate, an insulating substrate, a polymer substrate, or the like can be used.
Here, for example, a silicon substrate or the like can be used as the semiconductor substrate.
As the insulating substrate, for example, a glass substrate, a ceramic substrate, a paper substrate, a wood substrate, or the like can be used.
Examples of the polymer substrate include esters such as polyethylene terephthalate, polyamides, polycarbonates, fluoropolymers such as polyvinylidene fluoride and polytetrafluoroethylene (Teflon (registered trademark)), polyethers, polystyrene, polyethylene, and the like. Polyolefins and polyimides can be used.

  For example, when a thin film transistor (TFT) or the like is formed on the substrate 11 (for example, the matrix sensor 10, the detection data acquisition unit 40, the control unit 50, the memory unit 60, etc. are integrally configured (one-chip configuration). ), Etc.), it is preferable to ensure an electrical connection by forming an interlayer insulating layer in advance and forming a through hole by a photolithography method or the like.

(electrode)
The electrode 12 (the working electrode 121, the reference electrode 122, and the counter electrode 123) is formed inside the analysis unit 111 on the upper surface of the substrate 11 as shown in FIG. 6, for example, and the working electrode 121, the reference electrode 122, and the counter electrode are opposed to each other. It is connected to pads 124, 124, 124 provided corresponding to the electrode 123 through wiring.
For example, as shown in FIG. 6, the pad 124 is formed on the edge of the substrate 11 on the upper surface of the substrate 11.

The electrode 12, the pad 124, and the wiring connecting the electrode 12 and the pad 124 can be formed by, for example, forming a thin film for an electrode by a vapor deposition method or a sputtering method, and patterning in a photolithography process. Note that the creation of the electrode 12, the pad 124, and the wiring is not limited to the creation by the photolithography process, and may be performed simply using, for example, a screen printing technique.
Examples of the material for the electrode thin film include Al, Cr, Mo, Ta, Ti, W, Nb, Fe, Co, Ni, Cu, Ag, Au, Pd, Pt, Ru, RuO ₂ , C, and the like. At least one selected from alloys can be used.
Reference electrode 122 is preferably a silver / silver chloride electrode. The reference electrode 122, which is a silver / silver chloride electrode, may be prepared, for example, by applying a silver / silver chloride ink on the electrode thin film to be the reference electrode 122 and baking it, or by screen printing or vapor deposition. Alternatively, the silver electrode may be formed once by a method, a sputtering method, or the like, and then electrolyzed with a constant current or immersed in a second silver chloride aqueous solution.
In addition, from the viewpoint of improving contact characteristics and electrical conductivity, a laminate of different types of metal films may be used as the electrode thin film.

(Porous body)
The porous body 13 has, for example, pores 13 a penetrating in a direction substantially perpendicular to the substrate 11.
The porous body 13 is formed, for example, in a substantially circular shape in plan view. The size (diameter) of the porous body 13 in plan view is set to be the same as or smaller than the size (diameter) of the analysis unit 111, and the thickness (length in the vertical direction) of the porous body 13 is set to the electrode 12. Is set to be equal to or less than the distance between the permeable membrane 15 and the permeable membrane 15.

As the porous body 13, for example, a sheet-like, bulk-like, or membrane-like, particularly a sheet-like or membrane-like silica mesoporous material can be preferably used.
The silica-based mesoporous material can be composed of, for example, various metal oxides such as silicic acid and alumina, complex oxides of silicic acid and other types of metals, and the like.
For example, in the production of a silica-based mesoporous material composed of silicic acid, for example, layered silicate such as kanemite, alkoxysilane, silica gel, water glass, sodium silicate and the like can be preferably used.

  Specifically, the silica-based mesoporous material, for example, forms a surfactant / inorganic composite in which an inorganic material is mixed with a surfactant to form an inorganic skeleton around the micelles of the surfactant. Then, for example, the surface active agent is removed by baking at 400 ° C. to 600 ° C. or extraction with an organic solvent. Thereby, the silica-based mesoporous material has mesopore pores (pores 13a) having the same shape as the micelles of the surfactant in the inorganic skeleton.

In the production of a silica-based mesoporous material, when a silicon-containing compound such as silicic acid is used as a starting material, for example, a layered silicate such as kanemite is formed, and micelles are inserted between the layers. The pores 13a can be formed by connecting non-existing layers with silicate molecules and then removing the micelles.
In the production of a silica-based mesoporous material, when a silicon-containing substance such as water glass is used as a starting material, for example, silica is formed by collecting and polymerizing silicate molecules around micelles, and then, By removing the micelle, the pore 13a can be formed. In this case, the shape of the micelle is usually a columnar shape, and as a result, columnar pores 13a are formed in the silica-based mesoporous material.

In the silica-based mesoporous material, the inner diameter of the pores 13a can be controlled by changing the micelle diameter by changing the length of the alkyl chain of the surfactant in the production stage. Further, by adding a relatively hydrophobic molecule such as trimethylbenzene or tripropylbenzene together with the surfactant, the micelle can be swollen to form a pore 13a having a larger inner diameter.
The size of the pores 13a (the diameter of the pores 13a) of the silica-based mesoporous material is determined according to the size of the enzyme E to be immobilized (the diameter of the enzyme E). That is, for example, by producing a silica-based mesoporous material using a surfactant having a micelle size (micelle diameter) of 0.5 to 2.0 times that of enzyme E, the pores 13a A silica-based mesoporous material whose size is 0.5 to 2.0 times the size of the enzyme E to be immobilized can be obtained.

The penetration direction of the pores 13a in the silica-based mesoporous material is arbitrary as long as it includes at least a direction substantially perpendicular to the substrate 11, and may be random or as an aggregate of one-dimensional silica nanochannels. The directionality may be controlled.
Further, as a method for producing a silica-based mesoporous material, it may be formed individually as described above, or an external field such as precipitation by spin coating or nucleus growth, photo-alignment, electric field, magnetic field, shear flow, etc. In addition to the hole size, the substrate 11 and the electrode 12 can be directly used in a direction-controlled form.

As the types of silica-based mesoporous materials, known types such as KSW, FSM, SBA, MCM, HOM, etc., having the characteristics that the pores 13a are uniform in size and have a large porosity are adopted. can do.
Further, as a kind of the silica-based mesoporous material, the size of the pores 13a is uniform and the direction of the pores 13a (channels) is directed in one direction, for example, CTAB-M, Known types such as P123-M and F127-M can be employed. Specifically, CTAB-M, P123-M, F127-M, etc., for example, have the same channel direction as the direction of the alumina pores produced using a surfactant as a template in cylindrical alumina pores. It is a membranous silica-based mesoporous material filled with a mesoporous silica nanochannel aggregate (one-dimensional silica nanochannel aggregate).

The size of the pores 13a of the silica-based mesoporous material is set to such an extent that a change in the three-dimensional structure of the immobilized enzyme E can be prevented.
Specifically, the size of the pores 13a of the silica-based mesoporous material is, for example, about 0.5 to 2.0 times the size of the immobilized enzyme E (enzyme molecule or enzyme fragment containing an active site). It is preferable that the size is about 0.7 to 1.4 times the size of the enzyme E to be immobilized, and it is most preferable that the size is substantially the same as the size of the enzyme E to be immobilized. That is, the diameter (center pore diameter) of the pores 13a in the silica-based mesoporous material is preferably about 0.5 to 2.0 times the diameter of the enzyme E to be immobilized. The diameter is more preferably about 0.7 to 1.4 times the diameter, and most preferably the same as the diameter of the enzyme E to be immobilized. In addition, since the specific value of the center pore diameter is determined by the relationship with the diameter of the enzyme E, it cannot be defined uniformly, but can be, for example, about 1 to 50 nm.
Here, when the enzyme E forms a multimer, the size (diameter) of the enzyme E to be immobilized can be the size (diameter) of the multimer. Here, the multimer refers to a compound in which two or more enzymes (proteins) are bonded directly or via a small molecule such as water, and the bond includes a covalent bond, an ionic bond, a hydrogen bond, Coordination bonds are included. However, the type of these bonds is not particularly limited.

The size of the pores 13a of the silica-based mesoporous material is about 0.5 to 2.0 times (more preferably about 0.7 to 1.4 times, most preferably almost the same) as the size of the enzyme E to be immobilized. By doing so, it becomes easy to maintain the three-dimensional structure of the enzyme E to be immobilized, so that the enzyme E immobilized inside the pores 13a of the silica-based mesoporous material can be stabilized.
Furthermore, since the specific surface area of the silica-based mesoporous material is, for example, about 200 to 1500 m ² , the enzyme E is directly fixed to the surface of the electrode 12 by fixing the enzyme E to the silica-based mesoporous material. In comparison, since the detection layer 21 can contain a large amount of enzyme E, the detection of the detection target substance by the sensor unit 20 can be made highly sensitive.
Further, since the pores 13a of the silica-based mesoporous material include the pores 13a penetrating in the direction substantially perpendicular to the substrate 11, the pores 13a penetrating in the direction substantially perpendicular to the substrate 11 are not included. Compared to the case, since the electron transfer between the active center of the enzyme E and the electrode 12 (working electrode 121) becomes smooth, the detection of the detection target substance by the sensor unit 20 can be speeded up.

The porous body 13 is not limited to a silica-based mesoporous body, and may be any as long as it can fix the enzyme E and has at least pores 13a penetrating in a direction substantially perpendicular to the substrate 11. For example, hydrophilic membranes made of hydrophilic Teflon membrane, nylon membrane and other materials (eg cellulose mixed ester, polyvinylidene difluoride, polytetrafluoroethylene, polycarbonate, polypropylene, polyethylene terephthalate, etc.), porous It may be a porous body such as porous alumina or a mesh body such as nylon mesh. Further, the carrier for immobilizing the enzyme E is not limited to the porous body 13 and has a function equivalent to that of the porous body 13 (having a specific surface area larger than that of the electrode 12 and substantially perpendicular to the substrate 11. As long as it has pores 13a (flow paths) penetrating in the direction), and may be, for example, a fibrous aggregate such as a carbon nanotube.
Alternatively, a structure having pores 13a penetrating in a direction substantially perpendicular to the substrate 11 may be directly formed on the electrode 12 by a known method. Specifically, for example, anodized alumina that penetrates the substrate 11 in a substantially vertical direction can be formed by anodization, or a bundle of silica channels having a smaller pore diameter can be formed therein.

(enzyme)
The enzyme E is arbitrary as long as it is an enzyme that selectively reacts with the detection target substance, and can be appropriately changed depending on the type of the detection target substance.
Specifically, the enzyme E is an enzyme (enzyme protein) such as an oxidoreductase, a hydrolase, a transferase, and an isomerase.
The enzyme E may be a natural enzyme molecule or an enzyme fragment containing an active site, for example. The enzyme molecule or the enzyme fragment containing the active site may be, for example, extracted from animals or plants or microorganisms, may be cleaved if desired, or may be genetically engineered or chemically It may also be synthesized.

  Examples of the oxidoreductase include glucose oxidase, lactate oxidase, cholesterol oxidase, alcohol oxidase, formaldehyde oxidase, sorbitol oxidase, fructose oxidase, sarcosine oxidase, fructosylamine oxidase, pyruvate oxidase, xanthine oxidase, ascorbate oxidase, sarcosine. Oxidase, choline oxidase, amine oxidase, glucose dehydrogenase, lactate dehydrogenase, cholesterol dehydrogenase, alcohol dehydrogenase, formaldehyde dehydrogenase, sorbitol dehydrogenase, fructose dehydrogenase, hydroxybutyrate dehydrogenase, glycerol dehydrogenase Glutamate dehydrogenase, pyruvate dehydrogenase, malate dehydrogenase, glutamate dehydrogenase, can be used catalase, peroxidase, uricase, and the like. In addition, cholesterol esterase, acetylcholinesterase, butyrylcholinesterase, creatininase, creatinase, DNA polymerase, mutants of these enzymes, and the like can be used.

  As the hydrolase, for example, protease, lipase, amylase, invertase, maltase, β-galactosidase, lysozyme, urease, esterase, nuclease group, phosphatase group and the like can be used.

  As the transferase, for example, various acyltransferases, kinase groups, aminotransferase groups and the like can be used.

  As the isomerase, for example, racemase group, phosphoglycerate phosphomutase, glucose 6-phosphate isomerase and the like can be used.

The enzyme E fixed to the porous body 13 may be one type of enzyme or two or more types of enzymes.
Specifically, the enzyme E immobilized on the porous body 13 may be, for example, one type of enzyme or two or more types of enzymes having substantially the same molecular weight and / or size (diameter). Two or more kinds of enzymes having different sizes may be used. Further, when there are two or more types of enzymes E immobilized on the porous body 13, even if the enzyme E is, for example, two or more types of enzymes that act on the same type of detection target substance (substrate), different types of detection target substances It may be two or more types of enzymes that act on two or more types of enzymes that act on the same type and / or different types of detection target substances.

In addition, when there are two or more types of enzymes E immobilized on the porous body 13, even if the two or more types of enzymes are immobilized inside separate pores 13a in the porous body 13, the same pore 13a It may be fixed inside.
Here, in particular, when there are two or more types of enzymes E immobilized on the porous body 13 and the two or more types of enzymes act on different types of detection target substances, the sensor unit 20 detects the different types of detection target substances ( Two or more kinds of detection target substances) can be detected simultaneously.

Examples of the method for fixing the enzyme E to the porous body 13 include a dip method in which a solution containing the enzyme E is dropped into the porous body 13, a soaking method in which the porous body 13 is immersed in a solution containing the enzyme E, and an electric field. Although the method etc. which introduce | transduce the enzyme E into the porous body 13 using an external field are mentioned, it does not specifically limit. As a result, the enzyme E can be immobilized on the porous body 13 while maintaining the higher-order structure and activity.
Furthermore, if necessary, it can be used in combination with a known enzyme immobilization method (for example, an immobilization method using a conductive polymer, glutaraldehyde, a photocrosslinkable resin or the like).
Further, after the enzyme E is fixed to the porous body 13, the porous body 13 may be disposed on the electrode 12, or after the porous body 13 is disposed on the electrode 12, the enzyme E is fixed to the porous body 13. You may make it do.

Here, it is preferable that the detection layer 21 contains an electron carrier for facilitating the delivery of electrons between the enzyme E and the electrode 12 (working electrode 121).
The electron carrier is optional as long as it is contained in the detection layer 21. For example, the electron carrier may be contained in the detection layer 21 in a state of being dissolved in an electrolyte solution that fills the detection layer 21, or for example, a porous body. 13 may be contained in the detection layer 21 in a state of being introduced (fixed) inside the 13 pores 13a, for example, contained in the detection layer 21 in a state of being directly fixed to the electrode 12 (working electrode 121). May be.
Specifically, examples of the electron carrier include conductive polymers such as polyaniline, quinone compounds such as quinone and quinone derivatives (naphthoquinone and benzoquinone), ferrocene compounds such as ferrocene and ferrocene derivatives, potassium ferricyanide, Examples include osmium complexes, various vitamins, and viologen.

In addition, it is preferable that the detection layer 21 contains a coenzyme for catalyzing the expression of the activity of the enzyme E.
The coenzyme is optional as long as it is contained in the detection layer 21. For example, the coenzyme may be contained in the detection layer 21 in a state of being dissolved in an electrolyte solution that fills the detection layer 21. May be contained in the detection layer 21 in a state of being introduced (fixed) into the pores 13a, or may be contained in the detection layer 21 in a state of being directly fixed to the electrode 12 (working electrode 121), for example. May be.
In addition, the coenzyme 300 is included in the detection unit 10 together with, for example, various metal atoms, metal ions, metal complexes, various dyes and the like (eg, Fe ²⁺ , Mn ²⁺ , Cu ²⁺ , Zn ²⁺ , Co ^3+, etc.) as cofactors. It may be contained.

  For example, in the case of a reaction that does not proceed easily by the catalysis of the amino acid side chain of enzyme E, such as a reaction via an anxious intermediate, a low molecular weight organic small molecule that has an appropriate structure and is involved in the expression of the enzyme reaction And metal ions and metal complexes are often used as cofactors. Among the cofactors, small organic molecules and metal complexes are called coenzymes. In particular, when a coenzyme-dependent enzyme is used as the enzyme E, the enzyme reaction can be performed efficiently by introducing the coenzyme into the detection layer 21.

The coenzyme can be appropriately selected according to the type of enzyme E (coenzyme dependent enzyme). Specifically, examples of the coenzyme include nicotinamide adenine dinucleotide (NAD ⁺ ), nicotinamide adenine dinucleotide phosphate (NADP ⁺ ), coenzyme I, coenzyme II, flavin mononucleotide (FMN), and flavin. Adenine dinucleotide (FAD), lipoic acid, adenosine triphosphate (ATP), thiamine pyrophosphate (TPP), pyridoxal phosphate (PALP), tetrahydrofolate (THF, Coenzyme F), UDP glucose (UDPG), coenzyme A, Examples thereof include one or a combination of two or more of coenzyme Q, biotin, coenzyme B ₁₂ (cobalamin), S-adenosylmethionine and the like.

(Partition wall)
The partition wall 14 is formed, for example, in a substantially rectangular shape in plan view, and has an opening that penetrates in the vertical direction in a region corresponding to the analysis unit 111. The partition wall 14 is fixed on the substrate 11 by being thermocompression bonded or bonded to the upper surface of the substrate 11 (hydrophobic insulating film 112), for example.
The inside of the analysis part 111 and the inside of the opening part of the partition part 14 become the detection layer 21 of the sensor part 20. That is, the sensor units 20 are separated from each other by the partition wall 14 and the hydrophobic insulating film 112 on the upper surface of the substrate 11.

For example, the partition wall 14 can be formed by forming an opening in a semiconductor plate member, an insulator plate member, a polymer plate member, or the like by etching or the like.
Further, the partition wall 14 may be a structure having a through-hole penetrating in a direction substantially perpendicular to the substrate 11 such as anodized alumina.

The partition wall 14 may be formed integrally with the substrate 11.
That is, for example, the partition wall portion 14 may be formed on the substrate 11 by photolithography using a photo-curing resin or a thermosetting resin. For example, before the electrode 12 is formed on the substrate 11. Further, a recess may be formed on the upper surface of the substrate 11 by etching or the like, and this may be used as the detection layer 21 (opening portion of the partition wall portion 14). You may do it.

(Permeable membrane)
The permeable film 15 is formed in, for example, a substantially rectangular shape in plan view, and is fixed on the substrate 11 by being thermocompression bonded or bonded to the upper surface of the substrate 11 (hydrophobic insulating film 112), for example. .

  A region of the permeable membrane 15 corresponding to the analysis unit 111 is the transmissive layer 22 of the sensor unit 20, and separates the detection layer 21 and the supply layer 23. By separating the detection layer 21 and the supply layer 23 by the transmission layer 22, when the sample is a gas sample, for example, the electrolyte solution that fills the detection layer 21 is prevented from leaking during use of the sensor unit 20. It is possible to suppress evaporation of the electrolyte filling the detection layer 21 during use of the sensor unit 20. Further, when the sample is a liquid sample, for example, when the sensor unit 20 is used, the electrolytic solution that fills the detection layer 21 and the liquid sample supplied to the supply layer 22 are mixed. Can be prevented.

The detection target substance in the sample supplied to the supply layer 23 passes through the permeable layer 22 (the permeable membrane 15), moves to the detection layer 21, and reacts with the enzyme E included in the detection layer 21. Therefore, the permeable membrane 15 is arbitrary as long as it is a film through which at least the detection target substance permeates, and can be appropriately changed depending on the type of the detection target substance.
In particular, when the sample is a gas sample, the permeable membrane 15 is preferably a gas permeable membrane that transmits a detection target substance (detection target gas) but does not transmit a liquid such as an electrolytic solution.
Here, as the gas permeable film, for example, a polyethylene film or a Teflon film having air permeability can be used.

(Spacer)
The spacer 16 is formed in, for example, a substantially rectangular shape in plan view, and has an opening that penetrates in the vertical direction in a region corresponding to the analysis unit 111. The spacer 16 is fixed on the transmissive film 15 by being thermocompression-bonded or thermally fused or bonded to the upper surface of the permeable film 15, or an insulating photo-curing resin or thermosetting resin is used. Formed by photolithography, screen printing or the like.
The inside of the opening of the spacer 16 becomes the supply layer 23 of the sensor unit 20.

The spacer 16 is provided to dispose the permeable membrane 15 and the sealing member 17 apart from each other. Thereby, when the sealing member 17 is removed, it is possible to prevent the permeable membrane 15 from being damaged or the permeable membrane 15 from being removed.
If the permeable membrane 15 is not damaged or the permeable membrane 15 is not removed when the sealing member 17 is removed, the spacer 16 is omitted and the permeable membrane 15 is directly sealed on the permeable membrane 15. The member 17 may be disposed. Here, when the permeable membrane 15 is not damaged or the permeable membrane 15 is not removed when the sealing member 17 is removed, for example, a highly heat-resistant membrane is used as the permeable membrane 15. For example, a member having low heat resistance is used as the sealing member 17 and the sealing member 17 is removed by heating with heat such as voltage application.

  The spacer 16 can be formed, for example, by forming an opening in a semiconductor plate member, an insulator plate member, a polymer material plate member, or the like by etching or the like.

(Sealing member)
The sealing member 17 is formed in, for example, a substantially rectangular shape in plan view, and is fixed on the spacer 16 by being thermocompression bonded or bonded to the upper surface of the spacer 16, for example.

  The sealing member 17 is provided to block each of the plurality of sensor units 20 from the outside. Therefore, until the sealing member 17 that seals the sensor unit 20 is removed, no gas or liquid enters the sensor unit 20 from the outside, and no gas or liquid flows from the sensor unit 20 to the outside. It will not be released. Thereby, it can prevent that the electrolyte solution which satisfy | fills the detection layer 21 evaporates, or the enzyme E with which the detection layer 21 and the electrode 12 are deteriorated (oxidation etc.).

The sealing member 17 is arbitrary as long as it can block the sensor unit 20 from the outside, that is, any member that does not transmit gas and liquid. For example, a gas-impermeable film member or the like is used. Can do.
Here, examples of the gas-impermeable film-like member include a film-like member made of a polymer material such as a vinyl chloride film, an aluminum thin film, a laminate of the polymer material, and polymer materials having different characteristics. A laminate of these can be used.

(Cover member)
The cover member 18 has a supply port penetrating in the vertical direction for supplying a gas sample or a liquid sample to each sensor unit 20, and the sealing member 17 so that the supply port corresponds to the analysis unit 111. It is arranged or formed on the upper surface of. For example, the cover member 18 is fixed on the sealing member 17 by being thermocompression-bonded or heat-sealed or bonded to the upper surface of the sealing member 17, or an insulating photo-curing resin or thermosetting resin. Or the like using photolithography, screen printing or the like.

  The cover member 18 is provided, for example, to prevent the sealing member 17 from being removed or damaged when not intended, and the position of each sensor unit 20 can be recognized from the appearance of the matrix sensor 10. It is provided to

  For example, the cover member 18 can be formed by forming an opening in a semiconductor plate member, an insulator plate member, a polymer plate member, or the like by etching or the like. Alternatively, it can be directly formed by photolithography, screen printing, or the like using an insulating photo-curing resin or a thermosetting resin.

<Seal removal part>
For example, the seal removing unit 30 removes the sealing member 17 corresponding to the designated sensor unit 20 as a removing unit in accordance with a control signal input from the control unit 50.
Specifically, for example, as illustrated in FIG. 2, the seal removing unit 30 moves the moving unit 32 and the needle 31 that mechanically removes the sealing member 17, the moving unit 32 that moves the needle 31, and the moving unit 32. And a drive unit 33 to be configured.

  For example, the needle 31 is attached to the moving unit 32 so that the axis of the needle 31 is substantially parallel to the vertical direction and the tip of the needle 31 faces downward (on the matrix sensor 10 side). .

  The moving part 32 has, for example, a needle 31 attached to the tip thereof, and is disposed above the matrix sensor 10, for example. And the moving part 32 can move now in the up-down direction, the left-right direction, and the front-back direction, for example.

  The drive unit 33 uses, for example, a force generated from the drive source of the drive unit 33 to move the moving unit 32 to which the needle 31 is attached in the up-down direction, the left-right direction, and the front-rear direction. The unit is inserted into the sealing member 17 corresponding to the sensor unit 20 designated by the control unit 50 or pulled up from the sealing member 17.

  Here, the lower limit in the vertical direction of the moving unit 32 is such that the sealing member 17 provided in the matrix sensor 10 disposed below the moving unit 32 can be broken with the needle 31 to make a hole in the sealing member 17. In addition, the needle 31 is set so as not to contact the permeable membrane 15 provided in the matrix sensor 10.

<Detection data acquisition unit>
8 is a diagram illustrating a drive circuit of the detection data acquisition unit 40, FIG. 9 is a circuit diagram illustrating an addressable active element (AC) connected to the working electrode 121, and FIGS. 10 to 12 are illustrated in FIG. It is a circuit diagram which shows an example of an active element (AC).

8 to 12, “W _XY ” indicates the working electrode 121 of the sensor unit (X, Y), “R _XY ” indicates the reference electrode 122 of the sensor unit (X, Y), and “C _XY ″ represents the counter electrode 123 of the sensor unit (X, Y).

The detection data acquisition unit 40, for example, in accordance with a control signal input from the control unit 50, as detection means, detection data from the specified sensor unit 20 (the working electrode 121 and the counter electrode 123 provided in the specified sensor unit 20) (Detection data based on the amount of current flowing in between) is output to the control unit 50.
That is, for example, the detection data acquisition unit 40 applies a voltage having a predetermined voltage value to the working electrode 121 with respect to the reference electrode 122 for the designated sensor unit 20, and the current output from the working electrode 121 at that time Current value (response current value) is acquired and output to the control unit 50.

  Specifically, the detection data acquisition unit 40 includes, for example, a selection circuit 41, a potentiostat circuit 42, and the like as shown in FIG.

For example, the selector circuit 41 turns on the working electrode 121 included in the sensor unit 20 specified by the control unit 50 in accordance with a control signal input from the control unit 50.
Specifically, the select circuit 41, for example, as shown in FIG. 8, according to a selector switch 411 for turning on / off the connection between the working electrode 121 and the potentiostat circuit 42, and a control signal input from the control unit 50 A circuit 412 (a drive circuit (active element) and a shift register circuit) for controlling the selector switch 411, and the like are configured.

The selector switch 411 is configured by an active element (AC) connected to the working electrode 121, for example.
Active elements (AC), for example, as shown in FIG. 9, can is provided corresponding to the working electrode 121 each having a matrix sensor 10, it is connected to the signal line A _X and the signal lines B _Y addressing It has become.
As the active element (AC), for example, an active element composed of two diodes as shown in FIG. 10, an active element composed of a diode having a resistance connected to a capacitor as shown in FIG. An active element composed of MOS transistors as shown in FIG. 12 can be used.

The circuit 412 including the shift register converts, for example, serial format data input from the control unit 50 into parallel format data, and the working electrode 121 included in the sensor unit 20 designated by the control unit 50 is a potentiostat circuit. The selector switch 411 is controlled so as to be connected to the terminal 42. That is, it selects the signal line A _X and signal line B _Y corresponds to the selector signal sent from the control unit 50.
Specifically, circuit 412 includes a shift register, for example, when the control unit 50 rows (X) and column (Y) is specified, the signal is supplied to the corresponding signal line A _X and signal line B _Y Then, the connection between the working electrode 121 (W _XY ) included in the sensor unit (X, Y) and the potentiostat circuit 42 is turned ON.
More specifically, the circuit 412 including the shift register, for example, receives data indicating that “row (X) = 2, column (Y) = 5” is selected from the control unit 50, and then transmits the signal line A. ₂ and the signal line B ₅ are supplied to turn on the connection between the working electrode 121 (W ₂₅ ) provided in the sensor unit (2, 5) and the potentiostat circuit 42.

The potentiostat circuit 42 is, for example, a single channel potentiostat circuit. For example, the potentiostat circuit 42 applies a voltage having a predetermined voltage value to the working electrode 121 with respect to the reference electrode 122 in accordance with a control signal input from the control unit 50, and the current output from the working electrode 121 at that time Current value (response current value) is acquired and output to the control unit 50.
The potentiostat circuit 42 sequentially sets and outputs a voltage to the D / A converter 412, the control amplifier 422, and the potential measurement circuit 423 according to the signal and data from the control unit 50, and switches the selector switch 411 in synchronization therewith. By selecting the corresponding working electrode 121 and sequentially capturing current values sequentially, it is possible to capture the outputs of a plurality of sensors in a single channel and to serve as a multi-channel circuit. Therefore, cost and area can be significantly reduced.
Specifically, the potentiostat circuit 42 includes, for example, a D / A converter 421, a control amplifier 422, a potential measurement circuit 423, a current-voltage conversion circuit 424, and an A / D conversion, as shown in FIG. 425 and the like.

For example, when a digital signal related to a predetermined voltage value is input from the control unit 50, the D / A converter 421 converts the digital signal into an analog signal and supplies the predetermined voltage to the control amplifier 422 of the counter electrode 123. Output voltage signal of value.
The control amplifier 422 of the counter electrode 123 is connected to, for example, a potential measurement circuit 423 that measures the potential of the reference electrode 122, and the voltage input from the D / A converter 421 based on the potential of the reference electrode 122. A voltage value corresponding to the data is applied to the counter electrode 123.
Then, the response current output from the working electrode 121 at that time is converted into a voltage signal (analog signal) by the current-voltage conversion circuit 424, and converted into a digital signal by the A / D converter 425, for example. 50 is output.

<Control unit>
For example, as shown in FIG. 1, the control unit 50 includes a CPU (Central Processing Unit) 51, a RAM (Random Access Memory) 52, a storage unit 53, and the like.

  For example, the CPU 51 performs various control operations according to various processing programs for the sensor system 1 stored in the storage unit 53.

  The RAM 52 includes, for example, a program storage area for expanding a processing program executed by the CPU 51, a data storage area for storing input data, a processing result generated when the processing program is executed, and the like.

  The storage unit 53 includes, for example, a system program that can be executed by the sensor system 1, various processing programs that can be executed by the system program, data that is used when these various processing programs are executed, and processing results that are arithmetically processed by the CPU 51. The data etc. are memorized. The program is stored in the storage unit 53 in the form of a computer readable program code.

  Specifically, for example, as illustrated in FIG. 1, the storage unit 53 includes a deterioration determination program 531, a sensor unit designation program 532, a seal removal control program 533, a detection data acquisition control program 534, and a concentration calculation. A program 535 and the like are stored.

  For example, the deterioration determination program 531 causes the CPU 51 to realize a function of determining whether or not the sensor unit 20 from which the sealing member 17 has been removed by the sealing removal unit 30 has deteriorated.

  Specifically, for example, the CPU 51 determines whether or not the period after the sealing member 17 corresponding to the sensor unit 20 is removed exceeds a preset “effective use period of the sensor unit 20”. When it is determined that the effective usage period of the sensor unit 20 has been exceeded, it is determined that the sensor unit 20 has deteriorated.

Here, when the sealing member 17 that seals the sensor unit 20 is removed, the sensor unit 20 evaporates an electrolyte solution that fills the detection layer 21 or deteriorates (oxidizes) the enzyme E and the electrode 12 included in the detection layer 21. Etc.) and the sensitivity decreases. Therefore, the effective use period of the sensor unit 20 is, for example, a general requirement required after the sealing member 17 is removed until the degree of decrease in sensitivity of the sensor unit 20 exceeds a preset “allowable sensitivity range”. It is preferable to measure the period or the like in advance and store it in the memory unit 60 and use it.
The CPU 51 functions as a determination unit by executing the deterioration determination program 531.

  The sensor unit designation program 532 causes the CPU 51 to realize a function of designating a predetermined sensor unit 20 (for example, one predetermined sensor unit 20) among the plurality of sensor units 20, for example.

  Specifically, for example, when the CPU 51 that has executed the deterioration determination program 531 determines that the sensor unit 20 has deteriorated, the CPU 51 detects the sensor unit according to the preset “order of the sensor units 20 to be used”. 20 (sensor part 20 from which sealing member 17 is not removed) is designated.

Here, the order of the sensor units 20 to be used is arbitrary. Specifically, for example, “sensor unit (1, 1) → sensor unit (1,2) →... → sensor unit (1,5) → Sensor part (2, 1) → Sensor part (2, 2) → ... → Sensor part (2, 5) → Sensor part (3, 1) → Sensor part (3, 2) → ... → Sensor Part (3, 5) → sensor part (4,1) → sensor part (4,2) → ・ ・ ・ → sensor part (4,5) → sensor part (5,1) → sensor part (5,2) → ... → Sensor part (5, 5) ". The order of the sensor units 20 to be used is stored in the memory unit 60, for example.
The CPU 51 functions as a designation unit by executing the sensor unit designation program 532.

  The seal removal control program 533 is, for example, a function of inputting a control signal to the seal removal unit 30 and removing the sealing member 17 corresponding to the sensor unit 20 designated by the CPU 51 that has executed the sensor unit designation program 532. Is realized by the CPU 51.

  Here, the initial positions in the left-right direction and the front-rear direction of the moving unit 32 included in the seal removing unit 30 are set so that, for example, the needle 31 is positioned immediately above the sensor unit (1, 1) and moved. The initial position in the vertical direction of the portion 32 is set so that the tip of the needle 31 is located above the cover member 18 of the matrix sensor 10. When the CPU 71 controls the seal removing unit 30, the moving unit 32 moves, for example, from the initial position in the left-right direction and the front-rear direction to a position directly above the specified sensor unit 20, and then moves downward from the initial position in the vertical direction. The sealing member 17 is removed with the needle 31 by moving in the direction, and then moved back to the initial position in the up-down direction and back to the initial position in the left-right direction and the front-rear direction.

The detection data acquisition control program 534 inputs, for example, a control signal to the detection data acquisition unit 40 and the sensor unit 20 (the sensor unit from which the sealing member 17 has been removed) designated by the CPU 51 that has executed the sensor unit designation program 532. The CPU 51 is made to realize the function of acquiring the detection data according to 20) and outputting the detection data to the control unit 50.
Note that the CPU 51 stores the detection data input from the detection data acquisition unit 40 in, for example, the memory unit 60 or displays the detection data on the display unit 80.

Here, the method of supplying the sample to the matrix sensor 10 is arbitrary as long as the sample is supplied to the supply layer 23 of the sensor unit 20. Specifically, for example, the matrix sensor 10 is left in the sample. The sample may be naturally supplied to the supply layer 23, or the sample may be sprayed on the entire upper surface of the matrix sensor 10 using a tube or a capillary, or the sample may be applied to the upper surface of the sensor unit 20 to be used. The sample may be forcibly supplied to the supply layer 23 by spraying. In addition, when supplying a sample compulsorily, it is preferable that the supply rate of a sample is constant.
When the sample is forcibly supplied to the supply layer 23, the sample supply device for spraying the sample may be provided in the sensor system 1 or an external device of the sensor system 1. When the sample supply device is provided in the sensor system 1, for example, the CPU 51 that executes the detection data acquisition control program 534 controls the detection data acquisition unit 40 to detect the detection data from the designated sensor unit 20. And the sample supply device is controlled to supply the sample to the supply layer 23 of the designated sensor unit 20. When the sample supply device is provided in the sensor system 1, the sample supply device can be directly formed on the matrix sensor 10 as an integrated type using a known microfabrication technique such as MEMS.

  For example, the concentration calculation program 535 causes the CPU 51 to realize a function of calculating the concentration of the detection target substance based on the detection data acquired by the detection data acquisition unit 40.

  Specifically, for example, the CPU 51 calculates the concentration of the detection target substance based on the “calibration curve” acquired in advance and the detection data (response current value) acquired by the detection data acquisition unit 40. .

Here, the calibration curve is a calibration curve created in advance using the sensor unit 20 with the horizontal axis as the concentration of the detection target substance (substrate) and the vertical axis as the response current. It is remembered.
Note that the CPU 51 stores the calculated concentration of the detection target substance in, for example, the memory unit 60 or displays it on the display unit 80.
Further, when the concentration of the detection target substance cannot be calculated based on the calibration curve and the detection data, the CPU 51 displays a predetermined error display on the display unit 80, for example.
The CPU 51 functions as a calculation unit by executing the density calculation program 535.

<Memory part>
The memory unit 60 is configured by, for example, a magnetic recording medium, an optical recording medium, or a semiconductor memory, and stores predetermined data according to a control signal input from the control unit 50, for example.

<Operation unit>
The operation unit 70 includes, for example, operation keys and outputs an operation signal to the control unit 50 when operated by a user. Note that the operation unit 70 may include other operation devices such as a pointing device such as a mouse or a touch panel, a remote controller, or the like as necessary.

<Display section>
The display unit 80 includes, for example, an LCD (Liquid Crystal Display) panel, and performs a given display process according to a control signal input from the control unit 50, for example.

  The sensor system 1 may be configured as an integrated type on a chip using a known semiconductor technology. By doing so, it can be miniaturized and incorporated in portable equipment or the like, or data from a large amount of sensor system 1 can be acquired wirelessly and constantly monitored, environmental measurement, health monitoring, etc. Can be applied to other applications.

<Detection target substance concentration measurement process>
An example of processing related to the measurement of the concentration of the detection target substance by the sensor system 1 will be described with reference to the flowchart of FIG.

First, for example, when the user instructs to measure the concentration of the detection target substance in the sample by operating the operation unit 70, the CPU 51 uses the matrix sensor 10 in which the matrix sensor 10 incorporated in the sensor system 1 is not used. (That is, whether or not all the sensor units 20 included in the matrix sensor 10 in the sensor system 1 are sealed with the sealing member 17) (step S11).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1. Based on the above, it is determined whether or not the matrix sensor 10 is an unused matrix sensor.
Here, the usage history is, for example, matrix sensor identification information for identifying the matrix sensor 10 incorporated in the sensor system 1 and a sensor unit for identifying the sensor unit 20 from which the sealing member 17 has been removed. The identification information is information associated with the date and time when the sealing member 17 is removed, and is stored in the memory unit 60, for example.

  If it is determined in step S11 that the matrix sensor 10 incorporated in the sensor system 1 is an unused matrix sensor (step S11; Yes), the CPU 51 proceeds to the process of step S15.

On the other hand, if it is determined in step S11 that the matrix sensor 10 incorporated in the sensor system 1 is not an unused matrix sensor (step S11; No), the CPU 51 executes the deterioration determination program 531 to perform the previous detection. It is determined whether the used sensor unit 20 (the sensor unit 20 from which the sealing member 17 has been removed) is deteriorated (step S12).
Specifically, the CPU 51 uses, for example, the sensor used for the previous detection based on “usage history (for example, date and time when the sealing member 17 was removed)” of the matrix sensor 10 incorporated in the sensor system 1. It is determined whether the unit 20 has deteriorated.

  If it is determined in step S12 that the sensor unit 20 used for the previous detection has not deteriorated (step S12; No), the CPU 51 executes the sensor unit designation program 532 and uses the sensor unit used for the previous detection. 20 is designated (step S13), and the process proceeds to step S17.

On the other hand, if it is determined in step S12 that the sensor unit 20 used for the previous detection has deteriorated (step S12; Yes), the CPU 51 determines the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1. It is determined whether or not there is a sensor unit 20 from which the sealing member 17 has not been removed (step S14).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1. Based on the above, it is determined whether or not there is a sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10.

If it is determined in step S14 that there is no sensor unit 20 in which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1 (step S14; No), the CPU 51 This process ends.
Then, for example, the CPU 51 causes the display unit 80 to display a predetermined display indicating that the matrix sensor 10 incorporated in the sensor system 1 is to be replaced. Prompt to replace 10.

  On the other hand, if it is determined in step S14 that there is a sensor unit 20 in which the sealing member 17 is not removed among the sensor units 20 included in the matrix sensor 10 incorporated in the sensor system 1 (step S14; Yes), the CPU 51. Executes the sensor part designation program 532 and designates the sensor part 20 (the sensor part 20 from which the sealing member 17 is not removed) according to the preset order of the sensor parts 20 to be used (step S15).

  Next, the CPU 51 executes the sealing removal control program 533 to cause the sealing removal unit 30 to remove the sealing member 17 corresponding to the designated sensor unit 20 (step S16).

Next, the CPU 51 executes the detection data acquisition control program 534, and causes the detection data acquisition unit 40 to acquire detection data from the designated sensor unit 20 (step S17).
Specifically, for example, when voltage application to the working electrode 121 is started and a sample is forcibly supplied to the supply layer 23, sample supply to the supply layer 23 is started. When the response current from the working electrode 121 reaches equilibrium, the voltage application is terminated, and when the sample is forcibly supplied to the supply layer 23, the supply is terminated. This series of processing is performed on the designated sensor unit 20.

Next, the CPU 51 executes the concentration calculation program 535, calculates the concentration of the detection target substance based on the acquired detection data (step S18), and ends this process.
Then, for example, the CPU 51 stores the detection data acquired in step S <b> 17 or the concentration of the detection target substance calculated in step S <b> 18 in the memory unit 60 or displays it on the display unit 80.
Of course, if it is instructed to stop the measurement of the concentration of the detection target substance by the operation of the operation unit 70 by the user during step S11 to step S18, the CPU 51 ends this processing at that time.

  According to the sensor system 1 in the first embodiment described above, the plurality of sensor units 20 arranged in a two-dimensional matrix and the sealing member 17 that shuts off each of the plurality of sensor units 20 from the outside. The matrix sensor 10 having, the CPU 51 that has executed the sensor unit designation program 532 for designating the predetermined sensor unit 20 among the plurality of sensor units 20, and the sealing member 17 corresponding to the designated sensor unit 20 are removed. A sealing removal unit 30 and a detection data acquisition unit 40 that acquires detection data from the designated sensor unit 20 are provided.

Specifically, the sensor system 1 in the first embodiment includes a substrate 11, a plurality of sensor units 20 arranged in a two-dimensional matrix on the substrate 11, and a sensor unit arranged on the substrate 11. 20. A matrix having a partition wall 14 that separates 20 and 20 and a sealing member 17 that blocks each of the plurality of sensor units 20 from the outside by sealing the surface of the sensor unit 20 facing the substrate 11. The CPU 51 that has executed the sensor 10 and the sensor unit designation program 532 that designates the predetermined sensor unit 20 among the plurality of sensor units 20 and the sealing member 17 that removes the sealing member 17 corresponding to the designated sensor unit 20 A removal unit 30; and a detection data acquisition unit 40 that acquires detection data from the designated sensor unit 20. The sensor unit 20 selectively selects an electrolyte and a detection target substance. An enzyme E as response to reactant (biological materials), while containing, are cut off from the outside by the sealing member 17.
That is, since the sensor unit 20 is blocked from the outside by the sealing member 17, it is possible to prevent the sensor unit 20 from being deteriorated due to exposure to the atmosphere or the like until it is designated and the sealing member 17 is removed. In addition, since only the designated sensor unit 20 among the plurality of sensor units 20 is used, it is possible to prevent deterioration of the sensor unit 20 due to use until designated and used. Further, not all of the plurality of sensor units 20 included in the matrix sensor 10 are used at the same time, but only the designated sensor unit 20 among the plurality of sensor units 20 is used (used by removing the sealing member 17). Therefore, the matrix sensor 10 can be used until all of the plurality of sensor units 20 are used up. Therefore, even if the lifetime of each sensor unit is short, the lifetime of the matrix sensor 10 as a sensor can be significantly increased.
Further, since the sealing member 17 corresponding to the designated sensor unit 20 is automatically removed, there is no need for the user to remove the sealing member 17 at the time of detection, thereby reducing troublesomeness at the time of detection. can do.

Moreover, according to the sensor system 1 in the first embodiment described above, the CPU 51 that executes the deterioration determination program 531 that determines whether or not the sensor unit 20 from which the sealing member 17 has been removed is deteriorated is provided. When it is determined that the sensor unit 20 has deteriorated, the CPU 51 that has executed the sensor unit designation program 532 designates the sensor unit 20 from which the sealing member 17 has not been removed.
That is, only the designated sensor part 20 among the plurality of sensor parts 20 is used (used by removing the sealing member 17), and when the sensor part 20 deteriorates, the sensor part 20 to be used next (sealing) Since the sensor portion 20) from which the member 17 is not removed is designated, the lifetime of the matrix sensor 10 as a sensor can be significantly increased, and the reliability of the matrix sensor 10 as a sensor is enhanced. be able to.

Further, according to the matrix sensor 10 in the first embodiment described above, the substrate 11, the plurality of sensor units 20 arranged in a two-dimensional matrix on the substrate 11, and the substrate 11 are arranged. The sensor unit 20 and the partition wall part 14 that separates the sensor units 20 from each other. The sensor unit 20 is disposed on the electrode 12 as a detection element disposed on the substrate 11, and is substantially at least with respect to the substrate 11. A porous body 13 having pores 13a penetrating in the vertical direction, and an enzyme E as a reactive substance (biological substance) carried inside the pores 13a of the porous body 13 and selectively reacting with a detection target substance. And a predetermined change associated with the reaction is detected by the electrode 12.
That is, since the enzyme E that selectively reacts with the detection target substance is fixed to the porous body 13, the amount of the enzyme E included in the sensor unit 20 is smaller than when the enzyme E is directly fixed on the electrode 12. Even if the matrix sensor 10 is reduced in size, the sensor unit 20 becomes highly sensitive.
Therefore, as compared with the case where the enzyme E is directly fixed on the electrode 12, it is possible to provide a smaller highly sensitive matrix sensor 10, which is preferable.
Furthermore, since the porous body 13 is a porous body having pores 13a penetrating in a substantially vertical direction with respect to the substrate 11, the reactant (enzyme E) can be appropriately dispersed, and the diffusibility of the substrate and the product can be reduced. Therefore, improvement in sensor sensitivity can be expected.

[Second Embodiment]
Next, the sensor system 1A and the matrix sensor 10A included in the sensor system 1A according to the second embodiment will be described.
In the sensor system 1A of the second embodiment, the matrix sensor 10A includes a plurality of types of sensor units 20 having different detection density ranges as the plurality of sensor units 20 in the first embodiment. Different from the sensor system 1 of FIG. Therefore, only different parts will be described, and other common parts will be described with the same reference numerals.

<Sensor system>
FIG. 14 is a block diagram illustrating a functional configuration of the sensor system 1A according to the second embodiment.

  The sensor system 1A includes, for example, a matrix sensor 10A, a seal removal unit 30, a detection data acquisition unit 40, a control unit 50A, a memory unit 60, an operation unit 70, a display unit 80, and the like. Composed.

<Matrix sensor>
15 is a plan perspective view of the matrix sensor 10A, FIG. 16 is an exploded view of the matrix sensor 10A, and FIG. 17 is a cross-sectional view taken along line XVII-XVII in FIG.

The matrix sensor 10A includes, for example, five types of sensor units 20 having different detection concentration ranges in which a detection target substance can be detected.
Specifically, in the sensor system 1A, the 25 sensor units 20 included in the matrix sensor 10A include, for example, the sensor units 20 and 20 in the same column having the same detection density range and different sensor units 20 in the column. , 20 have different detection density ranges. That is, for example, the detection density range of the sensor unit (1,1), (2,1), (3,1), (4,1), (5,1) (= sensor unit (X, 1)) is Each is the same, and the detection density range of the sensor part (1, 2), (2, 2), (3, 2), (4, 2), (5, 2) (= sensor part (X, 2)) Are the same, and the detected concentrations of the sensor parts (1, 3), (2, 3), (3, 3), (4, 3), (5, 3) (= sensor part (X, 3)) The ranges are the same, and the detection of the sensor parts (1, 4), (2, 4), (3,4), (4, 4), (5, 4) (= sensor part (X, 4)) The concentration ranges are the same, and the sensor portions (1, 5), (2, 5), (3, 5), (4, 5), (5, 5) (= sensor portion (X, 5)) The detected concentration ranges are the same and the sensor unit ( 1), sensor unit (X, 2), sensor unit (X, 3), sensor unit (X, 4), and sensor unit (X, 5) have different detection density ranges. To do.

In the sensor system 1A, the 25 sensor units 20 included in the matrix sensor 10A are grouped, for example, with the sensor units 20 and 20 in the same row. That is, the 25 sensor units 20 include, for example, a group of sensor units (1, Y), a group of sensor units (2, Y), a group of sensor units (3, Y), and a sensor unit (4, 4). The group of Y) and the group of sensor units (5, Y) are grouped.
Therefore, the five sensor units 20 belonging to one group include five types of sensor units 20 having different detection density ranges.

  Specifically, the matrix sensor 10A includes, for example, the substrate 11, the electrode 12 (the working electrode 121, the reference electrode 122, and the counter electrode 123), the porous body 13, the enzyme E, the partition wall 14, and the permeable membrane 15. And an adjustment permeable membrane 19 disposed on the permeable membrane 15, a spacer 16, a sealing member 17, a cover member 18, and the like.

(Permeation membrane for adjustment)
The adjustment permeable membrane 19 is formed, for example, in a substantially rectangular shape in plan view, and is set so that the size in plan view can cover the analysis unit 111. The adjustment permeable membrane 19 is fixed on the permeable membrane 15 by, for example, a region other than the region corresponding to the analysis unit 111 in the adjustment permeable membrane 19 being thermocompressed or bonded to the upper surface of the permeable membrane 15. ing.

The region corresponding to the analysis unit 111 in the permeable film 15 or the region corresponding to the analysis unit 111 in the adjustment permeable film 19 and the permeable film 15 is the transmissive layer 22 of the sensor unit 20 and is supplied to the detection layer 21. The layer 23 is separated.
The adjustment permeable membrane 19 is for adjusting the detection density range of the sensor unit 20. The detection concentration range of the sensor unit 20 depends on the diffusion of the detection target substance in the transmission layer 22 and the detection layer 21. That is, when the detection target substance is easy to diffuse, the detection concentration range of the sensor unit 20 is on the low concentration side, and when the detection target substance is difficult to diffuse, the detection concentration range of the sensor unit 20 is on the high concentration side. . Therefore, the detection concentration range of the sensor unit 20 can be changed by changing the transmittance when the substance to be detected passes through the transmission layer 22 by the adjustment permeable film 19.

The type of the adjustment permeable membrane 19 provided in the matrix sensor 10A is, for example, a first adjustment permeable membrane and a substance to be detected that is less permeable than the first adjustment permeable membrane (permeability coefficient than that of the first adjustment permeable membrane). A second adjustment permeable membrane, a third adjustment permeable membrane having a permeability coefficient lower than that of the second adjustment permeable membrane, and a fourth adjustment permeable membrane having a permeability coefficient lower than that of the third adjustment permeable membrane. For example, the first adjustment permeable membrane is provided at a position corresponding to the sensor portion (X, 2), and the second adjustment permeable membrane is provided at a position corresponding to the sensor portion (X, 3). The third adjustment permeable membrane is provided at a position corresponding to the sensor portion (X, 4), and the fourth adjustment permeable membrane is provided at a position corresponding to the sensor portion (X, 5).
Therefore, the transmittance when the detection target substance passes through the transmission layer 22 is as follows: sensor part (X, 1)> sensor part (X, 2)> sensor part (X, 3)> sensor part (X, 4)> The sensor part (X, 5) is the lowest density side of the sensor part (X, 1), and the highest density side of the sensor part (X, 5). Yes.

The detection target substance in the sample supplied to the supply layer 23 passes through the transmission layer 22 (the transmission film 15, or the adjustment transmission film 19 and the transmission film 15) and moves to the detection layer 21. It reacts with the enzyme E provided. Therefore, the adjustment permeable membrane 19 is arbitrary as long as it is a film that allows at least the detection target substance to pass therethrough, and can be appropriately changed depending on the type of the detection target substance.
In particular, when the sample is a gas sample, the adjustment permeable membrane 19 is preferably a gas permeable membrane that transmits a detection target substance (detection target gas) but does not transmit a liquid such as an electrolytic solution.
Here, as the gas permeable film, for example, a polyethylene film or a Teflon film having air permeability can be used.

<Control unit>
For example, as shown in FIG. 14, the control unit 50A includes a CPU 51, a RAM 52, a storage unit 53A, and the like.

  For example, as shown in FIG. 14, the storage unit 53A includes a deterioration determination program 531, a sensor unit designation program 532A, a seal removal control program 533, a detection data acquisition control program 534, a concentration calculation program 535A, and the like. Is remembered.

  For example, the sensor unit designation program 532A causes the CPU 51 to realize a function of designating the sensor units 20 belonging to a predetermined group (for example, a predetermined group) among the plurality of sensor units 20.

Specifically, for example, when the CPU 51 that has executed the deterioration determination program 531 determines that the sensor unit 20 has deteriorated, the CPU 51 selects a group according to a preset “order of groups to be used”. The sensor unit 20 belonging to the selected group (the sensor unit 20 from which the sealing member 17 has not been removed) is designated.
Here, the order of the groups to be used is arbitrary. Specifically, for example, “sensor part (1, Y) group → sensor part (2, Y) group → sensor part (3, Y) group → sensor part” (4, Y) group → sensor part (5, Y) ″ and the like.
The CPU 51 functions as a designation unit by executing the sensor unit designation program 532A.

  For example, the sensor unit 20 belonging to a predetermined group is designated by the CPU 51 that has executed the sensor unit designation program 532A. Therefore, the seal removing unit 30 includes five types of sensor units 20 belonging to the one group. The sealing member 17 corresponding to each (five types of sensor units 20 having different detection density ranges) is removed, and the detection data acquisition unit 40 has five types of sensor units 20 belonging to the one group (the detection density range is Detection data from each of the five different types of sensor units 20) is acquired.

  For example, the concentration calculation program 535A causes the CPU 51 to realize a function of calculating the concentration of the detection target substance based on the detection data acquired by the detection data acquisition unit 40.

  Specifically, the CPU 51, for example, based on a preset “allowable current range” and detection data (response current value) obtained by each of the five types of sensor units 20 acquired by the detection data acquisition unit 40. The sensor unit 20 having the optimum detection density range is determined from the five types of sensor units 20.

Here, for example, when a calibration curve as shown in FIG. 18 is acquired as the calibration curve of the sensor unit 20, the CPU 51 determines, for example, that the detection concentration range is C1 to C4, and the response current corresponding to the detection concentration range. Is determined as I1 to I4.
And as a calibration curve of each of the five types of sensor units 20 with different detection concentration ranges, for example, a calibration curve as shown in FIG. 19 (five types of sensor units 20 with different detection concentration ranges (for example, sensor unit A, sensor unit) B, sensor unit C, sensor unit D, sensor unit E) each calibration curve), the CPU 51 determines, for example, a response current range corresponding to each detection concentration range, and sets the allowable current range as A range (for example, I2 to I3) that falls within the entire response current range corresponding to each detection concentration range is determined. The allowable current range is a range that falls within all of the response current ranges corresponding to each detection concentration range, that is, a response current range corresponding to the detection concentration range of sensor unit A and a detection concentration range of sensor unit B. Corresponding to the corresponding response current range, the response current range corresponding to the detection concentration range of the sensor unit C, the response current range corresponding to the detection concentration range of the sensor unit D, and the detection concentration range of the sensor unit E Any response current can be used as long as it is within the range of the response current.
Then, the CPU 51 compares the determined allowable current range (I2 to I3) with the response current values obtained by the five types of sensor units 20 acquired by the detection data acquisition unit 40, and the response current value is the allowable current. The sensor unit 20 within the range is determined as the sensor unit 20 having the optimum detection density range. That is, for example, the response current value by the sensor units (1, 1) and (1, 2) is “response current value> I3”, and the response current value by the sensor unit (1, 3) is “I2 ≦ response current value”. When ≦ I3 ”and the response current value by the sensor units (1, 4) and (1, 5) is“ response current value <I2 ”, the CPU 51 detects the sensor unit 20 having the optimum detection density range as the sensor unit 20 Part (1,3) is determined.

Next, the CPU 51, for example, among the “calibration curve” acquired in advance, the calibration curve corresponding to the determined concentration range of the sensor unit 20 and the detection data (equilibrium state) by the determined sensor unit 20. The concentration of the detection target substance is calculated based on
When a plurality of sensor units 20 are determined as the sensor unit 20 having the optimum detection density range, for example, the CPU 51 selects one sensor unit 20 of the determined plurality of sensor units 20, The concentration of the detection target substance may be calculated based on the detection data by the selected one sensor unit 20, or the concentration of the detection target substance based on the determined detection data of each of the plurality of sensor units 20 May be obtained, a predetermined statistical process (for example, a process for obtaining an average value) is performed using the obtained concentration, and a result of the predetermined statistical process may be used as the calculated concentration of the detection target substance.
The CPU 51 functions as a calculation unit by executing the density calculation program 535A.

The predetermined statistical process is not limited to the process of obtaining an average value, and may be, for example, a process of obtaining an intermediate value, or a process of obtaining a probability of a value from an average, variance, standard deviation, or the like. Alternatively, it may be a process of adding each detection data, or a process of obtaining a difference between each detection data.
Here, the process of adding each detection data is, for example, a process of preparing a plurality of sensor units 20 having different detection target substances and calculating the sum of the detection data by each sensor unit 20. Specifically, the detection target substance of sensor part A is formaldehyde, the detection target substance of sensor part B is benzene, the detection target substance of sensor part C is xylene, and the detection target substance of sensor part D is toluene. In this case, the sum of the detection data by each sensor unit 20 is defined as VOC (volatile organic compound), and the concentration of VOC can be calculated based on this sum.
Moreover, the process which takes the difference of each detection data is a process which prepares the several sensor part 20 from which a detection target substance differs, and takes the difference of the detection data by each sensor part 20, for example. Specifically, when the detection target substance of the sensor unit A is a hydrogen compound and a sulfur-based substance, and the detection target substance of the sensor unit B is only a sulfur-based substance, based on the difference in detection data of each sensor unit 20 The concentration of the hydrogen compound can be calculated.

<Detection target substance concentration measurement process>
An example of processing related to the measurement of the concentration of the detection target substance by the sensor system 1A will be described with reference to the flowchart of FIG.

First, for example, when the user instructs to measure the concentration of the detection target substance in the sample by operating the operation unit 70, the CPU 51 detects that the matrix sensor 10A incorporated in the sensor system 1A is not used. (That is, whether or not all the sensor units 20 included in the matrix sensor 10A in the sensor system 1A are sealed with the sealing member 17) (step S21).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10A incorporated in the sensor system 1A. Based on the above, it is determined whether the matrix sensor 10A is an unused matrix sensor.

  If it is determined in step S21 that the matrix sensor 10A incorporated in the sensor system 1A is an unused matrix sensor (step S21; Yes), the CPU 51 proceeds to the process of step S25.

On the other hand, if it is determined in step S21 that the matrix sensor 10A incorporated in the sensor system 1A is not an unused matrix sensor (step S21; No), the CPU 51 executes the deterioration determination program 531 and performs the previous detection. It is determined whether or not the sensor unit 20 belonging to the used group (the sensor unit 20 from which the sealing member 17 has been removed) is deteriorated (step S22).
Specifically, the CPU 51 uses, for example, the group used for the previous detection based on “use history (for example, date and time when the sealing member 17 was removed)” of the matrix sensor 10A incorporated in the sensor system 1A. It is determined whether or not the sensor unit 20 belonging to is degraded.

  If it is determined in step S22 that the sensor unit 20 belonging to the group used for the previous detection has not deteriorated (step S22; No), the CPU 51 executes the sensor unit designation program 532A to perform the previous detection. The sensor unit 20 belonging to the used group is designated (step S23), and the process proceeds to step S27.

On the other hand, if it is determined in step S22 that the sensor unit 20 belonging to the group used for the previous detection has deteriorated (step S22; Yes), the CPU 51 includes the matrix sensor 10A incorporated in the sensor system 1A. It is determined whether there is a sensor unit 20 in which the sealing member 17 is not removed in the sensor unit 20 (step S24).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10A incorporated in the sensor system 1A. Based on the above, it is determined whether or not there is a sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10A.

When it is determined in step S24 that there is no sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10A incorporated in the sensor system 1A (step S24; No), the CPU 51 This process ends.
Then, for example, the CPU 51 causes the display unit 80 to display a predetermined display indicating that the matrix sensor 10A incorporated in the sensor system 1A is to be replaced. Prompt to replace 10.

  On the other hand, when it is determined in step S24 that there is a sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10A incorporated in the sensor system 1A (step S24; Yes), the CPU 51. Executes a sensor unit designation program 532A, selects a group according to a preset order of groups to be used, and belongs to the selected group of sensor units 20 (the sensor unit 20 from which the sealing member 17 has not been removed). Then, each type of sensor unit 20) having a different detection density range is designated (step S25).

  Next, the CPU 51 executes the sealing removal control program 533 to cause the sealing removal unit 30 to remove the sealing member 17 corresponding to the designated sensor unit 20 (step S26).

Next, the CPU 51 executes the detection data acquisition control program 534 to cause the detection data acquisition unit 40 to acquire detection data from the designated sensor unit 20 (step S27).
Specifically, for example, when the working electrode 121 included in the designated sensor unit 20 is selected, voltage application to the working electrode 121 is started, and the sample is forcibly supplied to the supply layer 23. Sample supply to the supply layer 23 is started. When the response current from the working electrode 121 reaches equilibrium, the channel is switched to select the working electrode 121 included in the sequentially designated sensor unit 20, and the same operation is repeated. Then, when the voltage application is finished and the sample is forcibly supplied to the supply layer 23, the supply is finished. This series of processing is performed for all the designated sensor units 20.
In addition, the response from all the channels can be acquired in a short time by sequentially switching the working electrode 121 sequentially using a pulse voltammetry method and sequentially applying an appropriate pulse corresponding to each sequence. You can also.

Next, the CPU 51 executes the density calculation program 535A to determine a sensor unit having an optimum detection density range from each type of sensor unit 20 based on the acquired detection data (step S28). Based on the detection data obtained by the sensor unit having the determined optimum detection concentration range, the concentration of the detection target substance is calculated (step S29), and this process is terminated.
Then, for example, the CPU 51 stores the detection data acquired in step S27 and the concentration of the detection target substance calculated in step S29 in the memory unit 60 or displays on the display unit 80.
Of course, during steps S21 to S29, if the user instructs to stop the measurement of the concentration of the detection target substance by operating the operation unit 70 or the like, the CPU 51 ends this processing at that time.

According to the sensor system 1A in the second embodiment described above, the plurality of sensor units 20 that detect the detection target substance, the detection data acquisition unit 40 that acquires the detection data by the sensor unit 20, and the detection data acquisition unit And a CPU 51 that executes a concentration calculation program 535A for calculating the concentration of the detection target substance based on the detection data acquired by the plurality of sensor units 20, and the plurality of sensor units 20 have a detection concentration range in which the detection target substance can be detected. A plurality of different types of sensor units 20 are grouped into a plurality of groups, and the plurality of sensor units 20 belonging to one group include each type of sensor unit 20 having a different detection density range, and detection data acquisition The unit 40 collects detection data from each type of sensor unit 20 belonging to one of a plurality of groups. Then, the CPU 51 that has executed the concentration calculation program 535A determines the sensor unit 20 having the optimum detection concentration range from the various types of sensor units 20 based on the detection data acquired by the detection data acquisition unit 40, and Based on the determined detection data by the sensor unit 20, the concentration of the detection target substance is calculated.
Therefore, the sensor system 1A (matrix sensor 10A) as a whole can have a wide range of detection concentration with a simple configuration including a plurality of types of sensor units 20 having different detection concentration ranges, and a plurality of types of sensor units 20 can be provided. Since the detection target substance can be detected by the sensor unit 20 having the optimum detection concentration range, the detection target substance is detected within the appropriate detection concentration range even if the concentration of the detection target substance is unknown. Thus, the concentration of the detection target substance can be calculated.
Further, only the designated group of the plurality of groups is used, and when the group deteriorates, the group to be used next is designated and newly used. Life can be extended.

[Third Embodiment]
Next, a sensor system 1B according to the third embodiment will be described.
The sensor system 1B according to the third embodiment performs predetermined statistical processing using detection data from each of the plurality of sensor units 20 having the same detection concentration range, and based on the result of the predetermined statistical processing. The point which calculates the density | concentration of a detection target substance differs from the sensor system 1 of 1st Embodiment. Therefore, only different parts will be described, and other common parts will be described with the same reference numerals.

<Sensor system>
FIG. 21 is a block diagram illustrating a functional configuration of a sensor system 1B according to the third embodiment.

  The sensor system 1B includes, for example, a matrix sensor 10, a seal removal unit 30, a detection data acquisition unit 40, a control unit 50B, a memory unit 60, an operation unit 70, a display unit 80, and the like. Composed.

Here, in the sensor system 1B, the 25 sensor units 20 included in the matrix sensor 10 have, for example, the same detection density range. The number of sensor units 20 used at one time is set in advance, for example, and the 25 sensor units 20 included in the matrix sensor 10 are grouped according to the number of sensor units 20 used at one time, for example. Suppose that
Specifically, for example, when the number of sensor units 20 to be used at a time is set to five, the 25 sensor units 20 included in the matrix sensor 10 include the five sensor units 20 as a set, It is assumed that it is grouped into five groups.

<Control unit>
For example, as shown in FIG. 21, the control unit 50B includes a CPU 51, a RAM 52, a storage unit 53B, and the like.

  For example, as shown in FIG. 21, the storage unit 53B includes a deterioration determination program 531, a sensor unit designation program 532B, a seal removal control program 533, a detection data acquisition control program 534, a concentration calculation program 535B, and the like. Is remembered.

  For example, the sensor unit designation program 532B causes the CPU 51 to realize a function of designating the sensor units 20 belonging to a predetermined group (for example, a predetermined one group) among the plurality of sensor units 20.

Specifically, for example, when the CPU 51 that has executed the deterioration determination program 531 determines that the sensor unit 20 has deteriorated, the CPU 51 selects a group according to a preset “order of groups to be used”. The sensor unit 20 belonging to the selected group (the sensor unit 20 from which the sealing member 17 has not been removed) is designated.
The CPU 51 functions as a designation unit by executing the sensor unit designation program 532B.

  For example, since the CPU 51 that has executed the sensor unit designation program 532B designates the sensor unit 20 belonging to a predetermined group, the seal removal unit 30 includes a plurality of sensor units 20 ( The sealing member 17 corresponding to each of the plurality of sensor units 20) having the same detection density range is removed, and the detection data acquisition unit 40 has a plurality of sensor units 20 belonging to the one group (the same detection density range). The detection data by each of the plurality of sensor units 20) is acquired.

  The concentration calculation program 535B causes the CPU 51 to realize a function of calculating the concentration of the detection target substance based on the detection data acquired by the detection data acquisition unit 40, for example.

Specifically, for example, the CPU 51 performs predetermined statistical processing using the detection data acquired by the detection data acquisition unit 40, and calculates the concentration of the detection target substance based on the result of the predetermined statistical processing. .
Here, the predetermined statistical processing is, for example, processing for obtaining an average value.
That is, for example, the CPU 51 obtains an average value of detection data (response current values in an equilibrium state) by a plurality of sensor units 20 having the same detection concentration range, and the average value and a calibration curve acquired in advance. Based on the above, the concentration of the detection target substance is calculated.
The CPU 51 functions as a calculation unit by executing the density calculation program 535B.

  The predetermined statistical process is not limited to the process of obtaining an average value, and may be, for example, a process of obtaining an intermediate value, or a process of obtaining a probability of a value from an average, variance, standard deviation, or the like. Alternatively, it may be a process of adding each detection data, or a process of obtaining a difference between each detection data.

<Detection target substance concentration measurement process>
An example of processing related to the measurement of the concentration of the detection target substance by the sensor system 1B will be described with reference to the flowchart of FIG.

First, for example, when the user instructs to measure the concentration of the detection target substance in the sample by operating the operation unit 70, the CPU 51 uses the matrix sensor 10 in which the matrix sensor 10 incorporated in the sensor system 1B is not used. (That is, whether all the sensor units 20 included in the matrix sensor 10 in the sensor system 1B are sealed with the sealing member 17) (step S31).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1B. Based on the above, it is determined whether or not the matrix sensor 10 is an unused matrix sensor.

  If it is determined in step S31 that the matrix sensor 10 incorporated in the sensor system 1B is an unused matrix sensor (step S31; Yes), the CPU 51 proceeds to the process of step S35.

On the other hand, if it is determined in step S31 that the matrix sensor 10 incorporated in the sensor system 1B is not an unused matrix sensor (step S31; No), the CPU 51 executes the deterioration determination program 531 and performs the previous detection. It is determined whether or not the sensor unit 20 belonging to the used group (the sensor unit 20 from which the sealing member 17 has been removed) has deteriorated (step S32).
Specifically, the CPU 51 uses, for example, the group used for the previous detection based on “use history (for example, date and time when the sealing member 17 was removed)” of the matrix sensor 10 incorporated in the sensor system 1B. It is determined whether or not the sensor unit 20 belonging to is degraded.

  If it is determined in step S32 that the sensor unit 20 belonging to the group used for the previous detection has not deteriorated (step S32; No), the CPU 51 executes the sensor unit designation program 532B to perform the previous detection. The sensor unit 20 belonging to the used group is designated (step S33), and the process proceeds to step S37.

On the other hand, if it is determined in step S32 that the sensor unit 20 belonging to the group used for the previous detection has deteriorated (step S32; Yes), the CPU 51 includes the matrix sensor 10 incorporated in the sensor system 1B. It is determined whether or not there is a sensor unit 20 in which the sealing member 17 is not removed in the sensor unit 20 (step S34).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1B. Based on the above, it is determined whether or not there is a sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10.

If it is determined in step S34 that there is no sensor unit 20 in which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1B (step S34; No), the CPU 51 This process ends.
Then, for example, the CPU 51 causes the display unit 80 to display a predetermined display indicating that the matrix sensor 10 incorporated in the sensor system 1B is to be replaced. Prompt to replace 10.

  On the other hand, if it is determined in step S34 that the sensor unit 20 in which the sealing member 17 is not removed is present in the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1B (step S34; Yes), the CPU 51. Executes the sensor unit designation program 532B, selects a group according to a preset order of groups to be used, and belongs to the selected group of sensor units 20 (the sensor unit 20 from which the sealing member 17 has not been removed). Then, a plurality of sensor units 20) having the same detection density range are designated (step S35).

  Next, the CPU 51 executes the sealing removal control program 533 to cause the sealing removal unit 30 to remove the sealing member 17 corresponding to the designated sensor unit 20 (step S36).

Next, the CPU 51 executes the detection data acquisition control program 534 to cause the detection data acquisition unit 40 to acquire detection data from the designated sensor unit 20 (step S37).
Specifically, for example, when the working electrode 121 included in the designated sensor unit 20 is selected, voltage application to the working electrode 121 is started, and the sample is forcibly supplied to the supply layer 23. Sample supply to the supply layer 23 is started. When the response current from the working electrode 121 reaches equilibrium, the channel is switched to select the working electrode 121 included in the sequentially designated sensor unit 20, and the same operation is repeated. Then, when the voltage application is finished and the sample is forcibly supplied to the supply layer 23, the supply is finished. This series of processing is performed for all the designated sensor units 20.
In addition, the response from all the channels can be acquired in a short time by sequentially switching the working electrode 121 sequentially using a pulse voltammetry method and sequentially applying an appropriate pulse corresponding to each sequence. You can also.

Next, the CPU 51 executes the concentration calculation program 535B to obtain the average value of the acquired detection data (step S38), calculates the concentration of the detection target substance based on the average value (step S39), The process ends.
The CPU 51 stores, for example, the detection data acquired in step S37, the average value obtained in step S38, and the concentration of the detection target substance calculated in step S39 in the memory unit 60 or displayed on the display unit 80. .
Of course, if it is instructed to stop the measurement of the concentration of the detection target substance by the operation of the operation unit 70 by the user during step S31 to step S39, the CPU 51 ends this processing at that time.

According to the sensor system 1B in the third embodiment described above, the plurality of sensor units 20 that detect the detection target substance, the detection data acquisition unit 40 that acquires the detection data by the sensor unit 20, and the detection data acquisition unit And a CPU 51 that executes a concentration calculation program 535B for calculating the concentration of the detection target substance based on the detection data acquired by the plurality of sensor units 20, and the plurality of sensor units 20 have a plurality of sensor concentration ranges having the same detection concentration range. 20, the detection data acquisition unit 40 acquires detection data from each of the plurality of sensor units 20 having the same detection concentration range, and the CPU 51 that has executed the concentration calculation program 535B has been acquired by the detection data acquisition unit 40. Predetermined statistical processing is performed using the detection data, and based on the result of the predetermined statistical processing, the concentration of the detection target substance It is adapted to calculate.
That is, the concentration measurement accuracy of the sensor system 1B can be improved because the concentration of the detection target substance is calculated based on the result of statistical processing of the detection data from each of the plurality of sensor units 20.

[Fourth Embodiment]
Next, the sensor system 1C and the matrix sensor 10C included in the sensor system 1C according to the fourth embodiment will be described.
In the sensor system 1C of the fourth embodiment, the matrix sensor 10C includes a plurality of sensor units 20 including the enzyme E, and a plurality of difference sensor units 20C (difference reference sensor units) that do not include the enzyme E. Are different from the sensor system 1 of the first embodiment. Therefore, only different parts will be described, and other common parts will be described with the same reference numerals.

<Sensor system>
FIG. 23 is a block diagram illustrating a functional configuration of a sensor system 1C according to the fourth embodiment.

  The sensor system 1C includes, for example, a matrix sensor 10C, a seal removal unit 30, a detection data acquisition unit 40C, a control unit 50C, a memory unit 60, an operation unit 70, a display unit 80, and the like. Composed.

<Matrix sensor>
24 is a plan perspective view of the matrix sensor 10C, and FIG. 25 is a cross-sectional view taken along the line XXV-XXV in FIG.

The matrix sensor 10C includes a plurality of sensor units 20 and a plurality of difference sensor units 20C. The difference sensor unit 20C included in the matrix sensor 10C has, for example, a configuration in which only the enzyme E is removed from the sensor unit 20 (see FIG. 5), as shown in FIG. The plurality of sensor units 20 included in the matrix sensor 10C all have the same detection density range.
Specifically, for example, as shown in FIG. 24, in the sensor system 1C, the sensor units (1, Y), (2, Y), and (3, Y) are sensor units 20 (detection sensor units). , Sensor portions (4, Y), (5, Y) are difference sensor portions 20C.
The configuration of the difference sensor unit 20C is the same as the configuration of the sensor unit 20 (see FIG. 5) except that the enzyme E is not provided as shown in FIG. Is omitted.

<Detection data acquisition unit>
The detection data acquisition unit 40C, for example, as detection means according to a control signal input from the control unit 50C, is detection data from the specified sensor unit 20 (the working electrode 121 and the counter electrode 123 included in the specified sensor unit 20). Detection data based on the amount of current flowing during the period of time, and outputs the detection data to the control unit 50C. As the difference acquisition means, the detection data by the specified difference sensor unit 20C (the specified difference sensor unit 20C Detection data based on the amount of current flowing between the working electrode 121 and the reference electrode 122 provided) is obtained and output to the control unit 50C.
That is, the detection data acquisition unit 40C applies, for example, a voltage of a predetermined voltage value to the working electrode 121 with respect to the reference electrode 122 for the designated sensor unit 20, and the current output from the working electrode 121 at that time Current value (response current value) is acquired and output to the control unit 50C, and a voltage having a predetermined voltage value is applied to the working electrode 121 with respect to the reference electrode 122 in the designated difference sensor unit 20C. In this case, the current value (response current value) of the current output from the working electrode 121 is acquired and output to the control unit 50C.

<Control unit>
For example, as illustrated in FIG. 23, the control unit 50C includes a CPU 51, a RAM 52, a storage unit 53C, and the like.

  For example, as shown in FIG. 23, the storage unit 53C includes a deterioration determination program 531C, a sensor unit designation program 532C, a seal removal control program 533C, a detection data acquisition control program 534C, a concentration calculation program 535C, and the like. Is remembered.

For example, the deterioration determination program 531C determines whether or not the sensor unit 20 from which the sealing member 17 has been removed by the sealing removal unit 30 has deteriorated, and the sealing member 17 has been removed by the sealing removal unit 30. The CPU 51 is caused to realize a function of determining whether or not the difference sensor unit 20C is deteriorated.
The CPU 51 functions as a determination unit by executing the deterioration determination program 531C.

The sensor unit designation program 532C specifies, for example, a predetermined sensor unit 20 (for example, one predetermined sensor unit 20) among the plurality of sensor units 20, and among the plurality of difference sensor units 20C. The CPU 51 is caused to realize a function of designating a predetermined difference sensor unit 20C (for example, a predetermined one difference sensor unit 20C).
The CPU 51 functions as a designation unit by executing the sensor unit designation program 532C.

  For example, the sealing removal control program 533C inputs a control signal to the sealing removal unit 30 to remove the sealing member 17 corresponding to the sensor unit 20 designated by the CPU 51 that has executed the sensor unit designation program 532C. The CPU 51 is caused to realize a function of removing the sealing member 17 corresponding to the difference sensor unit 20C designated by the CPU 51 that has executed the sensor unit designation program 532C.

  The detection data acquisition control program 534C inputs, for example, a control signal to the detection data acquisition unit 40C, and the sensor unit 20 (the sensor unit from which the sealing member 17 has been removed) designated by the CPU 51 executing the sensor unit designation program 532C. 20), the control unit 50C is made to acquire the detection data, and the control unit 50C executes the sensor unit designation program 532C, and the difference sensor unit 20C designated by the CPU 51 (the difference sensor unit 20C from which the sealing member 17 has been removed). The CPU 51 is made to realize the function of acquiring the detection data obtained by the above and outputting it to the control unit 50C.

  For example, the concentration calculation program 535 causes the CPU 51 to realize a function of calculating the concentration of the detection target substance based on the detection data acquired by the detection data acquisition unit 40C.

Specifically, for example, the CPU 51 calculates a difference between the detection data obtained by the sensor unit 20 acquired by the detection data acquisition unit 40C and the detection data obtained by the difference sensor unit 20C acquired by the detection data acquisition unit 40C. Based on the difference, the concentration of the detection target substance is calculated.
That is, for example, the CPU 51 takes the difference between the detection data (response current value) from the sensor unit 20 and the detection data (response current value) from the difference sensor unit 20C, and changes the difference over time in an equilibrium state. The response current value is acquired, and the concentration of the detection target substance is calculated based on the response current value in the equilibrium state and the “calibration curve” acquired in advance.
The CPU 51 functions as a calculation unit by executing the density calculation program 535C.

<Detection target substance concentration measurement process>
An example of processing related to the measurement of the concentration of the detection target substance by the sensor system 1C will be described with reference to the flowchart of FIG.

First, for example, when the user instructs to measure the concentration of the detection target substance in the sample by operating the operation unit 70, the CPU 51 detects that the matrix sensor 10C incorporated in the sensor system 1C is not used. (That is, whether or not all the sensor units 20 and the differential sensor units 20C included in the matrix sensor 10C in the sensor system 1C are sealed with the sealing member 17) (step S41). .
Specifically, the CPU 51 identifies, for example, “usage history (for example, the sensor unit 20 from which the sealing member 17 has been removed and the difference sensor unit 20C from the matrix sensor 10C incorporated in the sensor system 1C. Based on the sensor unit identification information), it is determined whether or not the matrix sensor 10 is an unused matrix sensor.

  If it is determined in step S41 that the matrix sensor 10C incorporated in the sensor system 1C is an unused matrix sensor (step S41; Yes), the CPU 51 proceeds to the process of step S45.

On the other hand, if it is determined in step S41 that the matrix sensor 10C incorporated in the sensor system 1C is not an unused matrix sensor (step S41; No), the CPU 51 executes the deterioration determination program 531C and uses the previously used sensor. It is determined whether or not the part 20 and the difference sensor part 20C (the sensor part 20 and the difference sensor part 20C from which the sealing member 17 has been removed) are deteriorated (step S42).
Specifically, the CPU 51, for example, based on the “use history (for example, date and time when the sealing member 17 was removed)” of the matrix sensor 10C incorporated in the sensor system 1C, It is determined whether or not the difference sensor unit 20C is deteriorated.

  If it is determined in step S42 that the sensor unit 20 and the difference sensor unit 20C used last time have not deteriorated (step S42; No), the CPU 51 executes the sensor unit designation program 532C and uses the sensor unit used last time. 20 and the difference sensor unit 20C are designated (step S43), and the process proceeds to step S47.

On the other hand, when it is determined in step S42 that the sensor unit 20 and the difference sensor unit 20C used last time have deteriorated (step S42; Yes), the CPU 51 includes sensors included in the matrix sensor 10C incorporated in the sensor system 1C. It is determined whether or not there are the sensor unit 20 and the difference sensor unit 20C from which the sealing member 17 is not removed in the unit 20 and the difference sensor unit 20C (step S44).
Specifically, the CPU 51 identifies, for example, “usage history (for example, the sensor unit 20 from which the sealing member 17 has been removed and the difference sensor unit 20 </ b> C) of the matrix sensor 10 incorporated in the sensor system 1. Based on the sensor unit identification information), ”it is determined whether or not the sensor unit 20 included in the matrix sensor 10 includes the sensor unit 20 and the difference sensor unit 20C from which the sealing member 17 has not been removed.

In step S44, if there is no sensor unit 20 and differential sensor unit 20C from which the sealing member 17 is not removed in the sensor unit 20 and differential sensor unit 20C included in the matrix sensor 10C incorporated in the sensor system 1C. If it judges (step S44; No), CPU51 will complete | finish this process.
Then, for example, the CPU 51 causes the display unit 80 to display a predetermined display indicating that the matrix sensor 10C incorporated in the sensor system 1C is to be replaced. Prompt to replace 10.

  On the other hand, in step S44, the sensor unit 20 and the difference sensor unit 20C in which the sealing member 17 is not removed are included in the sensor unit 20 and the difference sensor unit 20C included in the matrix sensor 10C incorporated in the sensor system 1C. When it is determined that there is (step S44; Yes), the CPU 51 executes the sensor unit designation program 532C, and the sensor unit 20 (the sealing member 17 is not removed) in accordance with the order of the sensor units 20 to be used that are set in advance. The sensor unit 20) is designated, and the difference sensor unit 20C (the difference sensor unit 20C from which the sealing member 17 has not been removed) is designated in accordance with a preset order of the difference sensor unit 20C to be used (step S20). S45).

  Next, the CPU 51 executes the sealing removal control program 533C to cause the sealing removal unit 30 to remove the sealing member 17 corresponding to the designated sensor unit 20 and differential sensor unit 20C (step S46).

Next, the CPU 51 executes the detection data acquisition control program 534C, and causes the detection data acquisition unit 40C to acquire detection data from the designated sensor unit 20 and difference sensor unit 20C (step S47).
Specifically, for example, when the working electrode 121 included in the designated sensor unit 20 is selected, voltage application to the working electrode 121 is started, and the sample is forcibly supplied to the supply layer 23. Sample supply to the supply layer 23 is started. When the response current from the working electrode 121 reaches equilibrium, the channel is switched to select the working electrode 121 included in the sequentially designated sensor unit 20, and the same operation is repeated. Then, when the voltage application is finished and the sample is forcibly supplied to the supply layer 23, the supply is finished. This series of processing is performed on the designated sensor unit 20 and difference sensor unit 20C.
In addition, the response from all the channels can be acquired in a short time by sequentially switching the working electrode 121 sequentially using a pulse voltammetry method and sequentially applying an appropriate pulse corresponding to each sequence. You can also.

Next, the CPU 51 executes the density calculation program 535C to take the difference between the acquired detection data from the sensor unit 20 and the acquired detection data from the difference sensor unit 20C (step S48), and to the difference Based on this, the concentration of the detection target substance is calculated (step S49), and this process is terminated.
Then, the CPU 51 stores, for example, the detection data acquired in step S47, the difference taken in step S48, and the concentration of the detection target substance calculated in step S49 in the memory unit 60 or displayed on the display unit 80.
Of course, if it is instructed to stop the measurement of the concentration of the detection target substance by the operation of the operation unit 70 by the user during step S41 to step S49, the CPU 51 ends this processing at that time.

According to the sensor system 1C in the fourth embodiment described above, the sensor unit 20 including the enzyme E that selectively reacts with the detection target substance and the electrode 12 that detects a predetermined change associated with the reaction, and the sensor Detection data based on a predetermined change detected by the difference sensor unit 20C obtained by removing the enzyme E from the unit 20 and the electrode 12 included in the sensor unit 20, and detected by the electrode 12 included in the difference sensor unit 20C. The detection data acquisition unit 40C that acquires detection data based on the predetermined change, and the CPU 51 that has executed the concentration calculation program 535C detects the detection data obtained by the sensor unit 20 acquired by the detection data acquisition unit 40C, and the detection data The difference between the difference detection unit 20C acquired by the acquisition unit 40C and the detection data is taken, and based on the difference. Te, and calculates the concentration of the target substance.
That is, the difference sensor unit 20C can detect only the drift observed when detecting a predetermined change associated with the reaction between the detection target substance and the enzyme E. Therefore, by taking the difference, only a predetermined change associated with the reaction between the detection target substance and the enzyme E can be detected, so that the concentration measurement accuracy of the sensor system 1C can be increased and the drift converges (back) Since there is no need to wait until the ground becomes stable, the concentration measurement by the sensor system 1C can be speeded up.

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

<1> Creation of Matrix Sensor First, the matrix sensor M was created. In this example, a matrix sensor for detecting formaldehyde gas was prepared as the matrix sensor M. As the enzyme, formaldehyde dehydrogenase (formaldehyde dehydrogenase), which is a coenzyme (NAD ⁺ ) -dependent enzyme, was used.

<1-1> Creation of Electrode Substrate First, 25 patterns of a three-electrode structure including a working electrode 121, a reference electrode 122, and a counter electrode 123 were created on the substrate 11.
Specifically, a glass substrate formed in a substantially rectangular shape in plan view was prepared as the substrate 11. And this board | substrate 11 was prebaked for 90 second at 95 degreeC using the hotplate. Next, 100 μL of a negative resist was applied using a spin coater, and a tripolar photomask pattern of the working electrode 121, the reference electrode 122 and the counter electrode 123 was transferred using an ultraviolet exposure apparatus. Subsequently, it was post-baked at 120 ° C. for 60 seconds, then developed with a developer for 70 seconds, and washed with distilled water. Next, an electrode thin film (platinum thin film) having a film thickness of 800 nm was formed by sputtering. Then, by a lift-off method, it was immersed in acetone and washed with ultrasonic waves for 30 minutes, and the resist was peeled off to form a platinum electrode. The deposition conditions for the platinum layer were a vacuum of 10 ⁻⁵ Pa, a substrate temperature of 60 ° C., and an argon gas flow rate of 40 sccm.

Next, a hydrophobic insulating film 112 was formed around the analysis unit 111, and a reference electrode 122 that was a silver / silver chloride electrode was formed.
Specifically, a hydrophobic insulating film is formed around the analysis unit 111 by forming a SiO thin film having a thickness of 500 nm in a region other than the region corresponding to the analysis unit 111 having a substantially circular shape in plan view by sputtering. 112 was created. Next, a silver / silver chloride ink (manufactured by BAS) was applied to the pattern of the reference electrode 122 and sintered at 120 degrees to create a reference electrode 122 which is a silver / silver chloride electrode, thereby creating an electrode substrate. .

<1-2> Creation of porous body for enzyme-immobilized membrane First, as the porous body 13, a membranous silica mesoporous body filled with an assembly of one-dimensional silica nanochannels was prepared.
Specifically, 1.0 g of PEG-PPG copolymer was mixed with 20 mL of ethanol, 2 mL of water, and 100 μL of concentrated hydrochloric acid, and then refluxed at 60 ° C. for 1 hour with stirring. Next, 2.1 g of tetraethyl orthosilicate (TEOS) was added and refluxed at 60 ° C. for 2 hours. Next, 4 mL of this solution was sampled, dropped onto a porous anodized alumina membrane (diameter 47 mm, thickness 60 μm, pore diameter 0.1 μm), suction filtered, and dried at room temperature in a desiccator for 20 minutes. . This was fired in an electric furnace at 500 ° C. for 5 hours to obtain a membranous silica mesoporous material.
As a result of measuring this membranous silica-based mesoporous material using a transmission electron microscope (TEM), silica nano-particles having an average pore diameter of about 8 nm along the alumina pore wall were placed in the pores of the anodized alumina membrane. It was confirmed that the channel was filled.

Next, the produced membranous silica mesoporous material was cut out to produce a porous material 13 for an enzyme-immobilized membrane.
Specifically, a porous body 13 for an enzyme-immobilized film was created by laser processing the created membranous silica-based mesoporous material into a substantially circular shape in plan view having substantially the same size as the analysis unit 111.

<1-3> Preparation of matrix sensor First, an enzyme solution was prepared.
Specifically, 0.5 U formaldehyde dehydrogenase, 0.25 μmol NAD ⁺ , 10 μmol naphthaquinone was dissolved in 1000 μL phosphate buffer (pH 7.4) containing 50% glycerin to obtain an enzyme solution. It was created.
Further, 0.25 μmol of NAD ⁺ , 10 μmol of naphthaquinone was dissolved in 1000 μL of phosphate buffer (pH 7.4) containing 50% glycerin to prepare a blank solution containing no enzyme.

Next, for example, a matrix sensor M was created as shown in FIG.
Specifically, first, a plate-like member (thickness: 200 μm, polyester) having an opening in a region corresponding to the analysis unit 111 and having a substantially rectangular shape in plan view having the same size as the substrate 11 is formed as the partition wall 14. Prepared). And this partition part 14 was adhere | attached on the said produced electrode substrate, and it dried at normal temperature overnight.
Next, each of the prepared porous bodies 13 for enzyme-immobilized membranes was installed in each opening of the partition wall 14.

Next, 20 μL of each of the prepared enzyme solutions was collected with a micropipette, and the sensor part (1, Y) (= sensor part (1,1), (1,2), (1,3), (1, 4), (1, 5)) and sensor part (2, Y) (= sensor part (2, 1), (2, 2), (2, 3), (2, 4), (2, 5) )), Sensor part (3, Y) (= sensor part (3,1), (3,2), (3,3), (3,4), (3,5))) and sensor part ( 4, Y) (= sensor portion (4,1), (4,2), (4,3), (4,4), (4,5)) It was dripped at the porous body 13 for forming a film. That is, in the matrix sensor M created in the present embodiment, the sensor units (1, Y), (2, Y), (3, Y), (4, Y) are the sensor unit 20 (detection sensor unit). is there.
Further, 20 μL each of the prepared blank solution was collected with a micropipette, and the sensor part (5, Y) (= sensor part (5, 1), (5, 2), (5, 3), (5, 5) 4) and (5, 5)) were dropped on the porous body 13 for the enzyme-immobilized membrane installed at the position corresponding to the above. That is, in the matrix sensor M created in the present embodiment, the sensor unit (5, Y) is the difference sensor unit 20C.

Next, as the permeable membrane 15, a gas permeable membrane (permeability coefficient: 1.44 cc · cm / (cm ² · min · kPa) formed in a substantially rectangular shape in plan view having substantially the same size as the substrate 11, thickness: 100 μm, Gore-Tech Prepared). The permeable membrane 15 was bonded onto the partition wall portion 14.

Next, as the adjustment permeable membrane 19 for adjusting the detection concentration range of the sensor unit 20, four types of gas permeable membranes having different permeability coefficients (permeability coefficient: 2.40 cc · cm / (cm ² · min · kPa) 1.11 cc · cm / (cm ² · min · kPa), 0.72 cc · cm / (cm ² · min · kPa), 0.13 cc · cm / (cm ² · min · kPa), thickness: 100 μm, Prepared by Gore-Tex). Then, each of these adjustment permeable membranes 19 was processed into a size capable of covering the analysis unit 111. Next, an adjustment permeable membrane 19 having a transmission coefficient of 2.40 cc · cm / (cm ² · min · kPa) is installed on the permeable membrane 15 at a position corresponding to the sensor portion (1, 2). , 3) is provided with an adjustment permeable membrane 19 having a transmission coefficient of 1.11 cc · cm / (cm ² · min · kPa) at a position corresponding to the sensor portion (1, 4). An adjustment permeable membrane 19 of 0.72 cc · cm / (cm ² · min · kPa) is installed, and the transmission coefficient is 0.13 cc · cm / (cm ² · min at a position corresponding to the sensor portion (1, 5). A permeable membrane 19 for adjustment of kPa) was installed and adhered on the permeable membrane 15.

  Next, as the spacer 16, a plate-like member (thickness: 200 μm, made of polyester) having an opening in a region corresponding to the analysis unit 111 and formed in a substantially rectangular shape in plan view having substantially the same size as the substrate 11 was prepared. And this spacer 16 was adhere | attached on the permeable membrane 15 to which the adjustment permeable membrane 19 was adhere | attached.

  Next, a gas-impermeable film-like member (thickness: 200 μm, made of Teflon) formed in a substantially rectangular shape in plan view having substantially the same size as the substrate 11 was prepared as the sealing member 17. Then, the sealing member 17 was bonded onto the spacer 16.

  Next, the cover member 18 is formed in a substantially rectangular shape in plan view having substantially the same size as that of the substrate 11 and having an opening having a substantially rectangular shape in plan view having substantially the same size as the analysis unit 111 in a region corresponding to the analysis unit 111. A plate-like member (thickness: 200 μm, made of polyester) was prepared. And the matrix sensor M was created by adhere | attaching this cover member 18 on the sealing member 17. FIG.

<2> Evaluation of Matrix Sensor and Sensor System Next, the matrix sensor M created above was used to evaluate the sensor system of the present invention and the matrix sensor included in the sensor system of the present invention.

First, the sensor system of the present invention and the measuring device N for evaluating the matrix sensor provided in the sensor system of the present invention will be described.
For example, as shown in FIG. 28, the measuring device N is generated by a seal removal unit 30, a detection data acquisition unit 40C, a formaldehyde gas generator N1 that generates formaldehyde gas of a specified concentration, and a formaldehyde gas generator N1. Teflon tube N2 for supplying the formed formaldehyde gas to the sensor unit 20 provided in the matrix sensor M and the supply layer 23 of the differential sensor unit 20C, and the like.

For example, as shown in FIG. 28, the tube N2 is provided in the measuring device N such that the tip of the tube N2 is fixed to the side surface of the needle 31 above the tip of the needle 31.
Thereby, after removing the sealing member 17 corresponding to one sensor unit 20 or one difference sensor unit 20C to be used with the needle 31, the one sensor unit 20 or one difference sensor unit 20C to be used is removed. A sample (formaldehyde gas generated by the formaldehyde gas generator M1) can be sprayed on the upper surface.

And the matrix sensor with which the sensor system of this invention and the sensor system of this invention were equipped was evaluated using the measuring apparatus N demonstrated above.
Specifically, the created matrix sensor M (matrix sensor M immediately after creation) was arranged below the needle 31 of the seal removal unit 30 and connected to the detection data acquisition unit 40C. Next, one of the 20 sensor units 20 included in the matrix sensor M is used, or one of the 5 difference sensor units 20C included in the matrix sensor M is used. For the part 20C, the sealing member 17 is removed, and a voltage of +650 mV is applied to the working electrode 121 with respect to the reference electrode 122 at room temperature (25 ° C.), and formaldehyde gas with a specified concentration is supplied to the supply layer 23. Measurement was carried out by measuring the current by amperometry.

<2-1> Response of sensor unit Using the sensor unit (1, 1), an experiment was performed to observe the response of the sensor unit 20 when formaldehyde gas was supplied.
Specifically, a voltage was applied to the working electrode 121 to generate and supply formaldehyde gas having a formaldehyde concentration of 20 ppb, and the response current was measured. The formaldehyde gas was supplied after the response current (charging current) was sufficiently stabilized after the voltage was applied to the working electrode 121 (specifically, 7 minutes after the voltage was applied to the working electrode 121). . The result is shown in FIG.

  In FIG. 29, the horizontal axis represents time (min) after voltage application, and the vertical axis represents response current (nA).

From the result of FIG. 29, it was found that the charging current flows immediately after the voltage is applied to the working electrode 121 of the sensor unit (1, 1), and the charging current settles in about 5 minutes after the voltage is applied.
And it turned out that a response electric current increases immediately after supplying formaldehyde gas to the detection layer 23 of a sensor part (1,1), and settles in an equilibrium state in about 2 minutes after introducing formaldehyde gas. Thereby, it turned out that a detection target substance can be detected by using the one sensor part 20 which the matrix sensor with which the sensor system (sensor system of the 1st-4th embodiment) of the present invention is provided.

<2-2> Demonstration of the effect of providing a plurality of types of sensor units with different detection density ranges Five types of sensor units 20 (sensor units (1, 1), (1, 2), ( 1, 3), (1, 4), and (1, 5)) were used to conduct experiments to demonstrate the effects of providing a plurality of types of sensor units 20 having different detection density ranges.
Specifically, a calibration curve was created by applying a voltage to the working electrode 121, sequentially generating and supplying formaldehyde gases having different formaldehyde concentrations, and measuring the response current. The concentration of the formaldehyde gas supplied was 1 ppb, 10 ppb, 20 ppb, 100 ppb, 200 ppb, 1000 ppb, 2000 ppb, 10,000 ppb, and 100000 ppb. The result is shown in FIG.

  In FIG. 30, the horizontal axis indicates formaldehyde concentration (ppb), the vertical axis indicates response current (nA), and the rhombus plot (◇) indicates the response current value in the equilibrium state of the sensor unit (1, 1), a square plot ( The response current value in the equilibrium state of the sensor unit (1, 2) in □), the response current value in the equilibrium state of the sensor unit (1, 3) in the triangle plot (△), the sensor unit ( The response current value in the equilibrium state of (1, 4) and the response current value in the equilibrium state of the sensor unit (1, 5) are shown by an inverted triangular plot (▽).

According to FIG. 30, the transmittance (detection target) of the transmissive layer 22 is the most among the sensor units (1, 1), (1, 2), (1, 3), (1, 4), (1, 5). It was found that the detection concentration range of the sensor unit (1, 1) having a high transmittance when a substance passes through the transmission layer 22 is 1 ppb to 100 ppb.
In addition, the sensor layer (1,1), (1,2), (1,3), (1,4), (1,5) is followed by the transmissive layer 22 after the sensor unit (1,1). It was found that the detection density range of the sensor part (1, 2) having a high transmittance is 10 ppb to 200 ppb.
In addition, the sensor layer (1,1), (1,2), (1,3), (1,4), (1,5) is followed by the transmissive layer 22 after the sensor unit (1,2). It was found that the detection density range of the sensor part (1, 3) having a high transmittance is 20 ppb to 1000 ppb.
In addition, the sensor layer (1,1), (1,2), (1,3), (1,4), (1,5) is followed by the transmissive layer 22 after the sensor portion (1,3). It was found that the detection density range of the sensor part (1, 4) having a high transmittance was 100 ppb to 2000 ppb.
Further, among the sensor parts (1, 1), (1, 2), (1, 3), (1, 4), (1, 5), the sensor part (1, The detected concentration range of 5) was found to be 200 ppb to 10000 ppb.

  From the results of FIG. 30, the sensor portions (1, 1), (1, 2), (1, 3), (1, 4), (1, 5) have a narrow detection density range, but are detected by each. It was found that the concentration range was different. Accordingly, the matrix sensor included in the sensor system of the present invention (the sensor system according to the second embodiment) includes five types of sensor units 20 (for example, sensor units (1, 1), (1, 2), (1 , 3), (1, 4), (1, 5)) or a plurality of types of sensor units 20 (for example, sensor units (1, 1), (1, It was found that by using (3) and (1,5)) at the same time, it can be used as a sensor having a wide detection concentration range. In addition, the detection target substance can be detected by an appropriate type of sensor unit 20 (sensor unit 20 having an optimal detection concentration range) among the plurality of types of sensor units 20 used, and the concentration of the detection target substance can be calculated. I understood.

Here, since the concentration of the detection concentration range in the sample is often unknown, a sensor having a wide detection concentration range is desired. However, in the conventional sensor, the wider the detection concentration range, the wider the detection concentration range. When the detection density range is partially viewed, the accuracy is poor and the detection error tends to increase.
On the other hand, in the sensor system of the present invention (the sensor system of the second embodiment), the matrix sensor includes a plurality of types of sensor units 20 having different detection density ranges. By simultaneously using the matrix sensor, the matrix sensor can be used as a sensor having a wide detection density range, and the detection density range of each sensor unit 20 is narrow, so that a detection error compared with a conventional sensor having a wide detection density range. It is preferable that the concentration of the detection target substance is calculated based on the detection data obtained by the sensor unit 20 having a small and optimal detection concentration range, whereby a more accurate concentration can be calculated.

<2-3> Demonstration of effect by calculating average value of detection data 15 sensor units 20 (sensor units (2, Y), (3, Y), (4, Y)) having the same detection concentration range ) Was used to demonstrate the effect of determining the average value of the detection data (response current value).
Specifically, a voltage was applied to the working electrode 121 to generate and supply formaldehyde gas having a formaldehyde concentration of 20 ppb, and the response current was measured. This series of processing was repeated 15 times. The result is shown in FIG.

  In FIG. 31, the horizontal axis indicates the number of measurements (N), the vertical axis indicates the response current (nA), and the triangular plot (Δ) indicates that one sensor unit 20 (sensor unit (2, 1)) is in an equilibrium state. Of the response current values of the 15 sensor parts 20 (sensor parts (2, Y), (3, Y), (4, Y)) in an equilibrium state in a circle plot (◯). Show.

  From the results of FIG. 31, even when the response current measurement was repeated 15 times, the response current value did not decrease. Thereby, it was found that the matrix sensor included in the sensor system of the present invention (the sensor systems of the first to fourth embodiments) can be detected with good reproducibility.

  In addition, from the result of FIG. 31, compared with the variation in the response current value of only one sensor unit 20 (sensor unit (2, 1)), 15 sensor units 20 (sensor unit (2, Y), It was found that the variation in the average value of the response current values of (3, Y) and (4, Y) was smaller. Further, when the standard deviation is calculated from the result of FIG. 31, the standard deviation of one sensor unit 20 is 2.80, and the average standard deviation of 15 sensor units 20 is 0.73, and 0.73 / 2 Since .80≈1 / √15, the average standard deviation of the 15 sensor units 20 is about “1 / √n (n: the number of sensor units 20)” of the standard deviation of one sensor unit 20. I found out that Thereby, in the sensor system of the present invention (the sensor system of the third embodiment), a process for obtaining an average value is performed using detection data from the plurality of sensor units 20, and based on the average value, the detection target substance is detected. It was found that a more accurate concentration can be calculated by calculating the concentration.

<2-4> Demonstration of effect by taking difference of detection data Using sensor unit 20 (sensor unit (1, 1)) and difference sensor unit 20C (sensor unit (5, 1)) An experiment was conducted to verify the effect of taking the difference of the detection data.
Specifically, a voltage was applied to the working electrode 121 to generate and supply formaldehyde gas having a formaldehyde concentration of 10 ppb, and the response current was measured. The formaldehyde gas was supplied before the response current (charging current) was stabilized after the voltage was applied to the working electrode 121 (specifically, 90 seconds after the voltage was applied to the working electrode 121). The result is shown in FIG.

  In FIG. 32, the horizontal axis shows the time (min) after the voltage is applied, the vertical axis shows the response current (nA), the broken line shows the change over time of the response current value of the sensor unit (1, 1), and the alternate long and short dash line Time-dependent change in response current value of sensor unit (5, 1), time difference of solid line (difference obtained by subtracting response current value of sensor unit (5, 1) from response current value of sensor unit (1, 1)) Showing change.

  From the result of FIG. 32, in the sensor unit 20 (sensor unit (1, 1)), the response current increases immediately after the formaldehyde gas is supplied, whereas the difference sensor unit 20C (sensor unit (5, 1)). Thus, it was found that the response current does not increase even when formaldehyde gas is supplied. This is because the detection layer 21 of the sensor unit 20 contains the enzyme E using formaldehyde as a substrate, whereas the detection layer 21 of the differential sensor unit 20C does not contain the enzyme E.

  Further, from the result of the sensor unit 20 (sensor unit (1, 1)) in FIG. 32, since the formaldehyde gas was supplied before the charging current was stabilized, a drift corresponding to the decrease in the charging current was observed after the formaldehyde gas was supplied. It was found that the equilibrium state was not reached even after 3 minutes had passed since the formaldehyde gas was supplied. On the other hand, from the result of the difference in FIG. 32, it was found that when the difference was taken, this drift was eliminated and the equilibrium state was settled in about one minute after the formaldehyde gas was supplied. Thereby, in the sensor system of the present invention (the sensor system of the fourth embodiment), the difference between the detection data by the sensor unit 20 and the detection data by the difference sensor unit 20C is taken, and detection is performed based on the difference. It was found that by calculating the concentration of the target substance, a stable equilibrium state can be obtained immediately without adjusting the zero point, and the detection time can be shortened.

  Here, when an electron carrier such as naphthoquinone is contained in the detection layer 21 as in the matrix sensor M, depending on the type of the electron carrier, a considerable time is required until the drift converges (background becomes stable). There is. In such a case, in particular, when the difference is taken as in the sensor system of the present invention (the sensor system of the fourth embodiment), the sample is supplied before the background stabilizes (before the charging current settles). Therefore, the detection time and the total measurement time can be shortened, which is preferable.

  The embodiment of the present invention should be considered that the embodiment disclosed this time is illustrative and not restrictive in all respects. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

<Modification 1>
In the first embodiment, the counter electrode 123 of the electrode 12 is not limited to those formed individually corresponding to the sensor units 20 as shown in FIGS. 6 and 8, for example, FIG. It may be integrally formed like the counter electrode 123D of the electrode 12D shown in FIG. Here, also in FIG. 33, as in FIG. 6, the portion filled with the dot pattern is the electrode 12D (the working electrode 121D, the reference electrode 122D, and the counter electrode 123D).
The same applies to the second to fourth embodiments.

Specifically, for example, as shown in FIGS. 33 and 34, the working electrode 121D of each electrode 12D is formed inside the analysis unit 111 on the upper surface of the substrate 11 and formed individually corresponding to each sensor unit 20. The reference electrode 122D of each electrode 12D is formed inside the analysis unit 111 on the upper surface of the substrate 11 and is formed individually corresponding to each sensor unit 20, and the counter electrode 123D of each electrode 12D is It is integrally formed inside the analysis unit 111 and outside the analysis unit 111 on the upper surface of the substrate 11. A portion of the counter electrode 123D formed inside the analysis unit functions as a counter electrode corresponding to each sensor unit 20.
In this case, the electrode 12D (the working electrode 121D, the reference electrode 122D, and the counter electrode 123D) is electrically connected to the wiring pattern on the back surface of the substrate 11 through a via hole by a known method.

  According to the modified example 1, since the counter electrode of each sensor unit 20 is integrally configured, for example, as illustrated in FIG. 34, the counter electrode of each sensor unit 20 is configured individually (FIG. 8). Compared to the above, there is no need to draw out the wiring individually, and the wiring between the matrix sensor 10 and the detection data acquisition unit 40 can be simplified, which can be simplified and integrated as a sensor chip. Can be miniaturized.

<Modification 2>
In the first embodiment, the detection target substance concentration measurement process is performed as a single detection target when the user instructs to measure the concentration of the detection target substance in the sample as shown in FIG. What measures the concentration of a substance (that is, when the sensor unit 20 is designated by the user instructed to detect the substance to be detected, voltage application to the working electrode 121 is started, and the response current from the working electrode 121 is When the voltage reaches equilibrium, the application of the voltage is not limited to this. For example, as shown in FIG. 35, the concentration of the detection target substance may be continuously measured.
The same applies to the second to fourth embodiments.

<Detection target substance concentration measurement process>
Another example of the processing related to the measurement of the detection target substance concentration by the sensor system 1 will be described with reference to the flowchart of FIG.

First, for example, when the user instructs to start the measurement of the concentration of the detection target substance in the sample by operating the operation unit 70, the CPU 51 uses the matrix sensor 10 incorporated in the sensor system 1 unused. It is determined whether or not the sensor is a matrix sensor (that is, whether or not all the sensor units 20 included in the matrix sensor 10 in the sensor system 1 are sealed with the sealing member 17) (step S51).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1. Based on the above, it is determined whether or not the matrix sensor 10 is an unused matrix sensor.

  If it is determined in step S51 that the matrix sensor 10 incorporated in the sensor system 1 is an unused matrix sensor (step S51; Yes), the CPU 51 proceeds to the process of step S55.

On the other hand, if it is determined in step S51 that the matrix sensor 10 incorporated in the sensor system 1 is not an unused matrix sensor (step S51; No), the CPU 51 executes the deterioration determination program 531 and performs the previous detection. It is determined whether the used sensor unit 20 (the sensor unit 20 from which the sealing member 17 has been removed) is deteriorated (step S52).
Specifically, the CPU 51 uses, for example, the sensor used for the previous detection based on “usage history (for example, date and time when the sealing member 17 was removed)” of the matrix sensor 10 incorporated in the sensor system 1. It is determined whether the unit 20 has deteriorated.

  If it is determined in step S52 that the sensor unit 20 used for the previous detection has not deteriorated (step S52; No), the CPU 51 executes the sensor unit designation program 532 and uses the sensor unit used for the previous detection. 20 is designated (step S53), and the process proceeds to step S57.

On the other hand, if it is determined in step S52 that the sensor unit 20 used for the previous detection has deteriorated (step S52; Yes), the CPU 51 determines the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1. It is determined whether or not there is a sensor unit 20 from which the sealing member 17 has not been removed (step S54).
Specifically, the CPU 51, for example, “use history (for example, sensor unit identification information for identifying the sensor unit 20 from which the sealing member 17 has been removed)” of the matrix sensor 10 incorporated in the sensor system 1. Based on the above, it is determined whether or not there is a sensor unit 20 from which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10.

If it is determined in step S54 that there is no sensor unit 20 in which the sealing member 17 is not removed in the sensor unit 20 included in the matrix sensor 10 incorporated in the sensor system 1 (step S54; No), the CPU 51 This process ends.
Then, for example, the CPU 51 causes the display unit 80 to display a predetermined display indicating that the matrix sensor 10 incorporated in the sensor system 1 is to be replaced. Prompt to replace 10.

  On the other hand, if it is determined in step S54 that there is a sensor unit 20 in which the sealing member 17 is not removed among the sensor units 20 included in the matrix sensor 10 incorporated in the sensor system 1 (step S54; Yes), the CPU 51. Executes the sensor part designation program 532 and designates the sensor part 20 (the sensor part 20 from which the sealing member 17 has not been removed) according to the preset order of the sensor parts 20 to be used (step S55).

  Next, the CPU 51 executes the sealing removal control program 533 to cause the sealing removal unit 30 to remove the sealing member 17 corresponding to the designated sensor unit 20 (step S56).

Next, the CPU 51 executes the detection data acquisition control program 534 to cause the detection data acquisition unit 40 to acquire detection data from the designated sensor unit 20 (step S57).
Specifically, for example, when voltage application to the working electrode 121 is started and a sample is forcibly supplied to the supply layer 23, sample supply to the supply layer 23 is started. This series of processing is performed on the designated sensor unit 20.

Next, the CPU 51 executes the concentration calculation program 535 and calculates the concentration of the detection target substance based on the acquired detection data (step S58).
Then, for example, the CPU 51 sequentially stores the detection data acquired in step S57 and the concentration of the detection target substance calculated in step S58 in the memory unit 60 or sequentially displays on the display unit 80.

Next, the CPU 51 executes the deterioration determination program 531 to determine whether or not the sensor unit 20 in use (the sensor unit 20 from which the sealing member 17 has been removed) has deteriorated (step S59).
Specifically, for example, the CPU 51 determines whether the sensor unit 20 in use is based on the “use history (for example, date and time when the sealing member 17 is removed)” of the matrix sensor 10 incorporated in the sensor system 1. Judge whether it has deteriorated or not.

  If it is determined in step S59 that the sensor unit 20 being used has not deteriorated (step S59; No), the CPU 51 repeats the processes in and after step S57.

On the other hand, if it is determined in step S59 that the sensor unit 20 in use has deteriorated (step S59; Yes), the CPU 51 repeats the processes in and after step S54.
Of course, if it is instructed to end the measurement of the concentration of the detection target substance by the operation of the operation unit 70 by the user during step S51 to step S59, the CPU 51 ends this processing at that time.

In the first embodiment, the arrangement of the sensor units 20 is not limited to a 5 × 5 two-dimensional matrix, and may be arbitrary as long as the matrix sensor 10 includes a plurality of sensor units 20. is there. That is, for example, the sensor unit 20 may be arranged in an X × Y two-dimensional matrix (X and Y are natural numbers, and X = Y or X ≠ Y). Good, X × Y × Z three-dimensional matrix (X, Y, and Z are natural numbers, X ≠ Y, X ≠ Y, Y = Z, Y ≠ Z Z, Z = X, or Z ≠ X.). In the case of an X × Y × Z three-dimensional matrix, the sensor matrix 10 according to the embodiment can be stacked. Of course, it is possible to create using a microfabrication technique such as MEMS and a semiconductor technique such as photolithography.
The same applies to the second to fourth embodiments.

Further, in the first embodiment, the plurality of sensor units 20 included in the matrix sensor 10 is not limited to an integrated unit formed on the same substrate, and the matrix sensor 10 includes the plurality of sensor units 20. If they are, they may be separate bodies.
The same applies to the second to fourth embodiments.

Moreover, in 1st Embodiment, the sealing member 17 which seals each sensor part 20 is not restricted to what was formed integrally, The corresponding sensor part 20 can be interrupted | blocked from the outside. If it is, it is arbitrary, for example, you may form separately corresponding to each sensor part 20, respectively.
The permeable membrane 15 is not limited to one integrally formed, and may be formed individually corresponding to each sensor unit 20, for example.
The same applies to the second to fourth embodiments.

In the first embodiment, the method of removing the sealing member 17 is not limited to mechanical removal using the needle 31, and the sealing member 17 corresponding to the designated sensor unit 20 is not used. As long as it can be removed, for example, it may be mechanically removed by inserting something other than the needle 31 into the sealing member 17, or a predetermined sealing member heating mechanism The sealing member 17 is thermally or electrically removed by baking or melting the sealing member 17 by using or by incorporating a resistor in the vicinity of the sealing member 17 or the sealing member 17 and applying a voltage in advance. Alternatively, it may be electrically removed by moving (sliding etc.) the sealing member 17 using a predetermined sealing member moving mechanism, or using a laser or the like, Sealing member with that pressure It may be removed by or burning off or break the 7. In addition, when removing the sealing member 17 by moving, it is preferable to form the sealing member 17 corresponding to each sensor part 20 individually.
The same applies to the second to fourth embodiments.

In the first embodiment, the method of determining the deterioration of the sensor unit 20 is not limited to the method of determining using the effective usage period of the sensor unit 20, and a sealing member that seals the sensor unit 20 It is optional as long as it can be determined that the sensor unit 20 has deteriorated when the degree of reduction in sensitivity after the removal of 17 exceeds a preset “allowable sensitivity range”. Alternatively, a detection target substance in a standard sample (a sample with a constant concentration of the detection target substance) may be detected, and determination may be made based on sensitivity (detection data (response current value)) at that time.
Also, before measuring the concentration of the detection target substance, the detection target substance in the standard sample (sample with a constant concentration of detection target substance) is detected, and based on the sensitivity (detection data (response current value)) at that time Thus, calibration may be performed. In this case, even if the sensor unit 20 is deteriorated or the like and the sensitivity of the sensor unit 20 is lowered, the sensor unit 20 is used for detection until the sensor unit 20 cannot detect the detection target substance. Since the concentration of the target substance can be measured, the lifetime of the matrix sensor of the present invention can be extended, and the reliability of the matrix sensor of the present invention as a sensor can be improved. Here, the state in which the sensor unit 20 cannot detect the detection target substance is, for example, a state in which the response current does not increase even if the detection target substance is supplied.
The same applies to the second to fourth embodiments.

Furthermore, in all the embodiments, when the sensor unit 20 is, for example, a metal oxide semiconductor sensor or a solid electrolyte sensor, a plurality of sensor units 20 of the same type are simultaneously opened and used. If the sensor detects a reference gas present at a constant concentration in the environment, it can be determined that the reference gas sensor has deteriorated when the response output of the reference gas sensor falls below a certain value. The reference gas may be various gases including carbon monoxide and hydrogen sulfide. The applied voltage between the working electrode 121 and the reference electrode 122 may be set according to the gas type. Alternatively, in the case where the sensor unit 20 is a sensor used at a high temperature, a temperature sensor can be provided at the same time, and deterioration can be determined by calculation from relational data on temperature and life stored in advance in a memory.
Further, by operating the plurality of sensor units 20 at the same time according to the third embodiment without judging the first deterioration, and excluding those whose values are extremely deviated from the average as “failed sensor units” It is also possible to detect deterioration (the sensor unit 20 is not used thereafter).

Further, in the first embodiment, the porous body 13 having a vertical hole structure to which the enzyme E is fixed may be disposed at least on the upper surface of the working electrode 121. In particular, pores 13a penetrating in a substantially vertical direction with respect to the substrate 11 on the electrode 12, such as a method such as metal plating using anodization or a surfactant, or mesoporous silica whose direction is controlled by an external field. Organic / inorganic structures having the above may be directly formed. For example, anodized alumina that penetrates the substrate 11 in a substantially vertical direction can be formed by anodic oxidation of alumina, and a bundle of silica channels having a smaller nanopore diameter is formed in the pores. You can also.
Furthermore, in the first embodiment, the enzyme E may not be contained in the detection layer 21 in a state of being fixed to the porous body 13. For example, a carrier other than the porous body 13 (for example, a carbon nanotube or silica) In the detection layer 21 in a state of being fixed to a nanotube or the like, or in the detection layer 21 in a state of being directly fixed to the electrode 12, or in an electrolyte solution that fills the detection layer 21. You may contain in the detection layer 21 in the melt | dissolved state (state of a free enzyme).
The same applies to the second to fourth embodiments.

In the first embodiment, the electrolytic solution may not be contained in the detection layer 21 in advance, and may be introduced into the detection layer 21 after the sealing member 17 is removed, for example. In this case, enzyme E, electron carrier, coenzyme, etc. are previously contained in the detection layer 21 in a dry state, and an ink jet head, a dispenser, a syringe, a pipette, etc. are used immediately after the sealing member 17 is removed. It is better to supply electrolyte.
Furthermore, in the first embodiment, the enzyme E may not be contained in the detection layer 21 in advance, and may be introduced into the detection layer 21 after the sealing member 17 is removed, for example.
In the case where neither the electrolyte solution nor the enzyme E is contained in the detection layer 21 in advance, the sensor unit 20 may not be sealed with the sealing member 17. In this case, the introduction of the electrolyte solution or the enzyme E into the detection layer 21 can be performed by directly using a microfabrication technology such as MEMS or a semiconductor technology such as photolithography to directly place the microchannel or micropump on the chip. Alternatively, they can be formed separately and introduced using these.
The same applies to the second to fourth embodiments.

In the first embodiment, the electrode 12 is not limited to a tripolar structure (tripolar structure of the working electrode 121, the reference electrode 122, and the counter electrode 123). For example, the electrode 12 is not provided with the reference electrode 122. The structure (bipolar structure of the working electrode 121 and the counter electrode 123) may be used.
The same applies to the second to fourth embodiments.

In the first embodiment, the potentiostat circuit 42 included in the detection data acquisition unit 40 is not limited to a single-channel potentiostat circuit, and may be a multi-channel potentiostat circuit.
The same applies to the second to fourth embodiments.

Further, in the first embodiment, the sensor units 20 and 20 (detection layers 21 and 21) may be separated from each other only by the partition wall 14 without providing the hydrophobic insulating film 112 on the upper surface of the substrate 11.
The same applies to the second to fourth embodiments.

In the first embodiment, each of the sensor units 20 includes a temperature sensor and a temperature adjustment element (for example, a heater film or a Peltier element), and is configured so that the temperature control of the designated sensor unit 20 can be performed. Also good. In this case, since temperature management at the time of detection can be performed, the detection accuracy can be improved. The same applies to the second to fourth embodiments.

In the first embodiment, a part of the electrode 12 (for example, the reference electrode 122 and / or the counter electrode 123) is not the upper surface of the substrate 11 but the lower surface of the transmissive film 15 (the substrate 11 of the transmissive film 15 and It may be formed by sputtering or the like on the opposite surface.
The same applies to the second to fourth embodiments.

In the first embodiment, when the sample is a gas sample, an electrolyte solution in which the enzyme E is dissolved is held on a carrier (glass fiber or the like), and the carrier is supported on the detection layer 21 (on the working electrode 121). The working electrode 121 may be formed on the upper surface of the substrate 11, and the reference electrode 122 and the counter electrode 123 may be formed on the carrier. In this case, the porous body 13 and the permeable membrane 15 are not necessarily provided.
The same applies to the second to fourth embodiments.

Moreover, in 1st Embodiment, the structure of the sensor part 20 can be suitably changed according to the kind of detection target substance.
Specifically, the biological material contained in the detection layer 21 is not limited to the enzyme E, and may be any biological material that selectively reacts with the detection target material. Specifically, as the biological substance that selectively reacts with the detection target substance, for example, a biocatalyst such as enzyme E, an antigen, an antibody, a lipid, a cell, a fungus, DNA, a sugar chain, or the like can be used.
Furthermore, the reactive substance contained in the detection layer 21 is not limited to a biological substance, and any substance can be used as long as it selectively reacts with the detection target substance. Specifically, as the substance that selectively reacts with the detection target substance, for example, the biological substance, metal catalyst, organic catalyst, inorganic catalyst, various polymers, polymer complex, polyion complex, light-absorbing substance, fluorescent substance, and the like are used. be able to. In particular, as the metal catalyst, metals such as platinum, palladium, niobium, iridium, tantalum, nickel, iron, cobalt, beryllium, tungsten, rhodium, zirconium, copper, molybdenum, titanium, ruthenium, thallium, or alloys thereof, , Tin oxide SnO ₂ , zinc oxide ZnO, ferric oxide Fe ₂ O ₃ , triiron tetroxide Fe ₃ O ₄ , alumina Al ₂ O ₃ , magnesium oxide MgO, titanium oxide TiO ₂ , molybdenum dioxide MnO ₂ , three Any oxide such as molybdenum oxide MnO ₃ , nickel oxide Ni ₂ O ₃ , chromium oxide Cr ₂ O _3, porous metal oxide, or a composite oxide thereof can be used. The type of reactant contained in the detection layer 21 may be one type or a plurality of types.
Note that the electrolyte solution that fills the detection layer 21 can be changed as appropriate according to the type of reactant contained in the detection layer 21. Specifically, when the reactant contained in the detection layer 21 is a metal catalyst (metal oxide or the like), depending on the detection method of the sensor, such as a metal oxide semiconductor sensor, an electrolytic solution should not be added. . In some cases, the detection layer 21 and the supply layer 23 (a portion between the permeable membrane 15 and the sealing member 17) may be filled with a gas such as nitrogen.

In addition, the detection element is not limited to the electrode 12, and a predetermined change (for example, substance change, color change, endothermic change) associated with the reaction between the detection target substance and the reaction substance that selectively reacts with the detection target substance. Any change is possible as long as it can detect a heat generation change, a mass change, a resistance change, a capacitance change, etc. Specifically, as the detection element, for example, an electrode (hydrogen peroxide electrode, dissolved oxygen electrode, conductivity electrode, ion electrode, redox potential electrode, comb electrode, parallel plate electrode, etc.), semiconductor, light receiving element A thermal element, a piezoelectric element, a thermistor, a cantilever, an ion-sensitive field effect transistor (ISFET), a crystal resonator (QCM), a surface acoustic wave (SAW) device, or the like can be used.
Furthermore, the sensor unit 20 may not include a detection element. As a detection method in this case, for example, the detection target substance is detected by detecting chemiluminescence, absorption, fluorescence, plasmon phenomenon, etc. from the outside of the sensor unit 20 (matrix sensor 10) by an optical detection method or the like. Or the like can be used.

  The sensor unit 20 is not limited to one that functions as an electrode-type enzyme sensor, and may be any sensor that can detect a detection target substance. Examples of sensors that can detect a detection target substance include an electrochemical sensor, a solid electrolyte sensor, a catalytic combustion sensor, a metal oxide semiconductor sensor, a field effect transistor sensor, a crystal oscillator sensor, an electrode sensor, Examples include an ion sensitive field effect transistor (ISFET) type sensor, an optical sensor, and the like.

  Here, the electrochemical sensor is, for example, a sensor that detects a detection target substance by detecting a current generated in response to a reaction of the detection target substance dissolved in the electrolytic solution.

  The solid electrolyte sensor is a sensor that detects a detection target substance by detecting an electromotive force generated due to a concentration difference (difference in concentration of the detection target substance) on both sides separated by a fixed electrolyte, for example. .

  In addition, the catalytic combustion type sensor, for example, when a platinum wire coated with a noble metal (such as platinum or palladium) is heated to 300 ° C. to 400 ° C., the detection target substance that contacts the noble metal coated on the platinum wire is Although it burns by the catalytic action of a noble metal, it is a sensor that detects a detection target substance by detecting a resistance change accompanying a temperature change caused by this combustion.

  In the metal oxide semiconductor sensor, for example, oxygen adsorbed on the n-type semiconductor surface in the atmosphere is removed from the n-type semiconductor surface by the interaction between the n-type semiconductor and the detection target substance. It is a sensor that detects a substance to be detected by detecting a change in resistance of the n-type semiconductor accompanying this removal.

  The field effect transistor type sensor has a sensitive film (sensitive film that selectively reacts with the detection target substance) coated on the gate part of the field effect transistor (FET), for example, and the sensitive film of the detection target substance. It is a sensor that detects a detection target substance by detecting a change in drain current accompanying diffusion into the inside.

In addition, the quartz resonator type sensor detects, for example, a change in weight associated with the detection target material adhering to or detaching from the surface of the crystal resonator (QCM) as a frequency change of the crystal resonator, thereby detecting the detection target material. It is a sensor which detects. In addition, as a quartz crystal sensor, a sensitive film (an organic sensitive film or an inorganic sensitive film) that selectively reacts with a detection target substance or a biological material that selectively reacts with a detection target substance ( A carrier on which a biological substance is immobilized may also be known).
Similarly, the cantilever type sensor detects, for example, a change in surface stress caused by the interaction between the detection target substance and the cantilever surface by the deflection amount (displacement amount) of the cantilever. The cantilever detects the detection target substance. The sensor detects the detection target substance by measuring the amount of displacement of the cantilever before and after contact with.

In addition, an electrode type sensor is a target to be detected by, for example, applying a voltage to an electrode such as metal or carbon and measuring a diffusion current generated by electrochemically oxidizing or reducing the target substance to be detected. It is a sensor that detects a substance. As an electrode type sensor, for example, an electrode (hydrogen peroxide electrode, dissolved oxygen electrode, electrical conductivity electrode, ion electrode, oxidation-reduction potential electrode, etc.) and a sensitive film (organic sensitive film) that selectively reacts with a detection target substance. And a combination of a biological substance that selectively reacts with a detection target substance (or a carrier on which the biological substance is fixed), and the like are known. Specifically, for example, an electrode type that detects harmful substances (substances to be detected) by detecting the respiratory activity of microorganisms from the oxygen consumption of the microorganism fixed membrane by combining a dissolved oxygen electrode and a microorganism fixed membrane. Biosensors are known.
Here, among electrode type sensors, a combination of an electrode and an enzyme (biological substance) corresponds to the sensor unit 20 (electrode type enzyme sensor) of the embodiment.

  The ISFET sensor is, for example, a sensor in which a field effect transistor or a noble metal electrode is placed on a semiconductor or an insulating substrate, and an ion sensitive film is placed on the field effect transistor or a noble metal electrode. It can also be used as a sensor, and further a biosensor by immobilizing a biological substance (or a carrier on which the biological substance is immobilized) that selectively reacts with the detection target substance on the ion-sensitive membrane. Can also be used. Specifically, for example, the concentration of hydrogen ions generated when a specific organic substance (substance to be detected) present in a solution such as whole blood or a leachate leached from the surface of a living body undergoes a chemical reaction by the catalytic action of an enzyme or An ISFET type biosensor that detects a specific organic substance by detecting a change in electron concentration is known.

  The optical sensor captures the detection target substance by, for example, an identification element (such as a biological substance that selectively reacts with the detection target substance) and uses chemiluminescence, absorption, fluorescence, surface plasmon phenomenon, etc. It is a sensor that detects a detection target substance by detecting a change.

Here, when the sensor unit 20 functions as a catalytic combustion type sensor, a metal oxide semiconductor type sensor, or the like, it is not always necessary to seal the sensor unit 20 with the sealing member 17, but substances in the air ( Since the sensitivity decreases if the gas is adsorbed, it is preferable to seal with the sealing member 17.
In addition, when the sensor unit 20 functions as a catalytic combustion type sensor, a metal oxide semiconductor type sensor, or the like, it is not always necessary to include the partition wall part 14, but it is possible to prevent electrical crosstalk and to diffuse heat around the use part. From the standpoint of prevention, it is preferable to provide the partition wall 14.
In addition, since a catalyst combustion type sensor, a metal oxide semiconductor type sensor, etc. use an element at high temperature, generation | occurrence | production of the electrode deterioration by a use or peeling of a catalyst, a crack, etc. will become remarkable if it makes it small. Therefore, by using these as the matrix sensor of the present invention, the lifetime as a sensor can be greatly increased.

Then, by appropriately changing the configuration of the sensor unit 20 as described above, the matrix sensor 10 can be used as a sensor for detecting a desired detection target substance.
Further, the matrix sensor 10 may include a plurality of types of sensor units 20 having different types of detectable substances to be detected.
The same applies to the second to fourth embodiments.

In the first embodiment, when the sample is a liquid sample, each sensor unit 20 may be combined with a reactor or a flow cell, or may be formed in a micro channel or a channel in the micro reactor. good.
The same applies to the second to fourth embodiments.

  Further, in the second embodiment, the matrix sensor 10A is not limited to the five sensor units 20 having different detection density ranges, and may include a plurality of types of sensor units 20 having different detection density ranges. It ’s fine.

In the second embodiment, the method of adjusting the detection density range of the sensor unit 20 is not limited to the method using the adjustment permeable film 19, and the matrix sensor 10A has a plurality of types with different detection density ranges. It is optional as long as the sensor unit 20 can be provided. For example, the detection density range of the sensor unit 20 may be adjusted by adjusting the distance between the permeable membrane 15 and the electrode 12. In this case, the smaller the distance between the permeable membrane 15 and the electrode 12, the lower the detected concentration range, and the larger the distance between the permeable membrane 15 and the electrode 12, the higher the detected concentration range. Become.
Further, by providing the matrix sensor 10A with a plurality of types of sensor units 20 having different functions, the matrix sensor 10A may be provided with a plurality of types of sensor units 20 having different detection density ranges. That is, for example, the matrix sensor 10A includes a sensor unit 20 that functions as an electrode sensor (electrode type enzyme sensor), a sensor unit 20 that functions as a solid electrolyte sensor, and a sensor unit that functions as a metal oxide semiconductor sensor. 20 and the sensor unit 20 functioning as a crystal oscillator type sensor, the matrix sensor 10A may include a plurality of types of sensor units 20 having different detection density ranges.
Further, for example, in the first embodiment, the detection concentration range of the sensor unit 20 can be adjusted by changing the sample supply rate to the supply layer 23 of the sensor unit 20. In this case, the higher the supply speed, the lower the detection density range, and the lower the supply speed, the higher the detection density range.

In the second embodiment, the method of determining the sensor unit 20 (optimum sensor unit 20) having the optimum detection density range is determined by the allowable current range and a plurality of types acquired by the detection data acquisition unit 40. The sensor unit 20 is not limited to the response current value determined by each of the sensor units 20, and the sensor unit 20 having the detection concentration range including the concentration of the detection target substance can be determined as the optimum sensor unit 20. It is optional if possible. That is, for example, the concentration of the detection target substance is 500 ppm, the sensor unit 20 (sensor unit A) having a detection concentration range of 1 ppm to 100 ppm, and the sensor unit 20 (sensor unit C) having a detection concentration range of 20 ppm to 1000 ppm, If there is, it is optional as long as the sensor unit B can be determined as the optimum sensor unit 20.
Specifically, for example, there are a sensor unit A (detection concentration range is 1 ppm to 100 ppm), a sensor unit B (detection concentration range is 10 ppm to 200 ppm), and a sensor unit C (detection concentration range is 20 ppm to 1000 ppm). If the detection density range of A is the lowest density side and the detection density range of the sensor part C is the highest density side, is the sensor unit 20 optimal in the order of sensor part C → sensor part B → sensor part A? It may be determined whether or not the optimum sensor unit 20 is determined. More specifically, for example, based on the detection data of the sensor unit C, it is determined whether or not the sensor unit C is the optimal sensor unit 20, and the sensor unit C is determined to be the optimal sensor unit 20 Furthermore, the sensor unit C is determined as the optimum sensor unit 20. When it is determined that the sensor unit C is not the optimal sensor unit 20, it is determined whether the sensor unit B is the optimal sensor unit 20 based on the detection data of the sensor unit B, and the sensor unit B is optimal. When it is determined that it is the sensor unit 20, the sensor unit B is determined as the optimum sensor unit 20. When it is determined that the sensor unit B is not the optimal sensor unit 20, it is determined whether the sensor unit A is the optimal sensor unit 20 based on the detection data of the sensor unit A, and the sensor unit A is the optimal sensor unit A. When it is determined that the sensor unit 20 is the sensor unit A, the sensor unit A is determined as the optimal sensor unit 20, and when it is determined that the sensor unit A is not the optimal sensor unit 20, for example, a detection error is displayed. . In this way, the optimal sensor unit 20 may be determined. The order of determination is not limited to the order of sensor unit C → sensor unit B → sensor unit A. For example, the order may be sensor unit A → sensor unit B → sensor unit C.

  Further, in the second embodiment, when the concentration range of the detection target substance is known in advance, each type of sensor is based on detection data from each type of sensor unit 20 belonging to one group. It is not necessary to determine the sensor unit 20 having the optimum detection density range from the unit 20. That is, when the concentration range of the detection target substance is known in advance, for example, the sensor unit 20 having the detection concentration range including the concentration range of the detection target substance is replaced with the sensor unit having the optimum detection concentration range. It may be determined as 20.

Further, the second embodiment may be combined with the third embodiment.
Specifically, for example, using the matrix sensor 10A of the second embodiment, detection data by each of the plurality of sensor units 20 having the optimum detection density range is acquired, and the acquired detection data is used. A predetermined statistical process may be performed, and the concentration of the detection target substance may be calculated based on the result of the predetermined statistical process.
In this case, the measurement accuracy of the detection target substance can be increased.

Further, the second embodiment may be combined with the fourth embodiment.
Specifically, for example, a difference sensor unit 20C is provided in the matrix sensor 10A of the second embodiment, and detection data by the sensor unit 20 having an optimum detection density range and detection data by the difference sensor unit 20C are provided. And the concentration of the detection target substance may be calculated based on the difference.

Further, the second embodiment may be combined with the third embodiment and the fourth embodiment.
Specifically, for example, a difference sensor unit 20C is provided in the matrix sensor 10A of the second embodiment, and the matrix sensor 10A provided with the difference sensor unit 20C has an optimum detection density range. The detection data by each of the plurality of sensor units 20 is acquired, and the difference between the acquired detection data by each of the plurality of sensor units 20 and the detection data by the difference sensor unit 20C is obtained, and predetermined using the difference The concentration of the detection target substance may be calculated based on the result of the predetermined statistical processing.

The third embodiment may be combined with the fourth embodiment.
Specifically, for example, using the matrix sensor 10C of the fourth embodiment, detection data from each of the plurality of sensor units 20 having the same detection density range is acquired, and the acquired plurality of sensor units 20 is acquired. The difference between each of the detection data and the detection data by the difference sensor unit 20C is taken, and predetermined statistical processing is performed using the difference, and the concentration of the detection target substance is determined based on the result of the predetermined statistical processing. May be calculated.

It is a block diagram which shows the functional structure of the sensor system of 1st Embodiment. It is a figure showing typically the sensor system of a 1st embodiment. It is a top perspective view of the matrix sensor of a 1st embodiment. It is an exploded view of the matrix sensor of a 1st embodiment. It is sectional drawing in the VV line of FIG. It is a board | substrate with which the matrix sensor of 1st Embodiment is provided, Comprising: It is a top view of the board | substrate with which the electrode was formed. It is a figure for demonstrating the specific method of the sensor part which the matrix sensor of 1st Embodiment has. It is a figure which shows the drive circuit of the detection data acquisition part with which the sensor system of 1st Embodiment is provided. It is a circuit diagram which shows the addressable active element connected to the working electrode with which the matrix sensor of 1st Embodiment is provided. FIG. 10 is a circuit diagram showing an example of the active element shown in FIG. 9. FIG. 10 is a circuit diagram showing an example of the active element shown in FIG. 9. FIG. 10 is a circuit diagram showing an example of the active element shown in FIG. 9. It is a flowchart for demonstrating the process regarding the measurement of the density | concentration of the detection target substance by the sensor system of 1st Embodiment. It is a block diagram which shows the functional structure of the sensor system of 2nd Embodiment. It is a top perspective view of the matrix sensor of a 2nd embodiment. It is an exploded view of the matrix sensor of 2nd Embodiment. It is sectional drawing in the XVII-XVII line of FIG. It is a figure for demonstrating a detection density range and the range of the response current corresponding to a detection density range. It is a figure for demonstrating how to determine the allowable current range. It is a flowchart for demonstrating the process regarding the measurement of the density | concentration of the detection target substance by the sensor system of 2nd Embodiment. It is a block diagram which shows the functional structure of the sensor system of 3rd Embodiment. It is a flowchart for demonstrating the process regarding the measurement of the density | concentration of the detection target substance by the sensor system of 3rd Embodiment. It is a block diagram which shows the functional structure of the sensor system of 4th Embodiment. It is a top perspective view of the matrix sensor of a 4th embodiment. It is sectional drawing in the XXV-XXV line | wire of FIG. It is a flowchart for demonstrating the process regarding the measurement of the density | concentration of the detection target substance by the sensor system of 4th Embodiment. It is an exploded view of the matrix sensor created in the Example. It is a figure which shows typically the measuring apparatus used in the Example. It is a figure which shows the experimental result of the experiment for observing the response of the sensor part when the formaldehyde gas was supplied performed using the sensor part which the matrix sensor produced in the Example has. Experiment for demonstrating the effect of having a plurality of types of sensor units with different detection density ranges, using the sensor unit (a plurality of types of sensor units with different detection density ranges) included in the matrix sensor created in the example It is a figure which shows the experimental result of. The experimental result of the experiment for demonstrating the effect by calculating | requiring the average value of detection data performed using the sensor part (several sensor part with the same detection density range) which the matrix sensor created in the Example has is shown. FIG. It is a figure which shows the experimental result of the experiment for demonstrating the effect by taking the difference of detection data performed using the sensor part and the sensor part for difference which the matrix sensor produced in the Example has. It is a modification of the top view of the board | substrate with which a matrix sensor is provided, Comprising: The electrode was formed. It is a modification of the figure which shows the drive circuit of the detection data acquisition part with which a sensor system is provided. It is a flowchart for demonstrating the modification of the process regarding the measurement of the density | concentration of the detection target substance by a sensor system.

Explanation of symbols

1, 1A, 1B, 1C Sensor system 10, 10A, 10C Matrix sensor 11 Substrate 12 Electrode (detection element)
13 Porous body 13a Pore 14 Partition part 17 Sealing member 20 Sensor part 20C Difference sensor part 30 Seal removing part (removing means)
40 Detection data acquisition unit (acquisition means)
40C detection data acquisition unit (acquisition means, difference acquisition means)
51 CPU (determination means, designation means, calculation means)
531, 531C Deterioration judgment program (determination means)
532, 532A, 532B, 532C Sensor unit designation program (designation means)
535, 535A, 535B, 532C Concentration calculation program (calculation means)
E Enzyme (reactive substance (biological substance))

Claims (2)

A matrix sensor having a substrate, a plurality of sensor units arranged in a two-dimensional or three-dimensional matrix on the substrate, and a partition unit arranged on the substrate and separating the sensor units;
A calculation unit that performs predetermined statistical processing using detection data from each of the plurality of sensor units having the same detection concentration range, and calculates the concentration of the detection target substance based on a result of the predetermined statistical processing;
With
The sensor unit includes a detection element disposed on the substrate, a porous body disposed on the detection element and having at least a pore penetrating in a direction substantially perpendicular to the substrate, and a pore of the porous body And a reactive substance that selectively reacts with a substance to be detected , and detects a predetermined change accompanying the reaction by the detection element ,
The sensor system according to claim 1, wherein the porous body is a membranous silica-based mesoporous body formed independently of the detection element . A designating unit for designating a predetermined sensor unit among the plurality of sensor units;
Obtaining means for obtaining detection data by the sensor unit designated by the designation means;
With
The detection element is an electrode;
The sensor system according to claim 1, wherein the reactive substance is a biological substance.

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