JP2007057459A - Chemical sensing capacity sensor chip - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical sensing capacity sensor device formed into a chipped shape in its sensor part and using a chipped chemical sensing capacity sensor in order to provide an inexpensive small-sized a chemical sensing capacity sensor device simple to operate and possible to carry, and its measuring method. <P>SOLUTION: A reference electrode (0303) for the chemical sensing capacity sensor is provided which has a laminated structure that the internal solution of a liquid film type reference electrode is converted to a solid phase. Further, an integrative chemical sensing capacity sensor (0300) is provided which keeps the reference electrode for the chemical sensing capacity sensor and an acting electrode (0302) integrated on one support (0301). Furthermore, the small-sized and portable chemical sensing capacity sensor device is provided which has the chemical sensing capacity sensor. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a reference electrode for a chemosensory sensor, a chemosensory sensor chip, a chemosensory sensor device having the chip, and a method for measuring the device.

  Regarding artificial sensors that act as one of the five senses of human beings, the taste sensors invented by the inventors shown in Patent Documents 1, 5, 7, 8, and 9 are known as known techniques. Further, Patent Documents 2, 3, 4, and 6 are already known as publicly known technologies for taste sensor device systems and taste measurement methods using these taste sensors and the like. The taste sensor of this patent document is a membrane potential measurement type sensor developed by applying the ion selective electrode technology. In other words, the taste sensor generates various membrane potentials for the basic tastes of salty taste, sweet taste, bitter taste, sour taste, and umami taste by using various types of lipid polymer membranes that mimic biological biological membranes as the working electrode. Can be made. In addition, the taste sensor device having the taste sensor acquires a membrane potential generated from the working electrode and a membrane potential generated from the reference electrode by immersing the taste sensor in an aqueous solution that is a measurement target. Digitization, visualization, and reproduction of taste can be performed by performing appropriate processing on the acquired membrane potential.

However, the membrane potential measurement type taste sensor device of the prior art is generally large, and a desktop size is required only for the sensor portion. Therefore, it is very difficult to carry and there is a problem that a large amount of valuable measurement samples are required. Furthermore, since the apparatus itself is expensive for general users and handling and measurement methods are complicated, the feeling of a measurement apparatus dedicated to a professional contractor cannot be denied, and there is a problem in the spread.
JP-A-3-54446 JP-A-3-163351 JP-A-4-64053 JP-A-4-297863 JP-A-4-324351 JP-A-5-99896 JP-A-6-18479 JP 7-5147 A JP-A-7-269826

  An object of the present invention is to reduce the size of a chemosensory sensor device. For that purpose, it is first necessary to downsize the sensor portion. Therefore, the first object of the present invention is to provide a reference electrode in which an internal solution of a conventional liquid film type reference electrode is solid-phased. Another object of the present invention is to provide a chemosensory sensor chip in which the solid-phased reference electrode and the working electrode are integrated. Furthermore, a third object of the present invention is to provide a chemosensory sensor device capable of improving portability and reducing the number of measurement samples by using the chemosensory sensor chip. Moreover, this invention makes it the further subject to provide the measuring method of a chemosensory sensor system when the said chemosensory sensor chip is utilized. By solving the above problems, the miniaturization of the target chemosensory sensor device is achieved.

  In the present invention, “chemosensory ability” means a function capable of accepting the properties of a chemical substance dissolved or mixed in an aqueous solution. For example, a function capable of sensing an aqueous solution in which a water-soluble chemical substance is dissolved as a taste, that is, a salty taste, sweet taste, sour taste, and umami taste, a function of measuring the hydrogen ion concentration of the aqueous solution, and the like are applicable.

  In order to solve the above problems, the invention of the present application provides a reference electrode for a chemosensory sensor having a laminated structure. Another invention of the present application provides a chemosensory sensor chip formed on one support having the reference electrode. A further invention of the present application provides a chemosensory sensor device having the chemosensory sensor chip. The invention of the present application provides a measurement method for the chemosensory sensor device. That is, the following invention is provided.

  (1) The present invention relates to a first conductor, a wetting layer in which an electrolyte solution capable of charge exchange between the first conductor is held in a wetting material, and the electrolyte solution held in the wetting layer is charged with external ions and charges. Provided is a reference electrode for a chemosensory sensor having a charge exchange preventing layer for preventing exchange and an electrolyte leakage preventing layer for preventing an electrolyte retained in a wet layer from leaking to the outside.

  (2) The present invention provides a reference electrode for a chemosensory sensor, wherein the wetting material of the wetting layer is a polymer.

  (3) The present invention provides a reference electrode for a chemosensory sensor, wherein the electrolyte of the wet layer is a KCl solution.

  (4) The present invention provides a reference electrode for a chemosensory sensor, wherein the first conductor is Ag or Ag / AgCl.

  (5) The present invention provides a reference electrode for a chemosensory sensor, wherein the electrolyte solution of the wet layer is a mixed solution of KCl and AgCl.

  (6) The present invention provides a reference electrode for a chemosensory sensor, wherein the charge exchange prevention layer comprises a polymer film material and a plasticizer.

  (7) The present invention provides a reference electrode for a chemosensory sensor, wherein the electrolyte leakage prevention layer is formed of a reverse osmosis membrane.

  (8) The present invention provides a reference electrode for a chemosensory sensor, wherein the charge exchange prevention layer and the electrolyte leakage prevention layer are composed of a single layer having both functions.

  (9) The present invention includes a support, one or more working electrodes formed on the support, the second conductor, and a lipid polymer membrane capable of charge exchange between the second conductor and A reference electrode for a chemosensory sensor according to any one of (1) to (8) formed on the support, and at least one reference electrode for a chemosensory sensor, and the working electrode And a chemosensory sensor chip having an isolating portion for electrically isolating the reference electrode for the chemosensory sensor.

  (10) The invention is characterized in that, when the number of working electrodes is two or more, each working electrode has a lipid polymer membrane that exhibits different responsiveness to one chemical substance from other working electrodes. A sensory sensor chip is provided.

  (11) In the present invention, the isolation part is a wall-like insulator provided around the first conductor and the second conductor, and the reference electrode for the chemosensory sensor is measured by the wall-like insulator. A chemosensory sensor chip, wherein only the electrolytic leakage prevention layer is left as a contact area with an object, and the working electrode is configured to leave only the lipid polymer film as a contact area with an object to be measured. I will provide a.

  (12) The present invention provides a chemosensory sensor chip characterized in that the wall-like insulator is formed by exposing photosensitive glass to an acid treatment after heat treatment.

  (13) The present invention provides a measurement probe having the chemosensory sensor chip according to any one of (9) to (12), and a reference electrode for acquiring a potential value from a reference electrode of the chemosensory sensor chip of the measurement probe A potential value acquisition unit, a working electrode potential value acquisition unit that acquires a potential value from each of one or more working electrodes of the measurement probe, and a potential value for each working electrode acquired by the working electrode potential value acquisition unit And a differential potential value acquisition unit that acquires a difference value between the potential value acquired by the reference electrode potential acquisition unit and a differential potential value acquired by the differential potential value acquisition unit for each working electrode, and Provided is a chemosensory sensor device having a differential potential value output unit that outputs a differential potential value pattern obtained based on a working electrode potential value.

  (14) In the present invention, in addition to the configuration of the chemosensory sensor device, an accumulation unit that accumulates a known differential potential value pattern for each working electrode of a known chemical substance, and an output from the differential potential value output unit A comparison unit for comparing the potential difference value pattern of the working electrode and the known difference potential value pattern stored in the storage unit, and a measurement target measured by the measurement probe based on the comparison result in the comparison unit There is provided a chemosensory sensor device having a determination unit for determining chemical characteristics of an object.

  (15) In the present invention, in addition to the configuration of the chemosensory sensor device of (13) or (14), the chemosensory sensor chip of any one of (9) to (12) can be attached to and detached from the measurement probe. Provided is a chemical sensory sensor device having a detachable part.

  (16) In the present invention, the pattern consisting of a plurality of potential values generated on the one or more working electrodes by the object to be measured is a lipid polymer membrane disposed on one or more working electrodes of the measurement probe. Provided is a chemosensory sensor device which is a lipid polymer film having a different pattern depending on a sweet solution, a salty solution, a sour solution, an umami solution, and a bitter solution as a product.

(17) The present invention provides a reference electrode potential value acquisition step of acquiring a potential value from a reference electrode of a chemosensory sensor chip in a measurement probe having the chemosensory sensor chip of any one of (9) to (12) A working electrode potential value acquisition step for acquiring a potential value from each of one or more working electrodes of the measurement probe, a potential value for each working electrode acquired in the working electrode potential value acquisition step, and a reference electrode potential acquisition A differential potential value acquisition step for acquiring a differential value from the potential value acquired in the step, and a differential potential value output step for outputting the differential potential value acquired in the differential potential value acquisition step for each working electrode;
A measurement method of a chemosensory sensor system having

  (18) In the present invention, after the differential potential value output step, an accumulation step of storing a known differential potential value for each working electrode by a known chemical substance, and a potential difference for each working electrode output from the differential potential value output step A comparison step for comparing the value pattern with the known differential potential value pattern stored in the accumulation step, and determining a chemical characteristic of the measurement object measured by the measurement probe based on a comparison result in the comparison step There is provided a measurement method of a chemosensory sensor system further comprising a determination step.

  According to the reference electrode for a chemosensory sensor of the present invention, the reference electrode can be reduced in size by solidifying the internal liquid of the conventional liquid film type reference electrode.

  According to the chemosensory sensor chip of the present invention, the reference electrode and the working electrode can be integrated on the support, and these electrodes can be integrated. In addition, the chemical sensory sensor unit can be reduced in size and weight. In addition, since the chemical sensory sensor unit can be mass-produced, the overall cost of the chemical sensory sensor device can be reduced.

  According to the chemosensory sensor device of the present invention, the use of the chemosensory sensor chip of the present invention can improve portability, reduce the measurement sample, reduce the cost, and simplify the handling and measurement method.

  According to the measurement method of the chemosensory sensor system of the present invention, the measurement method can be simplified.

  According to the measurement method of the chemosensory sensor device and the chemosensory sensor system of the present invention, the general user can easily use it by reducing the cost and improving the simplification of the measurement method. Thereby, the spread of the chemical sensory sensor device can be promoted. Furthermore, the database detected by the chemical sensory sensor device can be enriched, and the quality control of taste in food can be strictly performed.

  The best mode for carrying out each invention will be described below. The present invention is not limited to these embodiments, and can be implemented in various ways without departing from the scope of the invention.

  The first embodiment mainly relates to claims 1 to 8. The second embodiment mainly relates to claims 9 to 12. The third embodiment mainly relates to claims 13 and 15 to 17. The fourth embodiment mainly relates to claims 14 to 16 and 18.

<< Embodiment 1 >>
<Embodiment 1: Overview> Embodiment 1 will be described. The present embodiment relates to a reference electrode for a chemosensory sensor of a solid phase composed of a conductor and a plurality of layers having different properties. The plurality of layers include a wetting layer, a charge prevention layer, and an electrolyte leakage prevention layer. The reference electrode for this chemosensory sensor is characterized in that the wetting layer constituting the electrode performs the same function as the internal solution in the reference electrode of a conventional liquid membrane ion selective electrode device and is a solid phase. And

  <Embodiment 1: Configuration> FIG. 1A shows an example of the configuration of the present embodiment. As shown in this figure, the reference electrode (0100) for the chemosensory sensor of this embodiment has a first conductor (0101), a wet layer (0102), a charge exchange prevention layer (0103) as its configuration. And an electrolyte leakage prevention layer (0104). Hereinafter, each configuration will be described in detail.

  The “reference electrode for chemosensory sensor” (0100) generates a potential serving as a measurement reference upon contact with the object to be measured, like the reference electrode of the conventional liquid membrane ion selective electrode device. It is configured. The shape of the reference electrode for the chemosensory sensor is not particularly limited as long as it has a laminated structure as described above and only the electrolyte leakage preventing layer can contact the object to be measured. For example, in the cross-sectional view of the reference electrode for the chemosensory sensor of FIG. 1, it may have a shape surrounded by a support body (0105) to be described later, such as A, or one side of the support body as shown in B. It may be a semicircular shape with the electrolyte leakage prevention layer in contact only with the outermost layer, or a shape that does not require a support with the electrolyte leakage prevention layer as the outermost layer as in C. May be.

  The “first conductor” (0101) is constituted by a conductor. The material of the conductor may be any of an electronic conductor, an ionic conductor, or an electron / ion mixed conductor, but an electronic conductor is preferable in consideration of processing. In the case of an electronic conductor, for example, a metal such as aluminum (Al), chromium (Cr), copper (Cu), silver (hereinafter referred to as Ag), platinum (Pt), gold (Au), or carbon (C ). Ag or silver / silver chloride (hereinafter referred to as Ag / AgCl) is preferable because it is used as a general wiring material in a reference electrode of a liquid membrane ion selective electrode device and is easily available. In particular, Ag / AgCl is convenient because silver chloride (hereinafter referred to as AgCl) is generated or attached to the Ag surface and can suppress the polarization phenomenon when the first conductor is composed of Ag. The first conductor is a terminal portion of the wiring, and has a function of transmitting a potential value acquired by the reference electrode for the chemosensory sensor in the chemosensory sensor device to another part as an electric signal.

  The “wetting layer” (0102) is mainly composed of an electrolytic solution and a wetting material, and is configured on the first conductor. The wet layer is preferably formed so as to be in direct contact with the first conductor. Moreover, it is preferable that the thickness of the said wet layer is comprised within the range of 50-450 micrometers from the function and suppressing drying of electrolyte solution. The function of the wet layer is to perform charge exchange between the electrolytic solution held in the wet material and the first conductor. That is, the wet layer can perform the same function as the internal solution of the liquid film type reference electrode, which is a conventional liquid phase while being a solid phase.

  The “electrolytic solution” is a liquid having conductivity by dissolving an electrolyte in a solvent such as water. The type of electrolyte constituting the electrolytic solution is not particularly limited, but a potassium chloride (hereinafter referred to as KCl) solution is particularly preferable. This is because local cells are not easily generated in the wet layer because the transport numbers of cations (potassium ions) and anions (chlorine ions) constituting potassium chloride are almost equal. However, when the charge exchange sensitivity can be adjusted by unbalanced the transport number of the cation and the anion, the transport number does not necessarily have to be substantially equal. Moreover, when a part of said 1st conductor is comprised with a metal, it is preferable that it is a mixed solution of KCl and the metal salt of the said metal. For example, the electrolytic solution in the case where the first conductor is composed of Ag / AgCl is preferably a mixed solution of KCl and AgCl. This is to prevent the electrode from being consumed due to the ionization of Ag on the Ag / AgCl surface and to extend the life. The concentration of the electrolyte in the electrolytic solution is not particularly limited. Preferably, it is the maximum concentration that does not precipitate when the electrolyte is held in the wet layer. The maximum concentration may be appropriately adjusted according to the solubility of the electrolyte or the material of the wetting material described later. For example, when the electrolytic solution contained in the wet layer is a KCl solution, it is about 1.7M. Further, glycerin may be added to the electrolytic solution. Since glycerin has the property of being highly water-retentive and difficult to evaporate, the addition of this makes it possible to suppress water evaporation of the electrolyte. The amount of glycerin added is in the range of 5% to 50%, preferably 10% to 40%, more preferably 15% to 35% of the electrolyte volume. The function of the electrolytic solution is to exchange charges with the first conductor due to its conductivity.

  The “wetting material” is a substance that holds the electrolyte and has a structure as a matrix. The material of the wetting material is not particularly limited as long as the material can hold the electrolytic solution. For example, a porous body such as sponge, an aggregate of fibers having a capillary structure such as cotton or pulp, or a high molecular weight polymer is applicable. In consideration of the point that the electrolyte does not easily flow out even when pressurized and a large amount of electrolyte can be retained, a polymer is preferable.

  The “polymer polymer” of the present invention is a hydrophilic polymer having a network structure and capable of holding a large amount of electrolyte. Specifically, such as poly-hydroxyethyl methacrylate (hereinafter referred to as pHEMA), polyacrylate, polyacrylamide, and konnyaku-mannan. Examples thereof include polysaccharide polymer polymers, gelled proteins such as gelatin jelly. These polymer polymers can hold the electrolytic solution by adding the electrolytic solution to each monomer for polymerization. The mixing ratio of the polymer to the electrolyte is preferably such that the electrolyte has a capacity of 80 or more when the water retention limit capacity (saturated water content) in a certain amount of polymer is 100. . Since the amount of water that can be held varies depending on the type of the polymer, the capacity of the electrolytic solution may be appropriately changed according to the type of polymer used. At this time, it is preferable to add the glycerin to the electrolytic solution. The said high molecular polymer superposes | polymerizes by hold | maintaining electrolyte solution, and forms hydrogel.

  The “charge exchange prevention layer” (0103) is configured to be laminated on the wet layer. The charge exchange preventing layer is preferably configured to directly contact the wet layer. The function of the charge exchange preventing layer is as a buffer layer for preventing ions in the electrolyte retained in the wet layer from directly exchanging charges with the external ions, that is, ions existing in the measurement target. Function. The material for the charge exchange preventing layer is not particularly limited as long as it is a material having the above function. For example, a material obtained by mixing a polymer film material with a plasticizer may be used. Moreover, it is preferable that the thickness of the charge exchange prevention layer is functionally comprised within a range of 10 to 200 μm.

  The “polymer film material” is configured as a support member when a plasticizer is mixed and used as a charge exchange prevention layer. If the said polymer membrane material is a well-known polymer membrane material (refer patent document 1) used with a liquid membrane type ion selective electrode etc., and what does not have ion-exchange property in itself is used. Well, there is no particular limitation on the type. Further, unlike the polymer membrane material of the liquid membrane type ion selective electrode, the polymer membrane material needs not to carry an ionophore (ion transporter). Specifically, polyvinyl chloride (hereinafter referred to as PVC), polyvinylidene chloride (PVDC), polystyrene (PS), polyurethane (PU), polysulfone (PSF), polycarbonate (PC), polyarylate (PAR), polyamide Examples thereof include plastics such as (PA) and polyvinyl alcohol (PVA), and natural resins such as lacquer. Above all, PVC is easily available, and is easily dissolved in a solvent such as nitrobenzene, tetrahydrofuran (hereinafter referred to as THF), cyclohexanone, etc., and has advantages such as easy adjustment of softening and curing by a mixing ratio with a plasticizer described later. is there. For this reason, PVC is the most commonly used polymer membrane material for liquid membrane ion selective electrodes, and is also preferred as the polymer membrane material.

  The “plasticizer” is a substance that can plasticize the polymer film material. The plasticizer molecule has a structure having a polar region and a nonpolar region. The polar region is electrically connected to the molecules of the polymer film material, and the non-polar region increases the intermolecular distance of the polymer film material, thereby maintaining the flexibility of the polymer film material. In general, an ester compound or an ether compound is frequently used, but there is no particular limitation as long as it has a plasticizing property. Specifically, 2-nitrophenyl octyl ether (hereinafter referred to as NPOE), 4-nitrophenyl phenyl ether (NPPE), dioctyl phosphate (hereinafter referred to as DOP), di-n-octylphenyl phosphate (hereinafter referred to as DOPP). And dioctyl sebacate (DOS), dibutyl sebacate (DBS), tricresyl phosphate (TCP), and the like. The type of the plasticizer may be appropriately selected according to the desired ion selectivity and compatibility with the polymer membrane material to be used, plasticization efficiency, low migration, low volatility, and the like.

  For producing the charge exchange preventing layer in the reference electrode for the chemosensory sensor, for example, the polymer film material is dissolved in a solvent, and a plasticizer is added and mixed on the wet layer. Subsequently, the target layer may be formed by removing the solvent by air drying or the like and solidifying the polymer film material. Moreover, after forming a layer by the method similar to the above independent of a wet layer, you may mount so that it may laminate | stack on a wet layer.

  The “electrolyte leakage preventing layer” (0104) is configured to be laminated on the charge exchange preventing layer. The electrolyte leakage prevention layer is preferably configured to be in direct contact with the charge exchange prevention layer. Further, the electrolyte leakage prevention layer is configured to be in direct contact with the object to be measured. However, this is not the case in the case of a layer having the functions of the charge exchange prevention layer and the charge leakage prevention layer as described later. The material of the electrolyte solution leakage prevention layer is not particularly limited as long as it is a material that can prevent the electrolyte solution held in the wet layer from leaking to the outside, that is, a waterproof material. For example, a reverse osmosis membrane such as nitrocellulose (hereinafter referred to as CN) or an ion exchange membrane such as Nafion (manufactured by DuPont) may be used. The thickness of the electrolyte leakage prevention layer is preferably as thin as possible within the range in which its function can be fulfilled. However, in consideration of mechanical strength and the like, it is preferable to configure the thickness within the range of 1 to 100 μm. The function of the electrolyte leakage prevention layer is to prevent the electrolyte in the wet layer from leaking outside through the charge exchange prevention layer.

  The electrolyte leakage prevention layer in the chemosensory sensor reference electrode is prepared by, for example, applying CN dissolved in a solvent to the charge exchange prevention layer, then removing the solvent by air drying or the like and solidifying it. May be formed. Moreover, when using what was already formed as a film | membrane like Nafion, you may affix an electrolyte leakage prevention layer of a suitable size on the said charge exchange prevention layer.

In the reference electrode for a chemosensory sensor of the present invention, when the electrolyte solution in the wet layer leaks to the outside by the action of the two layers of the charge exchange preventive layer and the electrolyte solution leak preventive layer, external ions enter the wet layer. Inflow and outflow are prevented. Therefore, when the layer having the functions of the charge exchange prevention layer and the electrolyte leakage prevention layer is used in the reference electrode for the chemosensory sensor, the charge exchange prevention layer and the electrolyte leakage prevention layer are It can be replaced with one layer having the function of the two layers.
For example, the case where the charge exchange prevention layer has the same function as the electrolyte leakage prevention layer is applicable. Specifically, the case where the charge exchange prevention layer is composed of a polymer film material and a plasticizer corresponds to a case where the amount of the plasticizer mixed with the polymer film material is reduced and homogenized by stirring or the like. In such a charge exchange prevention layer, the intermolecular distance of the polymer film material is narrowed, and as a result, it is possible to simultaneously have a function of preventing leakage of the electrolytic solution. Thus, when it is replaced with one layer having the function of two layers, only the replaced one layer can come into contact with the object to be measured. That is, in the case of the above example, the charge exchange preventing layer can come into contact with the object to be measured. The “layer” referred to here means one of overlapping layers made of the same homogeneous material.

  <Embodiment 1: Effect> According to the reference electrode for a chemosensory sensor of the present embodiment, a wet layer in which an internal solution of a conventional liquid film type reference electrode is solid-phased is provided, and the charge between the wet layer and the outside is further provided. A reference electrode can be reduced in size by providing a layered structure in which a layer that prevents exchange and a layer that functions as filtering are provided. In addition, portability and simplicity of measurement can be improved thereby.

<< Embodiment 2 >>
<Embodiment 2: Overview> Embodiment 2 will be described. The present embodiment relates to an integrated chemosensory sensor chip in which the working electrode and the reference electrode for the chemosensory sensor of the first embodiment are formed on one support. At least one electrode is formed on one support, and each electrode is electrically isolated by an isolation part.

  FIG. 2 shows an example of the chemosensory sensor chip of this embodiment. The chemosensory sensor chip (0200) shown in FIG. 2 is a chemosensory sensor chip having a size smaller than that of the little finger using the glass substrate (0201) as a support. A reference electrode (0203) for a chemosensory sensor and a plurality of working electrodes (0202) are formed in a slit-shaped channel (0204) formed around the edge of one surface of the glass substrate. It is partitioned by a partition wall portion (0205) of glass. A connection terminal (0206) connected to the first conductor in each electrode or the second conductor is exposed at the other end of the glass substrate.

  <Embodiment 2: Configuration> FIG. 3 is a configuration example of the chemosensory sensor chip of the present embodiment, and is a cross-sectional view when cut perpendicular to the two types of electrode surfaces constituting the chemosensory sensor chip. It is. As shown in this figure, the “chemical sensory sensor chip” (0300) of this embodiment includes a support (0301), at least one working electrode (0302), and a reference electrode for chemical sensory sensor (0303). ) And an isolation part (0304). The working electrode (0302) has a second conductor (0305) and a lipid polymer membrane (0306). In FIG. 3, the working electrode and the thickness of the reference electrode for the chemosensory sensor are shown to be equal. However, the optimum thickness of each electrode varies depending on the constituent elements and the like. Absent. Hereinafter, each configuration will be described in detail.

  The “support” (0301) is configured as a base on which the working electrode and the reference electrode for the chemosensory sensor are formed. The material of the support is not particularly limited as long as it is an insulator and is water resistant. Specifically, it corresponds to glass, plastic, synthetic rubber, ceramics, water-resistant paper or wood. However, when the said support body is comprised from a composite material, as long as the outermost part is coat | covered with the water-resistant insulator, you may have a conductor. For example, a multilayer substrate having a laminated structure composed of an insulator and a conductor inside, and an outermost part made of a water-resistant insulator is applicable. The shape of the support is not particularly limited as long as the working electrode and the chemosensory sensor reference electrode can be formed. For example, it may be a plate-like substrate (0201) as shown in FIG. 2, or a spherical shape (A), a cubic shape (B), a capsule shape (C), or a conical shape (D) as shown in FIG. ), Pyramid shape (E), indefinite shape, or the like. Note that 0401 indicates a channel (groove) in which each electrode can be formed, and 0402 indicates a connection terminal.

  The “working electrode” (0302) is mainly composed of a second conductor and a lipid polymer membrane, and is formed on the support at least one or more.

  The “second conductor” (0305) is a solid electrode in the working electrode, and is constituted by a conductor. Since the material and function are the same as those of the first conductor (0101), the description thereof is omitted here. The material of the second conductor and the material of the first conductor are preferably the same.

  The “lipid polymer membrane” (0306) is a membrane in which lipid molecules are adsorbed or mixed on a polymer support member, and is configured to be able to exchange charges with the second conductor. The lipid polymer membrane may be a known lipid polymer membrane used in a liquid membrane ion selective electrode (see Patent Document 1). The type of the component constituting the lipid polymer membrane is not particularly limited as long as the lipid polymer membrane is appropriately selected according to the object to be measured. In addition, the method for producing the lipid polymer membrane may be in accordance with a known method for producing a lipid polymer membrane. The lipid polymer membrane has a lipid molecule, a plasticizer, and a polymer support member as main components. However, since the mixing ratio and mixing method of each component differ depending on the type, a known technique (see Patent Document 1). ) And adjust accordingly. For example, when the lipid molecule is tri-octylmethylammonium chloride (hereinafter referred to as TOMA), the plasticizer is DOPP, and the polymer support member is PVC, the weight ratio is 1: What is necessary is just to mix by about 3: 2. When producing the working electrode, for example, after adding and mixing TOMA and DOPP to PVC dissolved in THF, it may be formed on the second conductor by volatilizing and solidifying the THF. Alternatively, it may be formed separately by spreading it in the form of a film, volatilizing THF to solidify it, and then placing it on the second conductor.

  Among the components constituting the lipid polymer membrane, the polymer support member and the plasticizer are the same as the polymer membrane material and the plasticizer in the charge exchange prevention layer of the reference electrode for the chemosensory sensor, respectively. It may be a different kind.

  When there are two or more working electrodes on one chemosensory sensor chip, each working electrode preferably has a lipid polymer membrane that exhibits a different response to one chemical substance from the other working electrodes. The “chemical substance” mentioned here is a substance that is contained in the measurement object and can be measured by the chemical sensory sensor device. For example, water-soluble substances such as metal salts, amino acid salts, sugars, acids, alkalis, lipids, and the like are applicable.

  The working electrode is formed so that the lipid polymer film is in direct contact with the second conductor, but a buffer layer may be provided between the lipid polymer film and the second conductor. The configuration of the buffer layer may be the same as the configuration of the wet layer in the reference electrode for the chemosensory sensor. By using the buffer layer, the ion concentration around the second conductor can be made constant, and the second conductivity generated when ions in the object to be measured reach the second conductor through the lipid polymer membrane. This is convenient because it can suppress fluctuations in the potential between the body and the lipid polymer membrane.

  The function of the working electrode is the same as that of a conventional liquid membrane ion selective electrode. That is, the working electrode potential is generated by contact with the object to be measured. The working electrode potential varies depending on the components constituting the lipid polymer membrane constituting the working electrode.

  The “reference electrode for chemosensory sensors” (0303) is the reference electrode for chemosensory sensors according to the first embodiment, which is formed on at least one of the supports. One reference electrode may be present on one support, but two or more reference electrodes may be present on one support. In that case, each of the reference electrodes may have the same configuration or may have a different configuration.

  The “isolation portion” (0304) is made of an insulator. The function of the isolation part is to electrically isolate each electrode in the chemosensory sensor chip. The isolation part may be integrally molded with the support (0301), or may be molded independently of the support and then later integrated by bonding or the like. When the isolation part is molded independently of the support, the material is not particularly limited as long as the material is an insulator. For example, the same material as the support may be used, or a different material may be used.

  The shape of the isolation part is not particularly limited as long as each electrode can be electrically isolated. For example, the isolation portion may be formed so as to provide a wall-like insulator around the conductor. The “wall-shaped insulator” is an insulator having a height, and is configured to surround the first conductor and the second conductor. A channel is formed around each conductor by the wall insulator. Thereby, each layer of the reference electrode for chemosensory sensors and the lipid polymer membrane of the working electrode can be laminated in the channel. At that time, in order to functionally isolate each electrode, the reference electrode for the chemosensory sensor is configured to leave only the electrolytic leakage prevention layer as a contact area with the object to be measured, and the working electrode is covered. It is desirable that only the lipid polymer film is left as a contact region with the measurement object. That is, it is desirable that the reference electrode for the chemosensory sensor is laminated in the channel for the reference electrode with the electrolytic leakage preventing layer as the uppermost layer, and the other layers are not exposed to the outside. Further, it is desirable that only the lipid polymer membrane is exposed to the outside in the channel for the working electrode. The height of the wall-like insulator, that is, the depth of the channel, may be within a range of 100 μm to 1 mm in order to ensure a sufficient functional thickness for each layer of the reference electrode and the lipid polymer membrane of the working electrode. preferable.

  When the isolation part is formed so as to provide a wall-like insulator, the wall-like insulator may be formed by exposing the photosensitive glass to an acid treatment after heat treatment. “Photosensitive glass” is a glass in which a small amount of a photosensitive metal and a sensitizer are added to quartz glass. Examples of the photosensitive metal include silver and gold, and examples of the sensitizer include cerium chloride. The property of the photosensitive glass is that the metal ion in the exposed part is changed to a metal atom by the ultraviolet exposure. A metal colloid is produced by applying heat treatment at about 500 ° C., and the metal colloid serves as a crystal nucleus to precipitate lithium metasilicate crystals. Since this lithium metasilicate crystal can be easily dissolved by acid treatment such as a hydrogen fluoride (hereinafter referred to as HF) solution, the photosensitive glass can be wet-etched. In addition, since the photosensitive glass has a high etching rate selectivity in the vertical direction, the channel depth can be adjusted without unnecessarily widening the channel width by changing the etching processing time. And accurate chemical cutting can be performed. The wall-like insulator may be formed using these properties.

  <Embodiment 2: Effect> According to the chemosensory sensor chip of the present invention, the reference electrode and the working electrode can be integrally formed on the support. In addition, it is possible to simultaneously measure the objects to be measured by the working electrodes having different responsiveness of one chemosensory sensor chip. Furthermore, since the electrodes on the support can be integrated, the chemosensory sensor unit can be reduced in size and weight. Since the chemical sensory sensor chip of this embodiment can be mass-produced, it leads to a reduction in the cost of the entire chemical sensory sensor device. Further, by disposing the chemosensory sensor chip as a support or plastic or paper, it is possible to save the labor of cleaning. Furthermore, even if the sensory sensor chip is used and the chip is washed after use, there is a possibility that the object to be measured remaining in a trace amount may affect the measurement of the next object to be measured. However, by disposing the chemosensory sensor chip in a disposable manner, the problem can be solved and the accuracy of the measurement result can be increased on the object to be measured.

<< Embodiment 3 >>
<Embodiment 3: Overview> Embodiment 3 will be described. The present embodiment relates to a chemosensory sensor device having the chemosensory sensor chip of the second embodiment. The apparatus includes a reference electrode potential acquisition unit that acquires a potential value from a reference electrode for a chemosensory sensor by bringing a measurement probe into contact with an object to be measured, and an operation that acquires a potential value from each of a plurality of working electrodes. A differential potential value acquisition unit that acquires a difference value between a potential value acquired by the electrode potential value acquisition unit and the working electrode potential value acquisition unit and a potential value acquired by the reference electrode potential acquisition unit, and a differential potential value acquisition And a differential potential value output unit that outputs the differential potential value acquired by the unit for each working electrode. Further, the apparatus is characterized in that the chemical sensory sensor chip of the measurement probe can be attached / detached by the attaching / detaching part.

FIG. 5 shows an example of the chemosensory sensor device of the present embodiment. A chemosensory sensor device (0500) shown in FIG. 5 is a portable chemosensory sensor device imitating the shape of a micropipette. The tip portion (0501) constitutes a measurement probe, and the chemosensory sensor chip (0502) of Embodiment 2 is detachably mounted. The grip portion (0503) includes a reference electrode potential acquisition unit, a working electrode potential acquisition unit, a differential potential value acquisition unit, and a differential potential value output unit. The reference electrode potential value and working electrode potential value generated from the electrode are acquired by immersing the measurement probe at the tip of the object to be measured, and the potential value, the difference potential value, or the difference potential value pattern is output. .
The differential potential value and the differential potential value pattern obtained by the chemosensory sensor device may be configured to be visible on an output unit such as a liquid crystal monitor (0504) built in the grip unit or the like. In addition, a connection terminal such as a USB terminal (0505) is provided in the device so that it can be visually output via a cable to a display unit (0507) of an external electronic device such as a PC (0506), a PDA, or a mobile phone. You may comprise. Further, after being stored in a removable memory such as an SD card (0508), the removable memory may be connected to the external electronic device and output to a display unit or the like so as to be visible. In addition, a wireless transmission unit may be provided in the device, and the wireless transmission (0509) may be performed so that the device can be viewed with the display unit of the external electronic device. Further, if the external electronic device is a printer, it may be made visible by printing out the inputted differential potential value or differential potential value pattern.

  <Embodiment 3: Configuration> FIG. 6 is an example of a configuration of the present embodiment. As shown in this figure, the chemosensory sensor device (0600) of the present embodiment has, as its configuration, a measurement probe (0601), a reference electrode potential value acquisition unit (0602), and a working electrode potential value acquisition unit (0603). ), A difference potential value acquisition unit (0604), and a difference potential value output unit (0605). Moreover, you may have an attachment / detachment part (0606). Hereinafter, each configuration will be described in detail.

  The “measurement probe” (0601) has one or more chemosensory sensor chips of the second embodiment, and is configured such that the electrodes on the sensor chips can come into contact with the object to be measured. For example, all or part of the measurement probe may be contacted by directly immersing it in a solution that is the object to be measured, or the solution that is the object to be measured is dropped onto the sensor chip of the measurement probe. Thus, it may be possible to make contact with the electrode on the sensor chip. Further, the measurement probe may be waterproofed or waterproofed at necessary places. Further, the measurement probe is configured to be able to output a potential generated from each electrode on the chemosensory sensor chip to a reference electrode potential value acquisition unit (0602) and a working electrode potential value acquisition unit (0603) described later. Has been. Each electrode on the chemosensory sensor chip may be deteriorated by drying by being continuously exposed to the air. Therefore, the measurement probe may be configured to prevent the chemosensory sensor chip from drying. For example, at the time of non-measurement, it may be configured such that a dedicated cap with high hermeticity can be attached to all or a part of the measurement probe, or configured to be accommodated in a case containing a basic solution described later. The electrode may be sealed with an airtight film.

  When a plurality of working electrodes are arranged on the chemosensory sensor chip of the measurement probe, the lipid polymer membrane constituting each working electrode is configured to generate different potentials for different objects to be measured. It is preferable. In particular, when the object to be measured is a sweet solution, a salty solution, a sour solution, an umami solution, or a bitter solution, it is preferable that a plurality of potential values generated at the plurality of working electrodes show different values. For example, when three working electrodes A, B, and C are disposed on the chemosensory sensor chip of the measurement probe as shown in FIG. 6, the lipid polymer constituting the working electrodes A, B, and C What is necessary is just to comprise so that the component of a film | membrane may differ. Specifically, when all of the components of the lipid polymer membrane are made of PVC, the working electrode A is composed of a lipidic molecule and a plasticizer. -Decyl ester: hereinafter referred to as 2C10) and DOPP, and working electrode B is tetra-dodecyl ammonium bromide (hereinafter referred to as TDAB) and DOPP, and working electrode C is TOMA and DOPP, respectively. What is necessary is just to comprise.

  The measurement probe may have a “detachable portion” (0606). The attachment / detachment unit is configured so that the whole or a part of the measurement probe (such as the chemosensory sensor chip) can be attached / detached. For example, when only the chemical sensory sensor chip is detachable, the detachable part has a fixing member for fixing the chemical sensory sensor chip in the measurement probe and a connection terminal connectable to the terminal of the chip. It may be configured. Moreover, you may comprise the said attachment / detachment part so that there may be two or more in one chemical sensory ability sensor apparatus.

The “reference electrode potential value acquisition unit” (0602) acquires the reference electrode potential value V ₀ from the reference electrode for the chemosensory sensor on the chemosensory sensor chip, and outputs it to the differential potential value acquisition unit (0604) described later. It is configured as possible. The “reference electrode potential value” is a value of a potential generated at the reference electrode for the chemosensory sensor when the measurement probe is brought into contact with an object to be measured.

  The “working electrode potential value acquisition unit” (0603) is configured to acquire a working electrode potential value Vi (i is a natural number) from each of the plurality of working electrodes on the chemosensory sensor chip. The “working electrode potential value” is a value of a potential generated at a plurality of working electrodes of the chemosensory sensor chip when the measurement probe is brought into contact with an object to be measured.

  The reference electrode potential value acquisition unit and the working electrode potential value acquisition unit may be configured to amplify and output the acquired potential values. For example, if the potential value is amplified, a buffer amplifier may be included in each part. Further, the two acquisition units may be configured to perform A / D conversion and output the acquired analog potential value or the amplified potential value as necessary.

  The respective potential values acquired by the reference electrode potential value acquisition unit and the working electrode potential value acquisition unit may be output to the differential potential value acquisition unit, or may be directly output to a monitor or the like.

The “differential potential value acquisition unit” (0604) acquires a difference value between each working electrode potential value acquired by the working electrode potential value acquisition unit and the potential value acquired by the reference electrode potential acquisition unit. It is configured. The differential potential value may be based on a value obtained by subtracting the reference electrode potential value from each working electrode potential value, or based on a value obtained by subtracting each working electrode potential value from the reference electrode potential value. It may be a thing. “Based on” means to add, subtract, multiply, or divide a constant from the obtained value. FIG. 6 will be described as an example. The working electrode potential values generated from the working electrodes A, B, and C of the measurement probe and acquired by the working electrode potential value acquisition unit are V ₁ , V ₂ , and V ₃ , and the reference electrode for the chemosensory sensor It is assumed that the reference electrode generated by the reference electrode potential acquisition unit is V ₀ . At this time, the differential potential value acquisition unit acquires differential potential values ΔV ₁ , ΔV ₂ , ΔV ₃ obtained by subtracting the reference electrode potential value V ₀ from each of the acquired working electrode potential values V ₁ , V ₂ , V _3. To do. That is, in this example, the differential potential values are obtained as V ₁ −V ₀ = ΔV ₁ , V ₂ −V ₀ = ΔV ₂ , and V ₃ −V ₀ = ΔV ₃ .

The “differential potential value output unit” (0605) is configured to acquire the differential potential value acquired by the differential potential value acquisition unit and output the differential potential value for each working electrode. In addition, a differential potential value pattern obtained based on each working electrode potential value is output as a “differential potential value pattern”. The differential potential value pattern may be, for example, a pattern in which each differential potential value is plotted for each working electrode, or the working electrode potential value obtained from the same object to be measured having different concentrations in one working electrode. A pattern in which the differential potential value for each concentration based on the above is plotted may be used. FIG. 6 will be described as an example. The differential potential values ΔV ₁ , ΔV ₂ , ΔV ₃ obtained by the differential potential value acquisition unit are output together with the related working electrodes. That is, in FIG. 6, each differential potential value is output as working electrode A = ΔV ₁ , working electrode B = ΔV ₂ , and working electrode C = ΔV ₃ . Further, the differential potential value output unit plots the differential potential values ΔV ₁ , ΔV _2, and ΔV ₃ of each working electrode by plotting the working electrodes A, B, and C on the horizontal axis and the differential potential value on the vertical axis, respectively. A graph pattern connected by a line can also be output as a differential potential value pattern.

Further, in order to increase the accuracy of the differential potential value, the measurement probe may be immersed in the basic solution in advance to obtain the reference electrode potential value bV ₀ and the working electrode potential value bVi (i is a natural number) in the basic solution. Good. In this case, the differential potential value ΔVi is determined by the reference electrode potential value V ₀ and the working electrode potential value Vi obtained by bringing the measurement probe into contact with the measurement target following immersion in the basic solution, and the bV. Obtained from ₀ and bVi. For example, the differential potential value ΔVi may be obtained by ΔVi = (Vi−V ₀ ) − (bVi−bV ₀ ). That is, a value obtained by subtracting the difference potential value obtained from the reference solution from the difference potential value obtained from the measurement target object may be set as the target difference potential value.

  The basic solution is not particularly limited as long as it can stably maintain the state of each electrode of the chemosensory sensor chip, but is preferably a solution in which a 30 mM KCl solution and 0.3 mM tartaric acid are mixed.

  <Embodiment 3: Process Flow> The process flow of the chemosensory sensor system in the present embodiment will be described. FIG. 7 shows an example of the flow of processing in the third embodiment. As shown in this figure, first, a measurement probe having the chemosensory sensor chip described in the second embodiment is brought into contact with an object to be measured to generate a reference electrode formed on the chemosensory sensor chip. The obtained potential value is acquired (S0701: reference electrode potential value acquisition step). Next, a potential value generated from each of the one or more working electrodes formed on the chemosensory sensor chip is obtained (S0702: working electrode potential value obtaining step). Here, the order of processing of the reference electrode potential value acquisition step and the working electrode potential value acquisition step does not matter. That is, any step may be processed first. Further, when the acquired potential value is low as a whole, a step of amplifying by an amplifier after acquiring each potential value may be added. Subsequently, a difference value between the potential value of each working electrode acquired in the working electrode potential value acquisition step (S0702) and the potential value acquired in the reference electrode potential value acquisition step (S0701) is acquired. (S0703: Difference potential value acquisition step). Finally, the differential potential value acquired in the differential potential value acquisition step (S0703) is output for each working electrode (S0704: differential potential value output step). In the chemosensory sensor system in the present embodiment, the chemosensory information of the measurement object is measured by the above main steps.

The above processing can be executed by a program for causing a computer to execute the program, and the program can be recorded on a recording medium readable by the computer (the same applies throughout the present specification).
<Embodiment 3: Effect>

  According to the chemosensory sensor device of the present invention, it is possible to reduce the size of the sensor portion that has been conventionally desktop-sized by using the chemosensory sensor chip of the present invention. In addition, the portability of the apparatus can be improved and the required amount of measurement sample can be reduced. Furthermore, since the measurement probe and the chemical sensory sensor chip can be attached and detached by the attaching / detaching part, it is possible to easily perform cleaning of the sensor part after measurement, replacement with a chemical sensory sensor chip according to the object to be measured, etc. it can. Moreover, the cost of the device can be reduced by reducing the cost of the chemical sensory sensor chip itself. Furthermore, it becomes possible to make the chemical sensory sensor device into an IC card in which a chemical sensory sensor chip is embedded. The card-type chemosensory sensor device can be made disposable to obtain a highly accurate measurement value without the influence of contamination, similar to the effect of the second embodiment.

<< Embodiment 4 >>
<Embodiment 4: Overview> Embodiment 4 will be described. The present embodiment is based on the third embodiment, compares the difference potential value acquired by measurement with the known difference potential value accumulated in the accumulation unit, and compares the measured object based on the comparison result. The present invention relates to a chemosensory sensor device capable of determining a chemical characteristic of the sensor.

  <Embodiment 4: Configuration> FIG. 8 is an example of a configuration of the present embodiment. As shown in this figure, the configuration of the chemosensory sensor device (0800) of the present embodiment is based on the configuration of the third embodiment. That is, it has a measurement probe (0801), a reference electrode potential value acquisition unit (0802), a working electrode potential value acquisition unit (0803), a differential potential value acquisition unit (0804), and a differential potential value output unit (0805). In addition, the information processing apparatus further includes an accumulation unit (0806), a comparison unit (0807), and a determination unit (0808). Moreover, you may have an attachment / detachment part (0809). Since the difference potential value output unit (0805) and the detachable unit (0809) are the same as those in the third embodiment, the description thereof will be omitted. Here, the storage unit (0806) characteristic of the present embodiment and Each configuration of the comparison unit (0807) and the determination unit (0808) will be described in detail below.

The “accumulation unit” (0806) is configured to acquire and accumulate a known differential potential value pattern obtained for each working electrode by a known chemical substance from the differential potential value output unit. “Known chemical substances” are chemical substances whose specific properties are obvious. For example, acetic acid (CH ₃ COOH) which is clearly acidic and has a characteristic of giving a sour taste, sodium chloride (NaCl) which is clearly shown to have a characteristic of giving a salty taste by ionization in an electrolyte, and an amino acid salt which gives a taste This is applicable to sodium glutamate, which is clearly known to have, or a mixture of these known chemical substances. Further, the known chemical substance may be a chemical substance that has become known as a result of the determination by the determination unit of the chemosensory sensor device. The “known differential potential value pattern” is a differential potential value pattern obtained from a known chemical substance. The known differential potential value pattern is configured to obtain a known differential potential value pattern output from the differential potential value output unit. Moreover, it is comprised so that the known difference electric potential value pattern of the chemical substance known by the determination part can also be acquired. You may be comprised so that all the known difference electric potential value patterns to accumulate | store can be output to a comparison part. When measuring an object to be measured, a known chemical substance is measured in advance and a known differential potential value pattern is stored in the storage unit, or the storage unit of the device is connected to an external storage unit (via a connection terminal or the like). It is preferable to obtain a known differential potential value pattern from 0809).

  The “comparison unit” (0807) is configured to compare the differential potential value pattern acquired from the differential potential value output unit with the known differential potential value pattern stored in the storage unit. The comparison in the comparison unit is a comparison between the differential potential value pattern acquired from the differential potential value output unit by measuring the measurement target object and the known differential potential value pattern. For example, it is compared whether the difference potential value pattern obtained from the object to be measured and the shape and coordinate values of the known difference potential value pattern match, do not match, are similar, or are completely different. When comparing the difference potential value pattern and the known difference potential value pattern, it is desirable that the comparison region to be directly compared is a pattern acquired based on the same condition. For example, when the differential potential value pattern and the known differential potential value pattern are acquired from a plurality of working electrodes, the number of working electrodes in the comparison region and the lipid polymer membranes to be configured are the same between the two patterns. It is preferable. In addition, when the differential potential value pattern and the known differential potential value pattern are acquired as graph patterns with the working electrode as the horizontal axis and the differential potential value as the vertical axis, the number of digits or horizontal It is preferable that the number of working electrodes on the shaft and the distance between them are the same.

  The “determination unit” (0808) is configured to be able to determine the chemical characteristics of the measurement object measured by the measurement probe based on the comparison result in the comparison unit. “Chemical property” is a property specific to a chemical substance contained in an object to be measured. The criterion for determining chemical characteristics in the determination unit may be a category level to which a chemical substance belongs, or a level for specifying the chemical substance. For example, if the criterion is a category level to which a chemical substance belongs, if the object to be measured is a taste substance, it is determined whether the substance is a salty substance, sweet substance, sour substance, umami substance, or bitter substance . When the determination criterion is a level for specifying a chemical substance, if the object to be measured is an umami substance, it is sodium glutamate (hereinafter referred to as MSG) or sodium inosinate (sodium). inosinate) or other umami substances, etc., to identify and determine the chemical substance. These determinations in the determination unit may be performed as follows based on the comparison result of the difference potential value pattern obtained from the object to be measured in the comparison unit and the known difference potential value pattern. For example, in the case of the comparison result that the differential potential value pattern obtained from the measurement target object matches the known differential potential value pattern, the chemical substance contained in the measurement target object indicates the known differential potential value pattern. You may determine with having the same chemical characteristic as a chemical substance. In addition, in the case of the comparison result that the difference potential value pattern and the shape of the known difference potential value pattern do not match, but all or part of them are similar, the chemical substance contained in the measurement object is the known difference potential value. It may be determined by analogy that the chemical substance showing the value pattern is related to the chemical characteristics. Furthermore, when the difference potential value pattern and the shape of the known difference potential value pattern are completely different, the chemical substance contained in the measurement target object is a chemical substance in which the difference potential value pattern is not accumulated in the accumulation unit. May be determined. In addition, even if the shape of the said difference electric potential value pattern and the said known difference electric potential value pattern is the same, the determination part in this embodiment is contained in the said to-be-measured object, when both patterns have shifted | deviated up and down. It is determined that the chemical substance to be processed is different from the chemical substance showing the known differential potential value pattern.

  <Embodiment 4: Process Flow> The process flow of the chemosensory sensor system in the present embodiment will be described. FIG. 9 shows an example of the flow of processing in the fourth embodiment. As shown in this figure, the processing flow of the present embodiment is based on the processing flow of the third embodiment. That is, first, the potential value is acquired from the reference electrode in the reference electrode potential value acquisition step (S0901) by bringing the measurement probe into contact with the measurement object. Next, a potential value is acquired from each of the one or more working electrodes in a working electrode potential value acquisition step (S0902). As in the third embodiment, the order of processing of the reference electrode potential value acquisition step and the working electrode potential value acquisition step does not matter. Here, when the acquired potential value is low as a whole, a step of amplifying by an amplifier after acquiring each potential value may be added. Subsequently, a difference value between the potential value acquired at the reference electrode in the differential potential value acquisition step (S0903) and the potential value acquired from each of the working electrodes is acquired. In the differential potential value output step (S0904), the differential potential value is output for each working electrode. Up to this point, the processing flow is the same as that of the third embodiment. In the present embodiment, subsequently, the potential difference value of each working electrode output from the differential potential value output step (S0904) is compared with the known differential potential value for each working electrode by a known chemical substance (S0905). : Comparison step). Finally, based on the comparison result in the comparison step (S0905), the chemical characteristic of the measurement object measured by the measurement probe is determined (S0906: determination step). In the chemosensory sensor system in the present embodiment, the chemosensory information of the measurement object is measured by the above main steps.

  <Embodiment 4: Effect>

  According to the measurement method of the chemosensory sensor device and the chemosensory sensor system of the present invention, it is possible to promote the spread of the chemosensory sensor device to general users by reducing the cost and simplifying the measurement method. Thereby, the database detected by the chemosensory sensor device can be enriched, and the quality control of taste in food can be strictly performed.

  The present invention will be specifically described with reference to the following Examples 1 to 5. However, the following examples are merely illustrative, and the present invention is not limited to these examples.

<Production of sensor chip for chemosensory sensor>
As an example of producing the sensor chip for the chemosensory sensor of the second embodiment having the reference electrode for the chemosensory sensor of the first embodiment, a production method in the case where a glass substrate is used as the support is shown below. A glass substrate cut into 13 mm × 38 mm was used.

(1) Preparation of glass substrate on which conductor is arranged FIG. 10 illustrates the manufacturing method. First, a 100 nm thick titanium layer (1002) was deposited on the glass substrate (1001) by electron beam deposition. Next, a 400 nm thick silver layer (1003) was deposited on the titanium layer by the same method (A). The reason why the titanium layer is provided here is that, since silver has poor adhesion to glass, titanium having high adhesion to both glass and silver is used as the adhesive layer in fixing the silver layer on the glass substrate. Because. Subsequently, a negative photoresist (OMR-83) (1004) having a thickness of 100 μm was applied on the silver layer by spin coating (B). Next, a photomask (1005) on which an electrode pattern was drawn was placed on the photoresist layer, and the photoresist layer was exposed to ultraviolet rays (1006) through the photomask (C). After the exposure processing, the photoresist other than the exposed portion is dissolved and removed by washing with a developing solution (1007). As a result, the electrode pattern was developed on the substrate (D). After the development, wet etching treatment (1008) was performed on the exposed silver layer and titanium layer using a 1: 1 mixed solution of NH ₃ and H ₂ O ₂ (E). Thereafter, the remaining photoresist was washed away (1009) with isopropanol (IPA) (F). The substrate was applied in KCl solution at 0.5 mA for 10 minutes. As a result, the silver layer is salified to form a silver / silver chloride layer (1010) (G). A glass substrate on which the conductor was arranged was produced by the above procedure.

(2) Production of isolation part The production method is illustrated in FIG. In this embodiment, a method for producing a separating part separately from the glass substrate by using photosensitive glass for the separating part will be described. First, a photosensitive glass (1101) having a thickness of 500 μm is cut into 13 mm × 13 mm squares (A), and exposed to ultraviolet rays through a photomask (1102) on which a pattern that matches or substantially matches all or part of the electrode pattern is drawn. (B). Next, heat treatment was performed using an electric furnace at 505 ° C. for 90 minutes and then at 535 ° C. for 2 hours (C). Lithium metasilicate crystal (1103) is deposited at the site exposed to ultraviolet rays by the heat treatment (D). Then, wet etching was performed by dissolving and removing the crystals with 5% HF using a stirrer (E). The etching time was 60 minutes. Through-holes can be formed in the photosensitive glass without increasing the channel width during this time. The isolation part was produced by the above procedure.

(3) Manufacture of chip substrate for chemosensory sensor On the glass substrate on which the photosensitive glass on which the isolation part of (2) has been formed is coated with silicone as an adhesive and the conductor of (1) is disposed The conductor wiring pattern was placed so that the channel pattern of the isolation portion substantially matched (F in FIG. 11). By drying the silicone, each conductor on the glass substrate can have a channel composed of a wall-like insulator. A chip substrate for a chemosensory sensor was produced by the above procedure.

(4) Preparation of reference electrode for chemosensory sensor First, a HEMA monomer mixture was prepared for preparation of a wet layer. The HEMA monomer mixture is composed of 60% (w / v) HEMA, 38% (w / v) ethylene glycol, 1% (w / v) acetophenone (DMPA), and 1 % (W / v) tetraethylene glycol dimethacrylate (tetraethylene glycol dimethacrylate) mixed with 100 μl, glycerin 10 μl, saturated KCl solution 50 μl, and a small amount of AgCl powder and mixed well with a stirrer It is. The prepared HEMA monomer mixture was filled into a channel for a reference electrode using a micropipette or the like. This was irradiated with ultraviolet rays for about 2 minutes for polymerization to obtain pHEMA. A wet layer was prepared by drying the pHEMA overnight. Next, a mixed solution of 50% (w / w) PVC and 50% (w / w) NPOE dissolved in THF was filled on the wet layer in order to produce a charge exchange prevention layer. After THF was removed by drying to solidify PVC / NPOE, the same treatment was performed again on the PVC / NPOE. Double PVC / NPOE formed by removing THF by air drying and solidifying again was used as a charge exchange prevention layer. Finally, a CN solution prepared to 5% with ethanol for producing an electrolyte leakage prevention layer was applied on the charge effect prevention layer. A layer formed by drying and removing ethanol was used as an electrolyte leakage prevention layer.

(5) Production of working electrode In producing the working electrode, it is first necessary to produce a lipid polymer membrane. As lipid molecules constituting the lipid polymer membrane, three types of TOMA, TDAB, and 2C10 were selected. As these plasticizers, DOP, DOPP, and tetradecyl alcohol (hereinafter referred to as TDA) were selected. Furthermore, PVC was selected as the polymer support member. Any one of the lipidic molecules, the corresponding plasticizer and PVC were dissolved in THF at a weight ratio of 1: 3: 2, respectively, and thoroughly mixed using a stir bar. The prepared mixed solution was filled into the working electrode channel using a micropipette or the like. It is formed by removing THF by air drying or the like and drying and solidifying again. The isolation part having a thickness of 500 μm can obtain a film thickness sufficient for measurement by filling the lipid polymer film in the channel even if the thickness of the second conductor part is subtracted.

<Confirmation experiment of potential stability of reference electrode for chemosensory sensor>
(Purpose) Measures whether the reference electrode for a chemosensory sensor of the present invention can generate a highly stable and reproducible potential for an object to be measured at a constant concentration, similar to a conventional liquid film type reference electrode. Check by changing the time.

(experimental method)
Preparation of reference electrode for chemosensory sensor The reference electrode for chemosensory sensor used in this example was prepared based on the method described in Example 1 above. The following two types of reference electrodes for chemosensory sensors were prepared according to the method described in Example 1 on one chemosensory sensor chip. The chemosensory sensor chip has only a chemosensory sensor reference electrode and no working electrode.
(1) Three reference electrodes for chemosensory sensors in which KCl is introduced as an electrolyte into the wet layer, that is, three reference electrodes for chemosensory sensors having the same composition as in the first embodiment (A, B, C).
(2) Five reference electrodes for a sensory sensory sensor (D, E, F, G, H) having the same composition as that of the first embodiment except that only water is not introduced into the wet layer. ).

Measurement method The object to be measured was a 1M KCl solution. The chemosensory sensor chip mounted on the chemosensory sensor device of Embodiment 3 is immersed in the solution, and the value of the potential generated from each chemosensory sensor reference electrode of the sensor chip is a reference electrode for 120 minutes. Obtained by the potential value obtaining unit. The obtained potential value was amplified by an operational amplifier (OPA129P) as an amplifier, and then input to a DAQ card 6036E (National Instrument) and sent to a PC as an external electronic device. The potential value data sent to the PC was processed by LabVIEW 7.0 software (National Instrument), which is software used to control the analytical instrument and analyze the analytical data. The measurement result was obtained from a PC monitor display or a printer.

  (Results) FIG. 12 shows the results of this example. In the reference electrode for chemosensory sensor (2) in which no electrolyte was introduced into the wet layer, the potential values of all electrodes did not match at all for 120 minutes. In addition, the potential generated in each electrode is very unstable, and the fluctuation range of the potential generated in one electrode within the time has reached about 200 mV at most. On the other hand, the reference electrode for the chemosensory sensor (1) in which the electrolytic solution KCl was introduced into the wet layer showed a stable potential value of about −150 mV for all the electrodes A, B, and C for 120 minutes. . The fluctuation range of the potential generated from one electrode within the time was about 3 mV. From the above results, it was proved that the potential generated by the chemosensory reference electrode of the present invention having the wet layer into which the electrolyte KCl was introduced was stable for at least 120 minutes. Moreover, the patterns of potentials generated from the independent electrodes were almost the same. This represents the high reproducibility of the results obtained with the reference electrode for a chemosensory sensor of the present invention. Therefore, it has been clarified that the chemosensory reference electrode of the present invention can perform the same function as a conventional liquid film type reference electrode for an object to be measured having a constant concentration.

<Operation confirmation experiment of chemosensory sensor chip>

  (Purpose) Whether the reference electrode for a chemosensory sensor of the present invention can generate a potential having high stability and reproducibility with respect to a change in the concentration of an object to be measured, like a conventional liquid film type reference electrode. Check. At the same time, it is confirmed whether the working electrode on the same chemosensory sensor chip can generate a potential corresponding to the change in the concentration of the object to be measured.

(experimental method)
-Production of reference electrode for chemosensory sensor The reference electrode for chemosensory sensor used in this example was produced with a working electrode on one chemosensory sensor chip according to the method described in Example 1. On the chip, three reference electrodes for chemosensory sensors (B, C, D) having the same composition as one working electrode (A) are formed. The lipid polymer membrane of the working electrode is produced according to the method of Example 1 using TDAB as a lipid molecule, DOPP as a plasticizer, and PVC as a polymer support member.

Measurement method The object to be measured was a KCl solution having three concentrations (1 M, 100 μM, 10 μM). The chemosensory sensor chip mounted on the chemosensory sensor device of Embodiment 3 was first immersed in a 1M solution. The potential of the working electrode was measured, and after the potential was stabilized, the chemosensory sensor chip was taken out of the solution. Next, it was immersed in a 100 μM solution. The potential of the working electrode was measured again, and after the potential was stabilized, the chemosensory sensor chip was taken out of the solution. Subsequently, it was immersed in a 0.01 M solution. The potential of the working electrode was measured again, and after the potential was stabilized, the chemosensory sensor chip was taken out of the solution. The above steps were repeated 3 cycles as 1 cycle. During this time, the potential values generated from the working electrode of the sensor chip and the reference electrodes for the chemosensory sensors were acquired by the working electrode potential value acquisition unit and the reference electrode potential value acquisition unit, respectively. The obtained potential value was processed by the same method as in Example 2 (the amplifier of this example is shared by the working electrode potential value acquisition unit and the reference electrode potential value acquisition unit).

  (Results) FIG. 13 shows the results of this example. a is a 1 M KCl solution immersion period, b is a 100 μM KCl solution immersion period, and c is a 10 μM KCl solution immersion period. The potential value of the working electrode changed significantly with respect to the change in the concentration of the KCl solution. In addition, changes in potential values obtained in three cycles performed within the measurement time all showed substantially the same pattern. This indicates that the working electrode of the chemosensory sensor chip has responsiveness to the object to be measured. On the other hand, the potential value of the reference electrode for the chemosensory sensor hardly changes with respect to the concentration change of the KCl solution, and the potential value within the measurement time is stable at about -100 mV for all of B, C, and D. Was. The fluctuation range of the potential generated from one electrode within the measurement time was about 2 mV for the most stable electrode. Thereby, it was shown that the reference electrode for a chemosensory sensor of the present invention generates a stable potential even with respect to a change in the concentration of the measurement object. In addition, the patterns of potentials generated from the independent reference electrodes are almost the same, indicating that the reproducibility is high. Further, although not shown in the drawings, the measurement target object is a bitter substance (see basic taste sample d in Example 4 described later) or an umami substance (see basic taste sample c in Example 4 described later). When the potential was measured by changing the concentration in the same manner as in the example, the potential generated from the chemosensory reference electrode was stable in any case. From the above results, the chemosensory reference electrode of the present invention generates a potential with high stability and reproducibility even when the concentration of the object to be measured changes, and performs the same function as a conventional liquid film type reference electrode. It became clear to get. Further, since the working electrode generates a highly reproducible potential according to the concentration of the measurement object, the practicality of the chemosensory sensor chip of the present invention was confirmed.

<Measurement experiment of basic taste with chemosensory sensor device>

  (Purpose) A basic sensory substance is measured as an object to be measured by the chemosensory sensor device having the chemosensory sensor chip of the present invention, and a differential potential value pattern based on the working electrode potential values obtained from a plurality of working electrodes is obtained. .

(experimental method)
-The solution below the basic taste sample solution was prepared.
(A) The salty basic taste sample solution is 300 mM KCl, and 0.3 mM tartaric acid,
(B) sour basic taste sample solution is 30 mM KCl, and 3 mM tartaric acid,
(C) The basic taste sample solution of umami is 30 mM KCl, 0.3 mM tartaric acid, and 10 mM MSG.
(D) The basic taste sample solution of bitterness is 30 mM KCl, 0.3 mM tartaric acid, and 0.1 mM quinine hydrochloride (quinine-HCl),
Are mixed. Also,
(E) The basic solution is a mixture of 30 mM KCl solution and 0.3 mM tartaric acid.

-Preparation method of chemosensory sensor chip Example 1 was followed. The components of the lipid polymer membrane of each working electrode are as follows.
(Channel 1) Lipid molecule: 2C10, Plasticizer: DOPP, Polymer support member: PVC
(Channel 2) Lipid molecule: TDAB, plasticizer: DOPP + TDA, polymer support member: PVC
(Channel 3) Lipid molecule: TOMA, Plasticizer: DOPP + DOP, Polymer support member: PVC
(Channel 4) Lipid molecule: TDAB, plasticizer: DOPP, polymer support member: PVC

Measurement Method First, a chemosensory sensor chip mounted on the chemosensory sensor device of Embodiment 3 was immersed in the basic solution. The potential of the solution was stabilized, and the reference electrode potential value bV ₀ and the working electrode potential value bVi (i is each channel number: 1, 2, 3, 4) at that time were measured. Next, after washing the electrode with the basic solution as a washing solution, the electrode is immersed in the basic taste sample solution of (a), and the reference electrode potential value V ₀ and the working electrode potential value Vi when the potential is stabilized with the solution are obtained. Each was measured. After washing the sensor with the washing solution, the same operation was sequentially performed on each of the basic taste sample solutions (b) to (d). Each obtained potential value was amplified by an amplifier in the same manner as in Example 2, and then input to DAQ card 6036E (National Instrument) and sent to a PC which is an external electronic device. The potential value data sent to the PC was processed by LabVIEW 7.0 software (National Instrument). In this process, the difference potential value ΔVi of each basic taste sample was calculated by ΔVi = (Vi−V ₀ ) − (bVi−bV ₀ ). A difference potential value pattern of each basic taste sample was created from the obtained difference potential values.

  (Result) FIG. 14 shows the result of the differential potential value pattern of this example. ■ Plot pattern (1401) is salty, ● Plot pattern (1402) is sour, ◆ Plot pattern (1403) is umami, ▼ Plot pattern (1404) is bitter, differential potential obtained from basic taste sample solution Represents a value pattern. The difference potential value pattern of the basic taste sample based on the working electrode potential value obtained from each working electrode showed almost the same tendency as the conventional taste sensor device (INSENT: taste recognition device SA402B). This indicates that the chemosensory sensor device of the present invention can perform the same function as the conventional taste sensor device for basic taste substances, confirming the practicality of the chemosensory sensor device of the present invention. . In the chemosensory sensor device according to the fourth embodiment, the differential potential value pattern of these basic taste substances is accumulated in the accumulation unit, and then the differential potential value pattern obtained when measuring the measurement target substance with unknown chemical characteristics. And the comparison unit can determine the chemical characteristics of the unknown substance to be measured.

<Measurement experiment for basic taste concentration change with chemosensory sensor device>

  (Objective) The potential value when the concentration of the basic taste substance is changed by the chemosensory sensor device having the chemosensory sensor chip of the present invention is measured, and the working electrode potential value obtained from each concentration at each working electrode A differential potential value pattern based on is obtained.

  (Experimental method) It carried out according to the said Example 4. The basic taste sample solutions are 0.001 times, 0.01 times, 0.1 times, 10 times, and 100 times the concentration sample solutions of Example 4 with the basic taste sample solutions (a) to (d) as 1. Prepared. The basic solution is the same as in Example 4. First, the potential value in the basic solution was obtained from each electrode. Then, the measurement probe was moved from the low concentration of each basic taste sample solution to the high concentration, and the potential value at each concentration was obtained. When the measurement probe was moved, the basic taste sample solution having a pre-concentration adhered to the solution immersion portion of the probe was washed with a washing solution. The difference potential value of each concentration obtained in each working electrode (channels 1 to 4) was calculated, and a difference potential value pattern with respect to the concentration change was created for each working electrode. In addition, the working electrode of a present Example has not necessarily measured with respect to all the basic taste sample solutions (a) to (d) of Example 4. In addition, a basic taste sample solution having a certain concentration may be measured twice or more using the same working electrode.

  (Result) FIG. 15 shows the result of the difference potential value pattern of each concentration based on the working electrode potential value generated from each working electrode of this example. When a basic taste sample solution having a certain concentration was measured twice or more using the same working electrode, all of them were plotted, and the average value was plotted as a differential potential value pattern. The plot shapes in each graph represent the differential potential values obtained from the basic taste sample solution, where the plot is salty, the plot is sour, the plot is umami, and the plot is bitter. Graph I shows the differential potential values for the working electrode channel 1, graph II for the working electrode channel 2, graph III for the working electrode channel 3, and graph IV for the working electrode channel 4 with respect to the concentration change of each basic taste sample solution. A differential potential value pattern is shown. All of these differential potential value patterns showed almost the same tendency as the conventional taste sensor device (INSENT: taste recognition device SA402B). Therefore, it has been shown that the chemosensory sensor device of the present invention can perform the same function as the conventional taste sensor device even with respect to the concentration change of the basic taste substance, and the chemosensory sensor device of the present invention is further practically used. The sex was confirmed.

The conceptual diagram of the reference electrode for chemosensory sensors of Embodiment 1. FIG. The conceptual diagram of the chemosensory sensor chip of Embodiment 2. FIG. FIG. 3 is a cross-sectional configuration diagram of a chemosensory sensor chip according to a second embodiment. The conceptual diagram which shows the shape of the support body of Embodiment 2. FIG. FIG. 5 is a conceptual diagram of a chemosensory sensor device according to a third embodiment. FIG. 6 is a conceptual diagram of a configuration of a chemical sensory sensor device according to a third embodiment. 10 is a flowchart of processing according to the third embodiment. The conceptual block diagram of the chemosensory sensor apparatus of Embodiment 4. 10 is a flowchart of processing according to the fourth embodiment. The conceptual diagram of the preparation methods of the glass substrate which has arrange | positioned the conductor of a chemical sensory sensor chip. The conceptual diagram of the preparation methods of the isolation part of a chemical sensory sensor chip. The measurement result of Example 2. The measurement result of Example 3. The measurement result of Example 4. The measurement result of Example 5.

Explanation of symbols

0300: Chemosensory sensor chip 0301: Support body 0302: Working electrode 0303: Reference electrode for chemosensory sensor 0304: Isolation part 0305: Second conductor 0306: Lipid polymer membrane Fig. 6-a: External electron such as PC Fig. 6-b: Object to be measured Fig. 8-a: External electronic device such as PC Fig. 8-b: Object to be measured Fig. 15-I: Working electrode potential generated from working electrode channel 1 at each concentration Result of differential potential value pattern based on value.
FIG. 15-II: the result of the differential potential value pattern based on the working electrode potential value generated from the working electrode channel 2 at each concentration.
FIG. 15-III: the result of the differential potential value pattern based on the working electrode potential value generated from the working electrode channel 3 at each concentration.
FIG. 15-IV: the result of the differential potential value pattern based on the working electrode potential value generated from the working electrode channel 4 at each concentration.

Claims (18)

A first conductor;
A wetting layer holding an electrolyte capable of charge exchange with the first conductor in a wetting material;
A charge exchange preventing layer that prevents the electrolyte retained in the wet layer from exchanging charges with external ions;
An electrolyte leakage preventing layer for preventing the electrolyte retained in the wet layer from leaking to the outside;
A reference electrode for a chemosensory sensor.   The reference electrode for a chemosensory sensor according to claim 1, wherein the wetting material of the wetting layer is a polymer.   The reference electrode for a chemosensory sensor according to claim 1 or 2, wherein the electrolyte solution of the wet layer is a KCl solution.   The reference electrode for a chemosensory sensor according to any one of claims 1 to 3, wherein the first conductor is Ag or Ag / AgCl.   The reference electrode for a chemosensory sensor according to claim 4, wherein the electrolyte of the wet layer is a mixed solution of KCl and AgCl.   The reference electrode for a chemosensory sensor according to any one of claims 1 to 5, wherein the charge exchange preventing layer comprises a polymer film material and a plasticizer.   The reference electrode for a chemosensory sensor according to any one of claims 1 to 6, wherein the electrolyte leakage preventing layer is formed of a reverse osmosis membrane.   The reference electrode for a chemosensory sensor according to any one of claims 1 to 7, wherein the charge exchange prevention layer and the electrolyte leakage prevention layer are formed of a single layer having both functions. A support;
At least one working electrode formed on the support and having a second conductor and a lipid polymer membrane capable of charge exchange between the second conductor;
One or more chemosensory sensor reference electrodes according to any one of claims 1 to 8, formed on the support;
An isolating portion for electrically isolating the working electrode from the chemosensory sensor reference electrode;
Chemosensory sensor chip having   The chemosensory sensor chip according to claim 9, wherein when there are two or more working electrodes, each working electrode has a lipid polymer film that exhibits a different response to one chemical substance from another working electrode.   The isolation part is a wall-like insulator provided around the first conductor and the second conductor, and the reference electrode for the chemosensory sensor contacts the object to be measured by the wall-like insulator. The chemosensory sensor chip according to claim 9 or 10, wherein only the electrolytic leakage prevention layer is left as a region, and the working electrode is configured to leave only the lipid polymer film as a contact region with an object to be measured.   The chemosensory sensor chip according to claim 11, wherein the wall insulator is formed by exposing photosensitive glass to an acid treatment after heat treatment. A measurement probe comprising the chemosensory sensor chip according to any one of claims 9 to 12,
A reference electrode potential value acquisition unit that acquires a potential value from a reference electrode of a chemosensory sensor chip in the measurement probe;
A working electrode potential value acquisition unit for acquiring a potential value from each of one or more working electrodes of the chemosensory sensor chip in the measurement probe;
A differential potential value acquisition unit that acquires a difference value between the potential value for each working electrode acquired by the working electrode potential value acquisition unit and the potential value acquired by the reference electrode potential acquisition unit;
A differential potential value output unit that outputs the differential potential value acquired by the differential potential value acquisition unit for each working electrode, and that outputs a differential potential value pattern obtained based on the working electrode potential value;
A chemical sensory sensor device. An accumulator that accumulates a known differential potential value pattern for each working electrode of a known chemical substance;
A comparison unit that compares the differential potential value pattern output from the differential potential value output unit with the known differential potential value pattern stored in the storage unit;
A determination unit for determining chemical characteristics of the measurement object measured by the measurement probe based on the comparison result in the comparison unit;
The chemosensory sensor device according to claim 13, comprising:   The chemosensory sensor device according to claim 13 or 14, wherein the measurement probe has an attaching / detaching part to which the chemosensory sensor chip according to any one of claims 9 to 12 can be attached and detached.   The lipid polymer membrane disposed on one or more working electrodes of the measurement probe is a sweet solution whose pattern consisting of a plurality of potential values generated on one or more working electrodes by the measurement object is the measurement object, The chemosensory sensor device according to any one of claims 13 to 15, which is a lipid polymer film having a different pattern depending on a salty solution, a sour solution, an umami solution, and a bitter solution. In the measurement probe having the chemosensory sensor chip according to any one of claims 9 to 12,
A reference electrode potential value acquisition step of acquiring a potential value from the reference electrode of the chemosensory sensor chip;
A working electrode potential value acquisition step of acquiring a potential value from each of one or more working electrodes of the chemosensory sensor chip;
A differential potential value acquisition step for acquiring a differential value between the potential value for each working electrode acquired in the working electrode potential value acquisition step and the potential value acquired in the reference electrode potential acquisition step;
A differential potential value output step for outputting the differential potential value acquired in the differential potential value acquisition step for each working electrode;
A method for measuring a sensory sensory sensor system. Following the differential potential value output step,
A comparison step of comparing a potential difference value pattern for each working electrode output from the differential potential value output step with a known differential potential value potential value pattern acquired and stored from a known chemical substance;
A determination step of determining chemical characteristics of the measurement object measured by the measurement probe based on the comparison result in the comparison step;
The method for measuring a chemosensory sensor system according to claim 17, further comprising:
An accumulation step for accumulating

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