WO2012017605A1 - 一酸化窒素検出エレメント及びその製造方法 - Google Patents
一酸化窒素検出エレメント及びその製造方法 Download PDFInfo
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- WO2012017605A1 WO2012017605A1 PCT/JP2011/003986 JP2011003986W WO2012017605A1 WO 2012017605 A1 WO2012017605 A1 WO 2012017605A1 JP 2011003986 W JP2011003986 W JP 2011003986W WO 2012017605 A1 WO2012017605 A1 WO 2012017605A1
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- WIPO (PCT)
- Prior art keywords
- nitric oxide
- element according
- detection
- detection element
- cobalt
- Prior art date
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- Y10T436/177692—Oxides of nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
- Y10T436/25875—Gaseous sample or with change of physical state
Definitions
- the present invention relates to a nitric oxide detection element used for detecting a minute amount of nitric oxide contained in a mixed gas, and a method for manufacturing the same.
- NO nitric oxide
- NO gas analysis in exhaled breath is attracting attention as a marker of airway inflammation caused by asthma and allergies that have been increasing in recent years.
- a non-invasive disease diagnosis can be performed without burdening the patient.
- the NO gas concentration in exhaled breath is 2 ppb to 20 ppb in normal adults, but is known to increase about 3 times during airway inflammation such as asthma and allergy.
- the NO gas concentration in the exhalation of children is lower than the NO gas concentration of normal adults. Therefore, it is necessary to measure a minute amount of NO gas concentration in exhaled breath. If a small and simple measuring device capable of measuring a trace concentration of NO gas can be realized, it can be used for determining the degree of airway inflammation of a patient and determining treatment guidelines for asthma such as the dosage of an asthma drug.
- Co ⁇ T tetrasulfothienylporphyrin cobalt
- ethyl silicate is slowly hydrolyzed in the presence of Co ⁇ T (S-ST) P ⁇ over 24 hours, and the resulting solution is placed on a glass substrate. And dried to form an amorphous silica film containing Co ⁇ T (S-ST) P ⁇ . Using the film as a NO sensor, 17 ppm NO gas was successfully detected at a sensor temperature of 200 ° C.
- the porous glass plate is dipped in a chloroform solution of tetraphenylporphyrin cobalt (5,10,15,20-tetraphenyl-21H, 23H-porphine cobalt: hereinafter referred to as CoTPP) and then dried so that the CoTPP is porous.
- CoTPP tetraphenylporphyrin cobalt
- a conventional sensor using an amorphous silica film or a porous glass plate and porphyrin by a sol-gel method it is possible to detect a small amount of NO gas with high sensitivity.
- the porphyrin that is the detection agent is contained in the amorphous silica film or is supported in the fine pores on the surface of the porous glass plate, so that NO gas from the detection agent is absorbed. Adsorption and desorption takes time, and there is a problem that when detecting a very small amount of NO gas of a few tens of ppb level, the response time becomes long and detection at high speed is impossible.
- the present invention provides a nitric oxide detection element capable of detecting at high speed even a very small amount of NO gas of a dozen ppb level contained in a mixed gas, and a method for manufacturing the same. Objective.
- the present invention is a nitric oxide detection element comprising a substrate and a detection film formed on the surface of the substrate,
- the detection film is composed of nitric oxide detection particles and a polymer adhesive
- the present invention relates to a nitric oxide detecting element, wherein the nitric oxide detecting particle is formed by adsorbing a pigment having a porphyrin skeleton and having divalent cobalt as a central metal on the surface of an inorganic particle.
- the nitric oxide detection element of the present invention even a very small amount of NO gas of several ppb to several tens of ppb can be detected at high speed and with high accuracy. This is considered to be due to the following reason.
- cobalt porphyrin is adsorbed on the surface of the inorganic particles, and this is fixed to the substrate surface with a polymer adhesive, so that it is easy for NO gas to approach cobalt porphyrin. Therefore, not the diffusion of NO gas, but the reaction on the particle surface becomes the rate-determining step, and the coordination bond accompanying the charge transfer between cobalt, which is the central metal of porphyrin, and NO gas can be increased rapidly.
- the present invention also provides the nitric oxide detection element, A gas introduction part for bringing the detection film surface of the nitric oxide detection element into contact with a measurement gas that may contain nitric oxide;
- the present invention also relates to a nitric oxide detection device including a light projecting unit that irradiates light to the detection film, and a light receiving unit that receives light reflected from the detection film or transmitted through the detection film.
- the present invention further includes a first step of initializing the nitric oxide detection element; After the first step, a second step of irradiating the detection film of the nitric oxide detection element with light and measuring the light absorption rate of the detection film; After the second step, the third step of contacting the detection film with a measurement gas that may contain nitric oxide; After the third step, a fourth step of irradiating the detection film with light and measuring the light absorption rate of the detection film; A fifth step of determining the concentration of nitric oxide contained in the measurement gas by comparing the light absorption rate obtained in the fourth step with the light absorption rate obtained in the second step. It also relates to a method for detecting nitric oxide.
- the present invention comprises a step of applying a polymer adhesive solution obtained by dissolving a polymer adhesive in a first solvent to the substrate surface; Nitric oxide detection in which the dye is adsorbed on the surface of the inorganic particles by mixing a dye having a porphyrin skeleton and having divalent cobalt as a central metal, inorganic particles, and a second solvent.
- a polymer adhesive solution obtained by dissolving a polymer adhesive in a first solvent to the substrate surface
- Nitric oxide detection in which the dye is adsorbed on the surface of the inorganic particles by mixing a dye having a porphyrin skeleton and having divalent cobalt as a central metal, inorganic particles, and a second solvent.
- Producing a preparation containing particles and the second solvent Adding the preparation to the polymer adhesive solution applied to the substrate surface; Drying the first solvent and the second solvent, and forming a sensing film comprising the nitric oxide sensing particles and the polymer adhesive on the substrate. It also
- nitric oxide detection element of the present invention even a very small amount of NO gas of several ppb to several tens of ppb can be detected at high speed and with high accuracy.
- the conceptual diagram which shows the structure of the nitric oxide detection apparatus containing the nitric oxide detection element of this invention.
- Cross-sectional conceptual diagram of the nitric oxide detection element of the present invention Enlarged conceptual diagram showing the relationship of materials constituting the detection film 11 Ultraviolet / visible light reflection spectrum of the nitric oxide detection element of the present invention
- the graph which shows the change of the light reflectance before and behind exposing the nitric oxide detection element of this invention to 1 ppm-NO gas.
- the graph which shows the relationship between the light absorption rate, NO sensitivity, and NO response time measured by exposing the nitric oxide detecting element of the present invention to 1 ppm-NO gas.
- the graph which shows the relationship between the number of cobalt atoms per unit area, NO sensitivity, and NO response time measured by exposing the nitric oxide detecting element of the present invention to 1 ppm-NO gas
- the graph which shows the relationship between NO / sensitivity and NO response time of the molar / weight ratio of the pigment
- the graph which shows the relationship between NO / sensitivity and NO response time, the molar / weight ratio of the pigment
- the graph which shows the relationship between the weight ratio of the nonionic surfactant with respect to an inorganic particle, NO sensitivity, and NO response time measured by exposing the nitric oxide detection element of this invention to 1 ppm-NO gas.
- the flowchart which shows the manufacturing process of the nitric oxide detection element of this invention.
- the graph which shows the relationship between sensor temperature, NO sensitivity, and NO response time measured by exposing the nitric oxide detecting element of the present invention to 1 ppm-NO gas
- nitric oxide detection element of the present invention and the manufacturing method thereof will be described based on each embodiment.
- FIG. 1 is a conceptual diagram showing a configuration of a nitric oxide detection device including a nitric oxide detection element 10A of the present invention.
- the nitric oxide detection element 10 ⁇ / b> A includes a base 12 such as a transparent plastic substrate and a detection film 11 fixed on the surface of the base 12.
- the detection film is composed of inorganic particles having a dye adsorbed on the surface, a polymer adhesive, and preferably a nonionic surfactant.
- the dye is, for example, tetramethoxyphenylporphyrin cobalt CoTP (OCH 3 ) 4 P (manufactured by Tokyo Chemical Industry Co., Ltd.) having divalent cobalt as the central metal.
- As the inorganic particles for example, NIPGEL (trademark) manufactured by Tosoh Silica Co., Ltd. can be used.
- the polymer adhesive is, for example, hydroxypropylcellulose (manufactured by Sigma-Aldrich, referred to as HPC).
- HPC hydroxypropylcellulose
- the nonionic surfactant is, for example, Triton X-100 (trademark, manufactured by GE Healthcare UK Ltd).
- the nitric oxide detection element 10A is disposed in the measurement cell 13.
- a measurement gas 30 that may contain nitric oxide (NO) is introduced into the measurement cell 13 from the gas inlet 14 and discharged from the gas outlet 15. In this process, the surface of the detection film 11 is exposed to the measurement gas 30.
- NO nitric oxide
- the nitric oxide measuring device shown in FIG. 1 is a light reflection type.
- the light projecting / receiving unit 18 is opposed to the nitric oxide detection element 10A. It is attached.
- the light projecting / receiving unit 18 is connected to the light source 16 through an optical fiber 20 and is connected to the light detecting unit 17 through another optical fiber 21.
- Light emitted from the light source 16 (preferably light including an optical wavelength of 400 nm to 450 nm) is irradiated from the light receiving unit 18 perpendicularly to the detection film 11 of the nitric oxide detection element 10A.
- the light reflected from the surface of the detection film 11 enters the light projecting / receiving unit 18 and is guided to the light detection unit 17.
- the light detection unit 17 includes, for example, a diffraction grating such as a prism or a grating and a CCD. Further, the light detection unit 17 may include an optical bandpass filter, a silicon photodiode, a photocurrent / voltage conversion circuit, and an amplification circuit (not shown). The detection light is converted into a light detection signal corresponding to the amount of reflected light and measured in any configuration of the light detection unit 17 described above.
- a temperature controller 24 is provided inside the measurement cell 13, whereby the temperature in the measurement cell 13 can be controlled.
- the temperature controller 24 includes a heater and a thermocouple for temperature detection (not shown).
- the light source 16, the light detection unit 17, and the temperature controller 24 are connected to the measurement controller 19 via control lines 22, 23, and 25, respectively, in order to control their operations.
- the configuration in which the light projecting unit and the light receiving unit are integrated has been described.
- the light projecting unit and the light receiving unit may be provided separately.
- the substrate is made of a material that transmits
- the light projecting unit and the light receiving unit can be placed facing each other with the nitric oxide detection element 10A interposed therebetween.
- FIG. 2 is a conceptual cross-sectional view of the nitric oxide detection element 10A.
- the detection film 11 is fixed to the surface of the substrate 12.
- the surface of the substrate 12 is patterned in advance and is divided into a detection film part 111 and a peripheral part 112.
- the detection film 11 is formed on the detection film unit 111.
- FIG. 3 is an enlarged conceptual diagram showing the relationship of materials constituting the detection film 11 of FIG.
- dye 102 is carry
- the pigment 102 is preferably agglomerated by the presence of the nonionic surfactant 104, dispersed, and supported on the surface of the inorganic particles 101.
- the nitric oxide detection particles 100 are combined with each other by the polymer adhesive 103 to form a detection film 11. And the detection film
- the weight of the nitric oxide detection particles 100 per unit area of the substrate 12 is preferably 0.2 mg / cm 2 to 2.0 mg / cm 2 . If it is less than 0.2 mg / cm ⁇ 2 >, the change of the optical spectrum with respect to a trace amount of NO gas will decrease, and NO sensitivity will be insufficient. If it exceeds 2.0 mg / cm 2 , the adhesion of the detection film 11 becomes weak, and cracks are likely to occur in the detection film 11.
- a dye 102 made of a porphyrin complex is used.
- the porphyrin complex is a complex having a porphyrin skeleton and having a metal at the center of the porphyrin skeleton.
- the porphyrin skeleton may be modified with various substituents.
- the absorption spectrum of a porphyrin complex has a Soret band (also called B-band) absorption in the optical wavelength region of 400 nm to 450 nm (ultraviolet light region) and a Q band absorption in the optical wavelength region of 500 nm or more (visible light region).
- Soret band also called B-band
- Q band absorption in the optical wavelength region of 500 nm or more (visible light region).
- the redox potential of the central metal affects the binding between the central metal of the porphyrin complex and NO gas.
- the molar extinction coefficient of the Soret band is about 10 5 (M ⁇ 1 ⁇ cm ⁇ 1 ) and the molar extinction coefficient of the Q band is about 10 3 (M ⁇ 1 ⁇ cm ⁇ 1 ). -1 ).
- the molar extinction coefficient has a relationship that increases in proportion to the NO sensitivity, that is, the NO gas concentration.
- the absorption in the Q band is less affected by the molecular structure of the porphyrin complex than the absorption in the Soret band, but the molar extinction coefficient is as low as 10 4 (M ⁇ 1 ⁇ cm ⁇ 1 ) or less.
- the central metal of the porphyrin complex is selected, and (2) the macrocyclic ⁇ -conjugated system at the center of the porphyrin structure is changed by changing the substituent of the porphyrin skeleton. It is conceivable to donate an electron (donating property) or attract a ⁇ -conjugated electron (attracting property).
- porphyrin complex having divalent cobalt as a central metal is used. It is presumed that the difference in reactivity with NO gas exhibited by porphyrin complexes having various metals depends on the difference between the oxidation-reduction potential of the central metal and the oxidation-reduction potential of NO gas.
- X1, X2, X3, and X4 each represent hydrogen (—H), a methoxy group (—OCH 3 ), or a hydroxyl group (—OH).
- CoTP (Xi) P represented by the above formula is a porphyrin complex having divalent cobalt as a central metal, and has four phenyl groups outside the porphyrin skeleton.
- Xi (i is an integer of 1 to 4) represents a substituent bonded to the phenyl group, and is any one selected from hydrogen (—H), methoxy group (—OCH 3 ), and hydroxyl group (—OH). It is the basis of.
- Xi -H
- Tetramethoxyphenylporphyrin cobalt 5,10,15,20-tetra (4-methoxyphenyl) -21H, 23H-porphine cobalt (CoTP (4-OCH 3 ) P)
- the same effect can be acquired even if it uses the mixture of both compounds. Both compounds are soluble in a halogen-based solvent which is a second solvent described later.
- the cobalt porphyrin complex is tetrahydroxyphenylporphyrin cobalt (5,10,15,20-tetra (4-hydroxyphenyl) -21H, 23H-porphine cobalt (CoTP (4-OH) P)).
- This porphyrin is soluble in an alcohol solvent that is a second solvent described later.
- the nonionic surfactant 104 can be used to suppress aggregation of the dye 102 and sufficiently disperse it.
- the nonionic surfactant has a hydrophilic-lipophilic balance (HLB value: a numerical value indicating the degree of affinity of the surfactant to water and oil) of 13 to 15. What shows the following is preferable.
- HLB value a numerical value indicating the degree of affinity of the surfactant to water and oil
- a hydrophilic nonionic surfactant and a lipophilic nonionic surfactant are mixed at an appropriate composition ratio to form a nonionic surfactant mixture exhibiting an HLB value suitable for use in the present invention. It is also possible to use this.
- TWEEN 80 manufactured by Tokyo Chemical Industry
- SPAN80 manufactured by Tokyo Chemical Industry
- performance equivalent to that of the Triton X-100 can also be achieved.
- the inorganic particles 101 are not particularly limited, but inorganic particles such as silica or ⁇ -alumina are preferable. Silica and ⁇ -alumina may be mixed and used together.
- the inorganic particles are preferably used after being subjected to water repellent treatment.
- a method for water-repellent treatment of inorganic particles a conventionally known method may be used.
- the water-repellent treated inorganic particles 101 can be obtained by chemically reacting the silane coupling agent and the particles or by boiling the particles with silicone oil.
- the degree of water repellency of these water-repellent treated particles can be confirmed with an infrared spectrometer.
- silica particles sharp infrared absorption derived from silanol groups (—Si—OH) is observed in the vicinity of a wave number of 3540 cm ⁇ 1, and the degree of water repellent treatment can be determined by the degree of the infrared absorption.
- the inorganic particles subjected to the water repellent treatment in the present invention when used, when the inorganic particles are mixed with the solvent in the manufacturing process of the nitric oxide detecting element, the inorganic particles are well dispersed in the solvent and are difficult to settle. Therefore, since the dye 102 is sufficiently dispersed and hardly aggregated, the NO sensitivity of the manufactured nitric oxide detection element can be further increased.
- the inorganic particles 101 preferably have a particle diameter of 6 ⁇ m to 12 ⁇ m.
- the particle size can be measured with a known particle size distribution measuring device, for example, a particle size distribution measuring device LA-950 (manufactured by Horiba, Ltd.).
- the upper limit and the lower limit of the particle diameter are the lower limit cumulative frequency median 10% diameter and the upper limit cumulative frequency median 90 in the cumulative frequency distribution curve of the particle size distribution obtained by a method according to JIS K 5600-9-3 (2006). It shall be read as% diameter.
- Either silica or ⁇ -alumina within the above particle diameter range, or mixed particles thereof can be preferably used in the present invention.
- Particles having a particle diameter of less than 6 ⁇ m have weak adhesion between particles and are easily peeled off, and the adhesion between the substrate 12 and the nitric oxide detection particles 100 tends to be weak.
- the polymer adhesive 103 in order to obtain a certain adhesion force, it is desired to dispose the polymer adhesive 103 between the particles or between the particles and the substrate and further increase the amount of the polymer adhesive used.
- increasing the amount of polymer adhesive increases the NO response time and slows the NO response.
- the particle diameter is preferably 6 ⁇ m or more.
- the particle diameter of the water-repellent treated particles is preferably 6 ⁇ m or more and 12 ⁇ m or less.
- the polymer adhesive 103 acts as an adhesive for adhering the nitric oxide detection particles to form a detection film, and an adhesive for adhering the nitric oxide detection particles to the substrate 12.
- the glass transition temperature (hereinafter referred to as Tg) of the polymer adhesive is preferably ⁇ 150 ° C. to 150 ° C.
- Polymer adhesives in this range are excellent in gas permeability. Due to the excellent gas permeability of the polymer adhesive, the NO response time can be shortened.
- Tg is lower than ⁇ 150 ° C., the adhesion of the detection film 11 to the substrate 12 is deteriorated.
- Tg 150 ° C. is exceeded, the gas permeability of the polymer adhesive is deteriorated and the NO response time is increased.
- the polymer adhesive is transparent to the detection light in producing the detection film of the nitric oxide detection element.
- the detection light it is preferably transparent in the region of the optical wavelength of 400 nm to 450 nm.
- HPC hydroxypropylcellulose
- Tg 19 ° C. to 125 ° C.
- Tg depends on the molecular weight
- the polymer adhesive includes
- the polymer adhesive can be used in combination with a plasticizer for the purpose of improving fluidity.
- a plasticizer for the purpose of improving fluidity.
- the base 12 is a material that exhibits heat resistance, and preferably has a sheet shape made of a material that reflects or transmits detection light.
- the detection light is preferably made of a material that reflects or transmits light having an optical wavelength of 400 nm to 450 nm.
- Such substrates include plastic substrates such as heat-resistant films such as polyethylene terephthalate film (PET), polyethylene naphthalate film (PEN, trademark, made by Teijin DuPont Film), Arton film (ARTON, trademark, JSR Corporation), etc.
- a ceramic substrate such as a glass substrate, a quartz substrate, or an alumina substrate; a metal substrate mainly composed of aluminum or silver; paper, woven fabric, nonwoven fabric, or the like can be used.
- complex which consists of these materials can also be used.
- a metal film mainly composed of silver or aluminum may be provided on the surface of the base 12. By forming the detection film 11 on the metal film, the power consumption of the light source 16 of the light projecting unit can be reduced.
- polymer adhesive solution “HPC” manufactured by Sigma-Aldrich
- alcohol solvents eg, methyl alcohol, ethyl alcohol, isopropyl alcohol,
- a polymer adhesive solution is prepared using a mixed solvent thereof.
- the usable polymer adhesive is not limited to HPC, and any of the compounds listed above can be used.
- the concentration of the polymer adhesive solution is preferably adjusted so that the weight ratio of the polymer adhesive to the inorganic particles described later is 0.07 g / g to 0.20 g / g.
- HPC is dissolved in the first solvent so as to be 6 mg / mL, and the amount of droplets of the polymer adhesive solution and the amount of droplets of the preparation solution containing the dye described below are further determined. adjust.
- Preparation of Preparation Solution Containing Dye dye CoTP (4-OCH 3 ) P [tetramethoxyphenylporphyrin cobalt], water-repellent treated silica particles having a particle diameter of 6 ⁇ m to 12 ⁇ m, and nonionic surface activity
- a preparation is prepared by mixing Triton X-100 having an HLB value of 13.5 as an agent with a halogen-based solvent (for example, chloroform or dichloromethane) as a second solvent.
- a halogen-based solvent for example, chloroform or dichloromethane
- the molar concentration of CoTP (4-OCH 3 ) 4 P in the preparation liquid is 3.3 ⁇ 10 ⁇ 5 mol / L to 3.3 ⁇ 10 ⁇ 4 mol / L, and the concentration of the water-repellent treated silica particles is 10 mg. / ML to 100 mg / mL, and the concentration of the nonionic surfactant is 0.16 mg / mL to 30 mg / mL.
- the molar weight ratio of the dye to the water-repellent treated silica particles is 1.0 ⁇ 10 ⁇ 6 mol / g to 1.0 ⁇ 10 ⁇ 5 mol / g, and the molar weight of the dye and the nonionic surfactant The ratio is 3.0 ⁇ 10 ⁇ 6 mol / g to 3.0 ⁇ 10 ⁇ 4 mol / g, preferably 3.3 ⁇ 10 ⁇ 6 mol / g to 5.9 ⁇ 10 ⁇ 5 mol / g, inorganic
- the weight ratio of nonionic surfactant to particles is 0.05 g / g to 1 g / g.
- Pattern formation on the substrate It is preferable to pattern the detection film unit 111 on the surface of the substrate 12 in advance. By forming the pattern, variation in the area of the detection film can be reduced, so that a minute amount of nitric oxide gas can be accurately measured.
- pattern formation photolithography or printing process used in a semiconductor process can be used, but is not limited thereto.
- the peripheral portion 112 surrounding the detection film portion is lyophobic and the detection film portion 111 is lyophilic.
- the detection film 11 can be formed with high accuracy, and thereby variation in the NO sensitivity of the detection film 11 can be reduced.
- the peripheral portion 112 is covered with a photoresist or metal, only the detection film portion 111 is exposed, and the detection film portion is mixed with a mixed gas containing oxygen gas as a main component.
- a method of forming unevenness on the surface of the detection film portion 111 by performing plasma etching There is also a method (ii) of forming a fluororesin film such as FS-1010 (trademark, Fluoro Technology Co., Ltd.) or a silicone oil film on the peripheral portion 112.
- a fluororesin film such as FS-1010 (trademark, Fluoro Technology Co., Ltd.) or a silicone oil film on the peripheral portion 112.
- a method of using a PEN film substrate as the substrate 12 and forming an FS-1010 fluororesin film on the peripheral portion 112 is preferable.
- any of the above methods can easily make the detection film portion 111 lyophilic as compared with the peripheral portion 112.
- the surface property of the substrate 12 can be confirmed by, for example, using a FACE contact angle meter of type CA-C manufactured by Kyowa Interface Science Co., Ltd. and dropping pure water onto the surface and measuring the contact angle.
- the pure water contact angle on the fluororesin film in the peripheral portion 112 is 115 ° to 118 °
- the pure water contact angle of the detection film portion 111 on the PEN substrate is 70 ° to 80 °.
- a liquid containing a polymer adhesive is dropped by dropping the polymer adhesive solution adjusted in (1) onto the sensing film part 111 that has been previously patterned.
- a droplet film is formed. Specifically, 10 ⁇ L to 30 ⁇ L of a polymer adhesive solution (for example, methyl alcohol in which HPC is dissolved) is dropped on the detection film portion 111 patterned to have a diameter of 8 mm.
- a polymer adhesive solution for example, methyl alcohol in which HPC is dissolved
- the first solvent constituting the polymer adhesive solution does not spread beyond the boundary between the liquid-repellent peripheral portion 112 and the lyophilic detection film portion 111, so that there is little area variation.
- a polymer adhesive droplet film can be realized.
- the droplet film formed by dropping may be semi-dried or completely dried.
- the detection film 11 is formed by air-drying and solidifying the liquid droplet detection film on the substrate 12.
- the temperature and humidity conditions at the time of drying are not particularly limited, and may be air-dried (room temperature and relative humidity 50%) under conditions that do not cause alteration of the substrate, the polymer adhesive, and the dye, or may be room temperature or higher. Temperature conditions may be sufficient and the heating conditions on a hotplate may be sufficient.
- the dropping amount of the polymer adhesive solution and the dye-containing preparation solution is preferably adjusted so that the weight ratio of the polymer adhesive to the inorganic particles is 0.07 g / g to 0.20 g / g.
- the ratio of the polymer adhesive is low, the adhesion between the nitric oxide detection particles is weak, and the particles tend to peel from the nitric oxide detection element.
- the proportion of the polymer adhesive increases, the NO response time of the detection film 11 tends to increase, although the adhesive force increases.
- FIG. 4 is a graph showing an ultraviolet / visible light reflection spectrum measured with a spectrophotometer MCPD7000 (manufactured by Otsuka Electronics Co., Ltd.) when CoTP (4-OCH 3 ) P is used as a dye.
- the sensor temperature is set to 150 ° C. by the temperature controller 24 while flowing nitrogen gas (flow rate 100 mL / min) through the nitric oxide detection element 10A, and heat treatment is performed for 10 minutes.
- an absorption band having a central wavelength of 413 nm derived from CoTP (4-OCH 3 ) P (hereinafter referred to as Co (II) TP (4-OCH 3 ) P) having divalent cobalt as a central metal. Is obtained (the spectrum described as “after initialization” in FIG. 4).
- Co CoTP (4-OCH 3 ) P
- Co Co TP (4-OCH 3 ) P
- An absorption band having a central wavelength of 438 nm derived from TP (4-OCH 3 ) P increases.
- the present invention is not limited to the sensor temperature and processing time described above.
- FIG. 5 is a graph showing changes in light reflectance before and after the initialized nitric oxide detection element of the present invention is exposed to NO gas. Specifically, a change in optical reflectance at a wavelength of 413 nm derived from Co (II) TP (4-OCH 3 ) P and a wavelength of 438 nm derived from Co (III) TP (4-OCH 3 ) P). The change of the optical reflectance of is shown.
- the light reflection spectrum of FIG. 4 is standardized assuming that the optical reflectance at a wavelength of 470 nm at which the dye does not react with NO gas is 100%, and the optical wavelength before 413 nm and the optical wavelength of 438 nm before exposure to NO gas, respectively. The value obtained by subtracting the optical reflectance after exposure to NO gas from the optical reflectance is shown.
- the NO gas exposure conditions at the time of measurement are a sensor temperature of 80 ° C., a nitrogen diluted NO gas concentration of 1 ppm-NO, and a flow rate of 200 ml / min.
- a value obtained by subtracting the saturation value of the light reflectance at a wavelength of 438 nm from the saturation value of the light reflectance at a wavelength of 413 nm when exposed to NO gas is referred to as “differential light reflectance”. Since this differential light reflectance depends on the NO concentration, the NO concentration can be determined from the differential light reflectance of CoTP (4-OCH 3 ) P generated by NO exposure.
- CoTP (4-OCH 3 ) P having divalent cobalt exhibiting reactivity with NO gas may be contained in the detection film 11 and CoTP (4-OCH containing divalent cobalt).
- CoTP (4-OCH 3 ) P containing trivalent cobalt may further be contained.
- the nitric oxide detection element 10A produced by the above-described method reacts with oxygen (O 2 ) or carbon monoxide (CO) in the atmosphere, so that Co (III) (4-OCH 3 ) P is a main component. turn into. As it is, the NO concentration cannot be measured with high accuracy. Therefore, it is desirable to perform initialization by heat treatment before measurement.
- the initial stage of the detection film 11 for changing cobalt in CoTP (4-OCH 3 ) P to divalent immediately before measuring NO gas Do.
- initialization in addition to the initialization by the heat treatment, there are light irradiation to the detection film 11 and electromagnetic irradiation such as microwaves, and these means may be combined.
- CoTP (4-OCH 3 ) P When CoTP (4-OCH 3 ) P is heated, gases such as O 2 and CO bonded to CoTP (4-OCH 3 ) P are desorbed, and cobalt in CoTP (4-OCH 3 ) P is divalent. Reduced to When heating, an inert gas such as N 2 gas or Ar gas, or air may be flowed. By flowing the gas, the desorbed gas such as O 2 and CO can be efficiently removed from the inside of the measurement cell 13.
- gases such as O 2 and CO bonded to CoTP (4-OCH 3 ) P are desorbed, and cobalt in CoTP (4-OCH 3 ) P is divalent.
- an inert gas such as N 2 gas or Ar gas, or air may be flowed. By flowing the gas, the desorbed gas such as O 2 and CO can be efficiently removed from the inside of the measurement cell 13.
- the heating temperature and heating time by the temperature controller 24 may be set so that the heat treatment can be performed quickly without deterioration of the dye, polymer adhesive and substrate.
- the range of the sensor temperature in the heat treatment is preferably 50 ° C. to 200 ° C.
- the heating temperature for initialization is less than 50 ° C.
- the time for the heat treatment becomes longer as the heating temperature decreases.
- the sensor temperature exceeds 200 ° C., the polymer adhesive is deteriorated.
- FIG. 6 is a graph showing the relationship between the light absorption rate after the heat treatment initialization, the NO sensitivity, and the NO response time.
- the NO sensitivity has a linear relationship with the differential light reflectance.
- the differential light reflectance on the vertical axis in FIG. 5A is a value obtained by subtracting (saturated value of reflectance at wavelength 413 nm) from (saturated value of reflectance at wavelength 413 nm) in FIG. 5 at the time of NO exposure. is there.
- This light absorptance reflects the amount of CoTP (4-OCH 3 ) P supported physically adsorbed on the inorganic particles. That is, if the light absorption rate is small, the carrying amount is small, and if the light absorption rate is large, the carrying amount is large.
- the vertical axis of FIG. 5B is the NO response time, and is the required time (seconds) of 10% to 90% of the difference light reflectance change at the wavelength of 413 nm in FIG.
- the differential light reflectance corresponding to NO sensitivity is set to 5% or more (first threshold), and the NO response time (10% ⁇ 90% value) was set to 20 seconds or less (second threshold).
- the flow rate of exhalation is defined as 3000 mL / min. Since the measurement conditions of the present embodiment are a flow rate of 200 mL / min, the collision probability between NO gas and divalent cobalt is increased 15 times at the flow rate specified in the asthma guidelines. Therefore, when the NO response time of 20 seconds in the present embodiment is converted into the guideline condition, it becomes about 1.3 seconds.
- the above set values are set as required performance of the nitric oxide detection element excellent in asthma determination, and do not mean that the nitric oxide detection element cannot be used unless these set values are satisfied.
- the amount of CoTP (4-OCH 3 ) P supported on the inorganic particles of the present invention has a light absorption rate after initialization (maximum light absorption rate) of 10 at an optical wavelength of 400 nm to 450 nm (Soret band). The supported amount is preferably from 30% to 30%.
- FIG. 7 shows the relationship between the number of cobalt atoms per unit area of the substrate surface, NO sensitivity, and NO response time in the nitric oxide detection element of the present invention.
- the number of cobalt atoms on the substrate surface can be measured with a known secondary ion mass spectrometer (referred to as SIMS).
- SIMS secondary ion mass spectrometer
- the surface area of the substrate is defined by the pattern formation described above, and the number of cobalt atoms per unit area of the substrate surface changed by changing the CoTP (4-OCH 3 ) P concentration in the preparation solution is shown on the horizontal axis.
- FIG. 6A shows that the number of cobalt atoms needs to be 1 ⁇ 10 15 atoms / cm 2 or more in order to satisfy the first threshold value of NO sensitivity.
- FIG. 5B shows that the number of cobalt atoms is required to be 1 ⁇ 10 16 atoms / cm 2 or less in order to satisfy the second threshold value of the NO response time.
- the number of cobalt atoms per unit area on the substrate surface is preferably 1 ⁇ 10 15 atoms / cm 2 to 1 ⁇ 10 16 atoms / cm 2 .
- FIG. 8 shows the relationship between the molar / weight ratio of CoTP (4-OCH 3 ) P to the water-repellent treated silica particles, NO sensitivity and NO response time in the nitric oxide detection element of the present invention.
- the data was obtained by changing the amount of the prepared liquid drop onto the PEN substrate having the detection film part having a diameter of 8 mm to 10 ⁇ L, 20 ⁇ L, or 30 ⁇ L.
- the vertical axis represents the differential light reflectance
- the horizontal axis represents the mole / weight ratio (mol / g) of CoTP (4-OCH 3 ) P to the water-repellent treated silica particles.
- FIG. 6A the vertical axis represents the differential light reflectance
- the horizontal axis represents the mole / weight ratio (mol / g) of CoTP (4-OCH 3 ) P to the water-repellent treated silica particles.
- the vertical axis is the NO response time, and the horizontal axis is the same as FIG.
- the mole ratio / weight ratio of CoTP (4-OCH 3 ) P to the water-repellent treated silica particles is 1.0 ⁇ 10 ⁇ 6 mole / It can be seen that a loading amount of g or more is necessary. It can also be seen that when the dropping amount is 10 ⁇ L and the mole / weight ratio is low, the dispersibility is poor and the NO sensitivity is lowered.
- the mole / weight ratio needs to be 1.0 ⁇ 10 ⁇ 5 mol / g or less in order to satisfy the second threshold value of the NO response time.
- the NO response time tends to increase. This is presumably because the NO response takes time because the dye aggregates as the amount of the dye supported increases.
- FIG. 9 shows the relationship between the molar / weight ratio of CoTP (4-OCH 3 ) P to nonionic surfactant, NO sensitivity, and NO response time in the nitric oxide sensing element of the present invention.
- the figure also shows data on a nitric oxide detection element produced without using water-repellent treated silica particles.
- FIG. 6A shows that the differential light reflectance, which is NO sensitivity, decreases as the mole / weight ratio increases. This is because the dispersibility of the dye becomes worse and the dye tends to aggregate due to a decrease in the relative amount of the nonionic surfactant used for the dye. From FIG.
- the mole / weight ratio is 3.0 ⁇ 10 ⁇ 6 mol / g to 3.0 ⁇ 10 ⁇ 4 mol / g, preferably Is required to be 3.3 ⁇ 10 ⁇ 6 mol / g to 5.9 ⁇ 10 ⁇ 5 mol / g.
- the use of a nonionic surfactant is not indispensable, and a nitric oxide detection element exhibiting relatively good NO sensitivity and NO response time can be obtained without using it.
- FIG. 10 shows the relationship between the weight ratio of the nonionic surfactant to the water-repellent treated silica particles in the nitric oxide detection element of the present invention, NO sensitivity, and NO response time.
- the figure also shows data on a nitric oxide detection element produced without using water-repellent treated silica particles.
- the preparation conditions of the preparation liquid were as follows: the molar concentration of CoTP (4-OCH 3 ) P was 1 ⁇ 10 ⁇ 6 mol / L to 3.3 ⁇ 10 ⁇ 4 mol / L, and the concentration of water-repellent treated silica particles was 10 ⁇ 100 g / L.
- the amount of dripping onto the detection film part having a diameter of 8 mm was 10 ⁇ L to 30 ⁇ L.
- the differential light reflectance which is NO sensitivity
- the NO response time decreases (that is, the NO gas response speeds up), and when the weight ratio is 0.05 g / g or more, the second threshold value is reached.
- a certain NO response time threshold of 20 seconds or less is satisfied.
- the nonionic surfactant is further increased and the weight ratio exceeds 1 g / g, the NO response time exceeds 20 seconds.
- the nonionic surfactant not only improves the dispersibility of CoTP (4-OCH 3 ) P as shown in FIG. 9, but also exhibits water-repellent treated particles as shown in FIG. It turns out that the dispersibility of is also improved.
- the concentration of the nonionic surfactant in the preparation solution was fixed at 7.5 g / L with respect to the second solvent chloroform.
- the differential light reflectance was measured under the conditions of a sensor temperature of 80 ° C., a nitrogen diluted NO gas concentration of 1 ppm-NO, and a flow rate of 200 ml / min.
- the peeled state in the detection film after fabrication was visually observed and evaluated based on the following evaluation criteria. 4: No peeling was observed on the detection film. 3: Peeling was observed only at the periphery of the detection film. 2: Peeling was observed on the entire detection film. 1: A detection film could not be formed, and peeling could not be observed.
- concentration (second solvent: chloroform) was 1 ⁇ 10 ⁇ 4 mol / L
- the ratio of the polymer adhesive (HPC) / water-repellent treated particles was 6 g / 90 g.
- the NO sensitivity satisfied the first threshold, but the NO response time was relatively long as 30 seconds, and the second threshold was not satisfied. However, this does not mean that it cannot be used as a nitric oxide detection element. Further, when the surface state of the detection film 11 was observed, a crack was generated on the entire surface of the detection film before exposure to NO. From the above, the overall judgment as a nitric oxide detection element was judged as “2”.
- Example 2 The same conditions as in Example 1 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 60 g. Both NO sensitivity and NO response time satisfied the threshold. Since a moderate crack occurred in the periphery of the detection film, the surface state was evaluated as “3”. The overall determination was “3”.
- Example 3 The same conditions as in Example 1 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 30 g. Both NO sensitivity and NO response time satisfied the threshold. Since a small crack was generated in the periphery of the detection film, the surface state was evaluated as “3”. The overall determination was “3”.
- Example 5 The same conditions as in Example 4 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 60 g. Both NO sensitivity and NO response time satisfied the threshold. Since the detection film was not peeled off and the surface condition was good, it was evaluated as “4”. The overall determination was “4”.
- Example 6 The same conditions as in Example 4 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 30 g. Both NO sensitivity and NO response time satisfied the threshold. Since the detection film was not peeled off and the surface condition was good, it was evaluated as “4”. The overall determination was “4”.
- Example 7 The same conditions as in Example 4 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 12 g / 30 g.
- the NO sensitivity was higher than that in Example 6, but the NO response time was relatively long as 40 seconds, and the second threshold value was not satisfied.
- the surface condition of the detection film was good.
- the overall judgment was judged as “2”. This is because the relative amount of polymer adhesive used for the water-repellent treated silica particles has increased, so the proportion of nitric oxide detection particles that have adsorbed the polymer adhesive has increased, and NO gas diffusion has become the rate-limiting step. It is assumed that the NO response time has become longer due to this.
- Example 9 The conditions are the same as in Example 8, except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 60 g. Both NO sensitivity and NO response time satisfied the threshold. Since a small crack was generated in the periphery of the detection film, the surface state was evaluated as “3”. The overall determination was “3”.
- Example 10 The same conditions as in Example 8 except that the ratio of the polymer adhesive (HPC) / water-repellent treated particles was changed to 6 g / 30 g. Both NO sensitivity and NO response time satisfied the threshold. Since the detection film was not peeled off and the surface condition was good, it was evaluated as “4”. The overall determination was “4”.
- Comparative Example 2 A detection film was formed by dispersing CoTP (4-OCH 3 ) P in the polymer adhesive HPC without using silica particles.
- the NO sensitivity satisfied the threshold value, but the NO response time was as extremely long as 50 seconds. This is thought to be because NO gas diffuses inside the polymer adhesive and reaches the pigment, and thus diffusion becomes a rate-limiting process.
- a nitric oxide detecting element having a high NO response speed cannot be produced even if a sensing film containing a dye is produced using only a polymer adhesive without using silica particles. The overall judgment was judged as “1”.
- a nitric oxide detection element excellent in NO sensitivity and NO gas response time can be obtained by using cobalt porphyrin, polymer adhesive, and inorganic silica particles in combination.
- the weight ratio of the polymer adhesive to the inorganic particles is in the range of 0.07 to 0.20 g, a detection film having a good surface condition can be obtained in addition to the NO sensitivity and the NO gas response time.
- the above describes the case where the porphyrin substituent is a methoxy group, but the present invention is not limited to this.
- the substituent may be an H group or an OH group. Hereinafter, these will be described.
- the NO sensitivity was about 25% smaller than the NO sensitivity when the light absorption after initialization of CoTP (4-OCH 3 ) P is the same, but the NO response time was almost the same.
- the reason why the NO sensitivity is lower than that of the methoxy group is that the hydrogen atom has a lower electron donating property to the macrocyclic ⁇ -conjugated system of the porphyrin skeleton than the methoxy group.
- an alcohol solvent for example, methyl alcohol or ethyl alcohol
- NO sensitivity and NO response time were comparable to those of CoTP (4-OCH 3 ) P.
- a polycarbonate-based modified urethane resin can also be used.
- sensor temperature is not limited to 80 degreeC, 40 degreeC or more and 80 degrees C or less higher than 37 degreeC of expiration temperature are preferable.
- Example 3 A polymer adhesive solution is prepared using a polycarbonate-based modified urethane resin as a polymer adhesive and ethyl alcohol as a first solvent at a concentration of 6 mg / mL, and a pattern formed on the surface of the PEN substrate is detected in advance with a diameter of 8 mm. 10 ⁇ L was dropped on the film part. After air-drying for 30 seconds (temperature 23 ° C., relative humidity 50%), the following preparation solution was dropped on the semi-dry polymer adhesive droplet film.
- CoTP (4-OCH 3 ) P and CoTPP were used in equimolar amounts as a cobalt porphyrin complex, and Triton X100 was dissolved in 7.5 mg of a nonionic surfactant and 1 mL of a chloroform solvent to prepare a preparation solution.
- the molar concentration of the cobalt porphyrin complex is 1 ⁇ 10 ⁇ 4 mol / L when the two porphyrins are combined.
- nitric oxide detecting element was installed in the nitric oxide detecting device shown in FIG. 1, and a NO gas concentration test was conducted.
- the sensor temperature of the detection film 11 was set to 150 ° C., and heating initialization was performed for 3 minutes while flowing 100 mL / minute of compressed air.
- the sensor temperature was set to 80 ° C., and a NO gas exposure test was performed while flowing compressed air 100 mL / min and 2 ppm NO gas (diluted with nitrogen) 100 mL / min.
- the sensor temperature was set to 60 ° C., and a NO gas exposure test was performed while flowing compressed air 100 mL / min and 2 ppm NO gas (nitrogen dilution) 100 mL / min.
- the sensor temperature was set to 40 ° C., and a NO gas exposure test was performed while flowing compressed air at 100 mL / min and 2 ppm NO gas (nitrogen dilution) at 100 mL / min.
- the sensor temperature was set to 115 ° C., and a NO gas exposure test was performed while flowing compressed air 100 mL / min and 2 ppm NO gas (nitrogen dilution) 100 mL / min.
- FIG. 12 shows the relationship between the sensor temperature, NO sensitivity, and NO response time when exposed to NO. From FIG. 5A, it can be seen that the NO sensitivity increases as the sensor temperature is lowered from 115 ° C. to 40 ° C. In particular, at a sensor temperature of 40 ° C., the NO sensitivity increases by about 1.5 times compared to the case of 80 ° C. shown so far. On the other hand, it can be seen from FIG. 5B that the NO response time has a maximum value when the sensor temperature is 80 ° C., and the NO response tends to increase as the NO response time decreases from 80 ° C. to 40 ° C.
- the nitric oxide detection element according to the present invention is useful for detecting nitric oxide gas in medicine, pharmacy, pharmaceutical development, environmental measurement, and chemical safety evaluation.
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Abstract
Description
前記検知膜が、一酸化窒素検出粒子と、高分子接着剤とからなり、
前記一酸化窒素検出粒子が、ポルフィリン骨格を有し、かつ中心金属として2価のコバルトを有する色素を、無機粒子の表面に吸着させることで形成されたものである、一酸化窒素検出エレメントに関する。
前記一酸化窒素検出エレメントの前記検知膜表面を、一酸化窒素を含む可能性がある測定ガスと接触させるガス導入部、
前記検知膜に光を照射する投光部、及び
前記検知膜から反射された光又は前記検知膜を透過した光を受光する受光部、を含む、一酸化窒素検出装置にも関する。
第一工程の後、前記一酸化窒素検出エレメントの前記検知膜に対し光を照射し前記検知膜の光吸収率を測定する第二工程と、
第二工程の後、前記検知膜を、一酸化窒素を含む可能性がある測定ガスと接触させる第三工程と、
第三工程の後、前記検知膜に対し光を照射し前記検知膜の光吸収率を測定する第四工程と、
第四工程で得られた前記光吸収率と、第二工程で得られた前記光吸収率とを比較することで、前記測定ガスに含まれる一酸化窒素濃度を決定する第五工程と、を含む、一酸化窒素検出方法にも関する。
ポルフィリン骨格を有し、かつ中心金属として2価のコバルトを有する色素と、無機粒子と、第二の溶媒とを混合することで、前記無機粒子の表面に前記色素を吸着させた一酸化窒素検出粒子と前記第二の溶媒とを含む調製液を作製する工程と、
前記基体表面に塗布された前記高分子接着剤溶液に、前記調製液を添加する工程と、
前記第一の溶媒と前記第二の溶媒とを乾燥させ、前記基体上に、前記一酸化窒素検出粒子と前記高分子接着剤とからなる検知膜を形成する工程と、を含む、一酸化窒素検出エレメントの製造方法にも関する。
本発明ではポルフィリン錯体からなる色素102を使用する。ここでポルフィリン錯体とは、ポルフィリン骨格を有し、該ポルフィリン骨格の中心に金属を有する錯体である。前記ポルフィリン骨格は種々の置換基で修飾されていてもよい。
中心金属として鉄(Fe)、Mn(マンガン)、コバルト(Co)、Ni(ニッケル)、Zn(亜鉛)を有するポルフィリン錯体が示すNO感度を検討したところ、コバルト以外の元素を中心金属とするポルフィリン錯体は、NOガスとの反応性が悪く、NO感度が低かった。一方、コバルトを中心金属とするポルフィリン錯体は、高いNO感度を示すことが判明した。Co(II)TPPの場合、Soretバンドでのモル吸光係数は、2.8x105(M-1・cm-1)であり、一方、Qバンドでのモル吸光係数は、1.2x104(M-1・cm-1)である。そこで本発明では、中心金属として2価のコバルトを有するポルフィリン錯体を利用する。種々の金属を有するポロフィリン錯体が示すNOガスとの反応性の差異は、中心金属の酸化還元電位と、NOガスの酸化還元電位との差に依存すると推察している。
次に、中心金属がコバルトであり、かつ対称性の高い分子構造を持つポルフィリン錯体を選択し、ポルフィリン骨格における置換基がNO感度に及ぼす効果を検討した。この検討で用いたコバルトポルフィリン錯体:CoTP(Xi)Pの構造は以下の化学式によって表される。
非イオン性界面活性剤104は、色素102の凝集を抑制し、十分に分散させるために用いることができる。この目的のため、非イオン性界面活性剤としては、親水性親油性バランス(Hydrophilic-lipophilic Balance:HLB値という:界面活性剤の水と油への親和性の程度を示す数値)が13以上15以下を示すものが好ましい。一例として、HLB値が13.5であるTriton X-100(商標、GE Healthcare UK Ltd製)の使用が好ましいが、これに限定されない。
無機粒子101としては特に限定されないが、シリカ又はα-アルミナ等の無機粒子が好ましい。シリカとα-アルミナは混合して併用してもよい。
高分子接着剤103は、一酸化窒素検出粒子同士を接着させて検知膜を形成するための接着剤、及び、基体12に一酸化窒素検出粒子を接着させるための接着剤として作用する。
基体12は、耐熱性を示す材料であって、検知光を反射又は透過する材料から構成されるシート形状のものが好ましい。検知光として光学波長400nm以上450nm以下の光を用いる場合には、光学波長400nm~450nmの光を反射又は透過する材料から構成されることが好ましい。
高分子接着剤103として、「HPC」(Sigma-Aldrich製)を用い、第一の溶媒として、アルコール系溶媒(例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、又はこれらの混合溶媒)を用いて高分子接着剤溶液を作製する。使用可能な高分子接着剤は、HPCに限定されず、上掲したいずれの化合物でも用いることができる。高分子接着剤溶液の濃度は、後述の無機粒子に対する高分子接着剤の重量比が0.07g/g~0.20g/gとなるように調整することが好ましい。具体的には、HPCを第一の溶媒に対して6mg/mLとなるように溶解させて、さらに高分子接着剤溶液の液滴量と、後述の色素を含む調製液の液滴量とを調整する。
一例として、色素CoTP(4-OCH3)P[テトラメトキシフェニルポルフィリンコバルト]と、粒子径6μm~12μmの撥水処理されたシリカ粒子と、非イオン界面活性剤としてHLB値が13.5のTriton X-100とを、第二の溶媒であるハロゲン系溶媒(例えば、クロロホルム、ジクロロメタン)に混合して、調製液を作製する。調製液における各成分の含有量は、例えば以下のとおりである。調製液中のCoTP(4-OCH3)4Pのモル濃度は3.3×10-5モル/L~3.3×10-4モル/L、撥水処理されたシリカ粒子の濃度は10mg/mL~100mg/mL、非イオン性界面活性剤の濃度は0.16mg/mL~30mg/mLである。色素と撥水処理されたシリカ粒子とのモル重量比は、1.0×10-6モル/g~1.0×10-5モル/g、色素と非イオン性界面活性剤とのモル重量比は、3.0×10-6モル/g~3.0×10-4モル/g,好ましくは3.3×10-6モル/g~5.9×10-5モル/g、無機粒子に対する非イオン性界面活性剤の重量比は、0.05g/g~1g/gである。
基体12の表面において検知膜部111を予めパターン形成することが好ましい。パターン形成することにより、検知膜の面積ばらつきを低減できるため、微量の一酸化窒素ガスを精度良く測定できる。パターン形成には、半導体プロセスで用いられるフォトリソグラフィや印刷プロセスを用いることができるが、これらに限定されない。
まず、予めパターン形成された検知膜部111に、(1)で調整した高分子接着剤溶液を滴下することで、高分子接着剤を含む液滴膜を形成する。具体的には、直径が8mmとなるようにパターニングされた検知膜部111に対し、高分子接着剤溶液(例えばHPCを溶解したメチルアルコール)を10μL~30μL滴下する。
次いで、(2)で作製した色素含有調製液を前記高分子接着剤液滴膜に10μL~30μL滴下する。この際、前記調製液は、検知膜部111と周辺部112との境界を超えて広がることはなく、検知膜部111表面で第一の溶媒と調製液とのあいだで対流が生じ、一酸化窒素検出粒子を含む均一な液滴状検知膜が形成される。これは、第一の溶媒であるアルコール系溶媒が、第二の溶媒であるハロゲン系溶媒より比重が軽いためである。検知膜部111の直径が8mmの場合、第一の溶媒も第二の溶媒もともにその滴下量が30μL以下であると、液滴状検知膜は前記境界を超えて広がることはないので、面積ばらつきの少ない検知膜11を実現できる。
次に基体12上の液滴状検知膜を風乾し固化させて検知膜11を形成する。乾燥時の温度及び湿度条件は特に限定されず、基体、高分子接着剤、及び色素の変質を生じない条件下で、風乾(室温及び相対湿度50%)であってもよいし、室温以上の温度条件下であってもよいし、ホットプレート上の加熱条件下であってもよい。
ここでは、調製液中の非イオン性界面活性剤の濃度を、第二の溶媒クロロホルムに対して、7.5g/Lと固定した。差分光反射率は、センサ温度80℃、窒素希釈NOガス濃度1ppm-NO、流速200ml/分の条件下で測定した。
4:検知膜において剥離がまったく観察されなかった。
3:検知膜の周辺部のみにおいて剥離が観察された。
2:検知膜全面において剥離が観察された。
1:検知膜を形成することができず、剥離を観察することができなかった。
4:一酸化窒素検出エレメントとして極めて良好。
3:一酸化窒素検出エレメントとして良好。
2:一酸化窒素検出エレメントとして可。
1:一酸化窒素検出エレメントとして使用不可。
コバルトポリフィリン錯体を置換基=Hの場合のCoTPPに変えて、他は同じ条件で一酸化窒素検出エレメントを作製した。NO感度は、CoTP(4-OCH3)Pの初期化後の光吸収率が同じ場合のNO感度に比べて、約25%程度小さくなったが、NO応答時間は、ほぼ同等であった。NO感度がメトキシ基の場合に比べて小さいのは、水素原子がメトキシ基に比べて、ポルフィリン骨格の大環状π共役系への電子供与性が小さいためである。
コバルトポリフィリン錯体を置換基Xi=OHの場合のCoTP(OH)Pに変えて、一酸化窒素検出エレメントを作製した。この場合、調製液の第二の溶媒としてアルコール系溶媒(例えばメチルアルコール、エチルアルコール)を用いた。他の作製条件は同じである。NO感度及びNO応答時間いずれも、CoTP(4-OCH3)Pの場合と同程度であった。
ポリカーボネート系変性ウレタン樹脂を高分子接着剤とし、第一の溶媒としてエチルアルコールを濃度6mg/mLで使用して高分子接着剤溶液を作製し、PEN基体表面に予めパターン形成された直径8mmの検知膜部に10μL滴下した。30秒風乾(温度23℃、相対湿度50%)後、半乾きの高分子接着剤液滴膜に、以下の調製液を滴下した。
11 検知膜
12 基体
13 測定セル
14 ガス導入口
15 ガス排気口
16 光源
17 光検出部
18 投光受光部
19 計測コントローラ
20,21 光ファイバ
22,23,25 制御線
24 温度コントーラ
30 測定ガス
100 一酸化窒素検出粒子
101 無機粒子
103 高分子接着剤
104 非イオン性界面活性剤
111 検知膜部
112 周辺部
Claims (38)
- 基体と、前記基体の表面に形成された検知膜とを含む一酸化窒素検出エレメントであって、
前記検知膜が、一酸化窒素検出粒子と、高分子接着剤とからなり、
前記一酸化窒素検出粒子が、ポルフィリン骨格を有し、かつ中心金属として2価のコバルトを有する色素を、無機粒子の表面に吸着させることで形成されたものである、一酸化窒素検出エレメント。 - 前記無機粒子に対する前記高分子接着剤の重量比が0.07g/g以上0.20g/g以下である、請求項1に記載の一酸化窒素検出エレメント。
- 前記無機粒子に対する前記色素のモル重量比が1.0×10-6モル/g以上1.0×10-5モル/g以下である、請求項1に記載の一酸化窒素検出エレメント。
- 前記検知膜の単位面積あたりのコバルト原子数が、1015個/cm2以上1016個/cm2以下である、請求項1に記載の一酸化窒素検出エレメント。
- 前記一酸化窒素検出エレメントは、光学波長400nmから450nmの最大光吸収率が10%以上30%以下である、請求項1に記載の一酸化窒素検出エレメント。
- 前記検知膜が、非イオン性界面活性剤をさらに含む、請求項1に記載の一酸化窒素検出エレメント。
- 前記非イオン性界面活性剤に対する前記色素のモル重量比が3.0×10-6モル/g以上3.0×10-4モル/g以下である、請求項6に記載の一酸化窒素検出エレメント。
- 前記無機粒子に対する前記非イオン性界面活性剤の重量比が0.05g/g以上1g/g以下である、請求項6に記載の一酸化窒素検出エレメント。
- 前記非イオン性界面活性剤の親水性親油性バランス(HLB値)が13以上15以下である、請求項6に記載の一酸化窒素検出エレメント。
- 前記無機粒子が、シリカ若しくはα-アルミナであるか、又は、両粒子の混合物である、請求項1に記載の一酸化窒素検出エレメント。
- 前記無機粒子が、撥水処理された無機粒子である、請求項1に記載の一酸化窒素検出エレメント。
- 前記無機粒子の粒子径が、6~12μmである、請求項1に記載の一酸化窒素検出エレメント。
- 前記検知膜の単位面積あたりの前記一酸化窒素検出粒子の重量が0.2mg/cm2~2.0mg/cm2である、請求項1に記載の一酸化窒素検出エレメント。
- 前記色素が、中心金属として2価のコバルトに加えて3価のコバルトを有する、請求項1に記載の一酸化窒素検出エレメント。
- 前記色素が、テトラフェニルポルフィリンコバルト若しくはテトラメトキシフェニルポルフィリンコバルトであるか、又は、両化合物の混合物である、請求項1に記載の一酸化窒素検出エレメント。
- 前記色素が、テトラヒドロキシフェニルポルフィリンコバルトである、請求項1に記載の一酸化窒素検出エレメント。
- 前記高分子接着剤のガラス転移温度が-150℃~150℃である、請求項1に記載の一酸化窒素検出エレメント。
- 前記基体が、プラスチック基板、セラミックス基板、金属基板、紙、織布、又は不織布である、請求項1に記載の一酸化窒素検出エレメント。
- 請求項1に記載の一酸化窒素検出エレメント、
前記一酸化窒素検出エレメントの前記検知膜表面を、一酸化窒素を含む可能性がある測定ガスと接触させるガス導入部、
前記検知膜に光を照射する投光部、及び
前記検知膜から反射された光又は前記検知膜を透過した光を受光する受光部、を含む、一酸化窒素検出装置。 - 請求項1に記載の一酸化窒素検出エレメントを初期化する第一工程と、
第一工程の後、前記一酸化窒素検出エレメントの前記検知膜に対し光を照射し前記検知膜の光吸収率を測定する第二工程と、
第二工程の後、前記検知膜を、一酸化窒素を含む可能性がある測定ガスと接触させる第三工程と、
第三工程の後、前記検知膜に対し光を照射し前記検知膜の光吸収率を測定する第四工程と、
第四工程で得られた前記光吸収率と、第二工程で得られた前記光吸収率とを比較することで、前記測定ガスに含まれる一酸化窒素濃度を決定する第五工程と、
を含む、一酸化窒素検出方法。 - 高分子接着剤を第一の溶媒に溶解してなる高分子接着剤溶液を基体表面に塗布する工程と、
ポルフィリン骨格を有し、かつ中心金属として2価のコバルトを有する色素と、無機粒子と、第二の溶媒とを混合することで、前記無機粒子の表面に前記色素を吸着させた一酸化窒素検出粒子と前記第二の溶媒とを含む調製液を作製する工程と、
前記基体表面に塗布された前記高分子接着剤溶液に、前記調製液を添加する工程と、
前記第一の溶媒と前記第二の溶媒とを乾燥させ、前記基体上に、前記一酸化窒素検出粒子と前記高分子接着剤とからなる検知膜を形成する工程と、を含む、一酸化窒素検出エレメントの製造方法。 - 前記無機粒子に対する前記高分子接着剤の重量比が0.07g/g以上0.20g/g以下である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記無機粒子に対する前記色素のモル重量比が1.0×10-6モル/g以上1.0×10-5モル/g以下である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記検知膜の単位面積あたりのコバルト原子数が、1015個/cm2以上1016個/cm2以下である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記調製液を作製する工程において、さらに非イオン性界面活性剤を混合する、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記非イオン性界面活性剤に対する前記色素のモル重量比が3.0×10-6モル/g以上3.0×10-4モル/g以下である、請求項25に記載の一酸化窒素検出エレメントの製造方法。
- 前記無機粒子に対する前記非イオン性界面活性剤の重量比が0.05g/g以上1g/g以下である、請求項25に記載の一酸化窒素検出エレメントの製造方法。
- 前記非イオン性界面活性剤の親水性親油性バランス(HLB値)が13以上15以下である、請求項25に記載の一酸化窒素検出エレメントの製造方法。
- 前記無機粒子が、シリカ若しくはα-アルミナであるか、又は、両粒子の混合物である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記無機粒子が、撥水処理された無機粒子である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記無機粒子の粒子径が、6~12μmである、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記色素が、中心金属として2価のコバルトに加えて3価のコバルトを有する、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記色素が、テトラフェニルポルフィリンコバルト若しくはテトラメトキシフェニルポルフィリンコバルトであるか、又は、両化合物の混合物である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記第二の溶媒が、クロロホルム若しくはジクロロメタンであるか、又は、両化合物の混合物である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記色素が、テトラヒドロキシフェニルポルフィリンコバルトである、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記第二の溶媒が、メチルアルコール、エチルアルコール及びイソプロピルアルコールからなる群より選択される少なくとも1種である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記高分子接着剤のガラス転移温度が-150℃~150℃である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
- 前記第一の溶媒が、メチルアルコール、エチルアルコール及びイソプロピルアルコールからなる群より選択される少なくとも1種である、請求項21に記載の一酸化窒素検出エレメントの製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013217896A (ja) * | 2012-09-24 | 2013-10-24 | Metallogenics Co Ltd | リチウム試薬組成物、リチウム試薬キット、及びリチウムイオン測定方法。 |
JP2016521856A (ja) * | 2013-06-10 | 2016-07-25 | エフ.ホフマン−ラ ロシュ アーゲーF. Hoffmann−La Roche Aktiengesellschaft | 試験要素を産生するための方法およびデバイス |
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FR3055703B1 (fr) * | 2016-09-05 | 2020-12-18 | Elichens | Procede d’analyse d’un gaz |
CN112378885B (zh) * | 2020-12-08 | 2021-08-24 | 东北大学 | 一种三元混合溶液Soret系数测量装置与方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS498786Y1 (ja) * | 1969-11-08 | 1974-03-01 | ||
JPH09171011A (ja) * | 1995-03-20 | 1997-06-30 | Ebara Corp | ガス反応性色素、同反応性色素を用いるガス検知材、ガス検知方法又はガス検知装置 |
JP2002085969A (ja) * | 2000-09-14 | 2002-03-26 | Japan Science & Technology Corp | 一酸化窒素トラップ剤 |
JP2002222618A (ja) * | 2001-01-24 | 2002-08-09 | Fujikura Ltd | 印刷用ペースト、色素増感型太陽電池および半導体多孔膜の形成方法 |
JP2003227800A (ja) | 2002-02-04 | 2003-08-15 | Riken Keiki Co Ltd | ガス検知材 |
JP2006090861A (ja) * | 2004-09-24 | 2006-04-06 | Fuji Photo Film Co Ltd | 多層分析要素 |
JP2008530527A (ja) * | 2005-02-05 | 2008-08-07 | アピーロン インコーポレイティド | 迅速応答ガス検出素子 |
JP2010030944A (ja) * | 2008-07-28 | 2010-02-12 | Lion Corp | 色素含有造粒粒子、それを含有する錠剤、及び色素含有造粒粒子の製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS498786A (ja) | 1972-05-25 | 1974-01-25 | ||
US5603820A (en) * | 1992-04-21 | 1997-02-18 | The United States Of America As Represented By The Department Of Health And Human Services | Nitric oxide sensor |
KR20060002769A (ko) * | 2003-02-24 | 2006-01-09 | 유아사 마코토 | 활성산소종 등 측정장치 |
US7365007B2 (en) | 2004-06-30 | 2008-04-29 | Intel Corporation | Interconnects with direct metalization and conductive polymer |
JP5339305B2 (ja) * | 2008-11-26 | 2013-11-13 | パナソニック株式会社 | 窒素酸化物検出エレメント |
EP2380013B1 (en) * | 2008-12-16 | 2014-11-26 | Koninklijke Philips N.V. | Electronic sensor for nitric oxide |
JP4966435B2 (ja) * | 2010-08-05 | 2012-07-04 | パナソニック株式会社 | ガス分子検知素子、ガス分子検知装置及びガス分子検知方法 |
JPWO2012124269A1 (ja) * | 2011-03-11 | 2014-07-17 | パナソニックヘルスケア株式会社 | 窒素酸化物濃度測定装置 |
-
2011
- 2011-07-12 US US13/814,155 patent/US8828734B2/en not_active Expired - Fee Related
- 2011-07-12 WO PCT/JP2011/003986 patent/WO2012017605A1/ja active Application Filing
- 2011-07-12 EP EP11814245.4A patent/EP2602617A1/en not_active Withdrawn
- 2011-07-12 CN CN2011800375153A patent/CN103154724A/zh active Pending
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS498786Y1 (ja) * | 1969-11-08 | 1974-03-01 | ||
JPH09171011A (ja) * | 1995-03-20 | 1997-06-30 | Ebara Corp | ガス反応性色素、同反応性色素を用いるガス検知材、ガス検知方法又はガス検知装置 |
JP2002085969A (ja) * | 2000-09-14 | 2002-03-26 | Japan Science & Technology Corp | 一酸化窒素トラップ剤 |
JP2002222618A (ja) * | 2001-01-24 | 2002-08-09 | Fujikura Ltd | 印刷用ペースト、色素増感型太陽電池および半導体多孔膜の形成方法 |
JP2003227800A (ja) | 2002-02-04 | 2003-08-15 | Riken Keiki Co Ltd | ガス検知材 |
JP2006090861A (ja) * | 2004-09-24 | 2006-04-06 | Fuji Photo Film Co Ltd | 多層分析要素 |
JP2008530527A (ja) * | 2005-02-05 | 2008-08-07 | アピーロン インコーポレイティド | 迅速応答ガス検出素子 |
JP2010030944A (ja) * | 2008-07-28 | 2010-02-12 | Lion Corp | 色素含有造粒粒子、それを含有する錠剤、及び色素含有造粒粒子の製造方法 |
Non-Patent Citations (4)
Title |
---|
"ATS/ERS Recommendations for Standardized Procedures for the Online and Offline Measurement of Exhaled Lower Respiratory Nitric oxide and Nasal Nitric oxide", 2005, AMERICAN THORACIC SOCIETY DOCUMENTS |
"The Porphyrins", vol. III, ACADEMIC PRESS, INC., pages: 14 - 15 |
HIROMICHI ARAI ET AL.: "Optical Detection of Nitrogen Monoxide by Metal Porphine Dispersed Amorphous Silica Film", CHEMISTRY LETTERS OF THE CHEMICAL SOCIETY OF JAPAN, 1988, pages 521 - 524 |
MAKOTO MIYAMOTO; YOSHIO HANAZATO: "Nitrogen Monoxide Adsorption and Contact Decomposition Properties of Co(II) Complexes", JOURNAL OF THE CHEMICAL SOCIETY OF JAPAN, 1998, pages 338 - 345 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013217896A (ja) * | 2012-09-24 | 2013-10-24 | Metallogenics Co Ltd | リチウム試薬組成物、リチウム試薬キット、及びリチウムイオン測定方法。 |
JP2016521856A (ja) * | 2013-06-10 | 2016-07-25 | エフ.ホフマン−ラ ロシュ アーゲーF. Hoffmann−La Roche Aktiengesellschaft | 試験要素を産生するための方法およびデバイス |
US11697279B2 (en) | 2013-06-10 | 2023-07-11 | Roche Diagnostics Operations, Inc. | Method and device for producing a test element |
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