WO2020255580A1 - ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置 - Google Patents

ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置 Download PDF

Info

Publication number
WO2020255580A1
WO2020255580A1 PCT/JP2020/018649 JP2020018649W WO2020255580A1 WO 2020255580 A1 WO2020255580 A1 WO 2020255580A1 JP 2020018649 W JP2020018649 W JP 2020018649W WO 2020255580 A1 WO2020255580 A1 WO 2020255580A1
Authority
WO
WIPO (PCT)
Prior art keywords
ammonia
sample gas
gas
sensor
sample
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/018649
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
岳 今村
皓輔 南
弘太 柴
元起 吉川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute for Materials Science
Original Assignee
National Institute for Materials Science
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute for Materials Science filed Critical National Institute for Materials Science
Priority to EP20827748.3A priority Critical patent/EP3988913B1/en
Priority to JP2021527442A priority patent/JP7262849B2/ja
Priority to US17/619,024 priority patent/US12130270B2/en
Publication of WO2020255580A1 publication Critical patent/WO2020255580A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0054—Ammonia
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/06—Investigating concentration of particle suspensions
    • G01N15/0606—Investigating concentration of particle suspensions by collecting particles on a support
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/02—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/01—Indexing codes associated with the measuring variable
    • G01N2291/014—Resonance or resonant frequency
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/025—Change of phase or condition
    • G01N2291/0256—Adsorption, desorption, surface mass change, e.g. on biosensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/025—Change of phase or condition
    • G01N2291/0256—Adsorption, desorption, surface mass change, e.g. on biosensors
    • G01N2291/0257—Adsorption, desorption, surface mass change, e.g. on biosensors with a layer containing at least one organic compound
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0426—Bulk waves, e.g. quartz crystal microbalance, torsional waves
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0427—Flexural waves, plate waves, e.g. Lamb waves, tuning fork, cantilever
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a humidifying type high-sensitivity, high-selectivity ammonia detection method and a detection device using a nanomechanical sensor.
  • nanomechanical sensor refers to stress caused by adsorption or absorption of a detection target by a so-called receptor layer coated on the sensor surface, or displacement (mechanical deformation, deflection) caused as a result. ) Is a sensor that detects.
  • Various principles and structures have been proposed as nanomechanical sensors.
  • a membrane-type surface stress sensor Membrane-type Surface stress Sensor, MSS
  • Patent Document 1 has features that are easy to use for various purposes such as its high sensitivity and operational stability.
  • the chemical substance to be detected may be referred to as a "sample"
  • the interaction with the sample causes the above-mentioned minute change in physical quantity.
  • a desired sample is taken in as much as possible by adsorption or reaction, and a material that causes a change in physical quantity as large as possible by such uptake is selected and applied to the surface of the sensor body. Fix it in some form.
  • a substance that causes a physical quantity change that can be detected by the sensor body by being fixed on the surface of the sensor body in this way and a film thereof are referred to as a receptor and a receptor layer (in some cases, a sensitive material and a sensitive film, respectively). There is also).
  • One of the promising application fields of the nanomechanical sensor is, but not limited to, a sample released from the living body by breathing, sweating, excretion, etc., or a living body such as blood or various other body fluids.
  • There is analysis of the sample taken out from the inside confirmation of the presence of the target substance, its quantification, or determination of whether or not the amount exceeds a certain threshold).
  • various applications can be considered using the detection of components contained in this type of sample or emitted from the sample due to evaporation or the like.
  • the element portion is made to have a Hammett acidity function H 0 and is sensitive to a solid superacid substance of -11.93 or less as a main component. It has been proposed that the portion and a zeolite layer (surface layer) covering the sensitive portion are formed (Patent Document 2).
  • the ammonia sensor of Patent Document 2 applies an AC voltage to the electrodes and determines the ammonia concentration based on the change in impedance (Z) of the sensitive layer or the surface layer measured from the current value flowing between the electrodes at that time. It is detected, and it is necessary to heat the element portion to a high temperature of 300 ° C. or higher by using a heating means such as a heater during operation. Further, when the sensor is used repeatedly, it is also necessary to clean the element portion by heating it to a high temperature of about 600 ° C. It should be noted that the oxide semiconductor gas sensor using SnO 2 or the like referred to in Patent Document 2 also requires heating during operation. Therefore, these ammonia detection sensors do not meet the demand for small size and low power consumption.
  • Patent Document 2 by adopting the above configuration, even low-concentration ammonia of about 1 ppm (for example, 100 ppb (0.1 ppm) to 5 ppm) such as ammonia in exhaled breath can be detected with high accuracy.
  • the sensor of Patent Document 2 since the sensor of Patent Document 2 has sensitivity to basic gases other than ammonia only in the sensitive layer, a filter that selectively permeates ammonia is required, and as a result, the manufacturing process and structure are required. becomes complicated. Therefore, a sensor having a structure as simple as possible and having high sensitivity to ammonia and high selectivity is desired.
  • PAA Polyacrylic acid
  • Non-Patent Document 2 Polyacrylic acid
  • PAH poly (allylamine hydrochloride)
  • SiO 2 silica nanoparticles
  • Non-Patent Document 3 We have reported high-sensitivity ammonia detection with a detection limit of 0.72 ppm in a high humidity environment (relative humidity (RH) of about 65%) using a sensor made of a film (Non-Patent Document 3).
  • the QCM which does not require heating, achieves extremely high sensitivity, which is an important achievement, but higher sensitivity is desired especially for the detection of ammonia contained in exhaled breath and skin gas.
  • measurement was performed at a relatively large flow rate of 0.4 L / min, but in order to reduce the burden on exhaled breath and skin gas collection, a smaller amount of gas was used. Measurement is preferred. Further, an alternating laminated film is required when manufacturing a sensor, and a sensor that can be manufactured more easily and inexpensively is required.
  • Non-Patent Document 4 An example of high-sensitivity ammonia detection using a special material as a sensitive film is a sensor using copper bromide (CuBr) by Tsuboi et al. (Non-Patent Document 4). This uses the property that monovalent copper ions coordinate-bond with ammonia molecules to easily form complexes, and many studies have been conducted so far (M. Bendahan et al. Sens. And Actuators). B, 84, 6 (2002), Y. Zheng et al. J. Phys. Chem. C 115, 2014, (2011)).
  • Non-Patent Document 5 This is an application of the passive flux sampler (S. Furukawa, Y. Sekine et al., J. Chromatogr. B 1053, 60 (2017)) developed by Furukawa, Sekine and others. It is a device that has a structure in which a coloring reagent is fixed to a solid phase) and passively collects a target component in the air using the principle of molecular diffusion. The amount of emission of the target component gas is investigated from the color change caused by long-term exposure to a gas containing a target substance such as ammonia.
  • This passive indicator is capable of extremely simple measurement, and is expected to be more versatile and have higher performance by applying the technology of more than 600 types of gas detector tubes. On the other hand, in this method, it is necessary to recognize the change in color (colorimetric recognition), and a spectrocolorimeter or the like is required for accurate quantification. Further, the passive indicator has a built-in moisture removing agent in which a hygroscopic powder such as silica gel is supported on a non-woven fabric, and it is desired to support further simple measurement in a high humidity environment.
  • the measurement system is significantly downsized and has low power consumption. Can be realized.
  • it may be difficult to detect the sample due to the water content contained in the sample. Not limited to samples obtained from living organisms such as exhaled breath and skin gas, there is a large amount of water in the natural world, and water is used for many activities in daily life and industry, so samples are used in extremely many situations. Moisture is contained in a high proportion.
  • the present inventors have found a receptor material for a nanomechanical sensor capable of reducing such a negative effect of water, and even if the sample contains a high proportion of water, trace components Has been succeeded in facilitating the detection of (Patent Document 3).
  • the present inventors have conducted research on the selectivity of the receptor material for the nanomechanical sensor and the sample for the purpose of increasing the sensitivity of the nanomechanical sensor, and found a substance having particularly high selectivity for ammonia. It was.
  • other sample selection means such as a filter, which has better sensitivity in a water-containing state, that is, a humidified state than in a water-free state, can be used. It was found that ammonia was detected with high selectivity without addition, and the present invention was completed based on this.
  • the present invention includes the following aspects.
  • Poly (methyl vinyl ether-alt-maleic anhydride) is used as the material of the receptor layer to supply a sample gas that may contain ammonia to a nanomechanical sensor that detects stress or displacement, and the nano
  • the sample gas is a humidified sample gas whose relative humidity is controlled.
  • Ammonia detection method (2) The method for detecting ammonia according to (1), wherein the sample gas is a humidified sample gas obtained by adding water vapor to the sample gas.
  • Poly (methyl vinyl ether-alt-maleic anhydride) is used as the material of the receptor layer of the nanomechanical sensor, and by controlling the relative humidity of the sample gas, ammonia can be produced with a simple sensor structure. It can be detected with high sensitivity and high selectivity. In addition, such highly sensitive ammonia detection can be achieved under a low flow rate sample gas supply, which has not been verified in the past.
  • the conceptual diagram of the apparatus configuration which carried out the detection experiment of ammonia in an Example A result of an ammonia detection experiment under conditions where the relative humidity (RH) of the sample gas and the purge gas was 0%, 25%, and 50% using a sample gas containing 50 ppm of ammonia (Example 1). Results of a trimethylamine detection experiment under conditions where the relative humidity (RH) of the sample gas and purge gas was 0%, 25%, and 50% using a sample gas containing 50 ppm of trimethylamine (Comparative Example 1). A result of an ammonia detection experiment under the conditions of 50 ppm, 30 ppm, and 10 ppm of ammonia concentration in the sample gas using a sample gas having a relative humidity of 50% (Example 2).
  • Poly (methyl vinyl ether-alt-maleic anhydride) (poly (methyl vinyl ether-) represented by the following chemical structural formula is used as a material for the receptor layer of the nanomechanical sensor. Also called alt-maleic anhydride).) Is used.
  • a nanomechanical sensor (which does not resonate an element, operates in a so-called "static mode") detects the stress caused by the adsorption of some sample molecules by the receptor layer or the displacement caused as a result by the sensor body. .. Therefore, the sensor body that can be used in the present invention can change the physical parameters caused by the stress generated in the receptor layer by the receptor layer coated on the surface adsorbing the sample or the displacement caused by the stress. As long as it is detected, its structure, operation, etc. are not particularly limited. For example, when the nanomechanical sensor is a surface stress sensor, the receptor layer covering the surface of the sensor body detects the stress change caused in the receptor layer by adsorbing a sample or the like, and detects the stress change on the surface. The stress sensor outputs a signal.
  • the nanomechanical sensor coated by the receptor for example, various surface stress sensors described in Patent Document 1 can be mentioned, but the shape, material, size, etc. thereof are not particularly limited, and any object can be used. Can be used.
  • a flaky member supported at one or a plurality of locations can be preferably exemplified.
  • various forms such as a flaky object supported at two or more places such as a double-sided beam, a film body, and the like can be adopted.
  • a crystal oscillator Quartz Crystal Microbalance, QCM
  • QCM Quadrat Crystal Microbalance
  • SPR surface plasmon resonance
  • metal nanoparticles Poly (methyl vinyl ether-) is also used as a material for the receptor layer in sensors that measure the electrical conductivity of conductive materials such as carbon black and other conductive materials, electric field effect transistors, and sensors that apply the principle.
  • conductive materials such as carbon black and other conductive materials, electric field effect transistors, and sensors that apply the principle.
  • alt-maleic anhydride the effect of the present invention can be obtained.
  • MSS is exclusively used as the nanomechanical sensor in the examples described below, it should be noted that there is no intention to limit the nanomechanical sensor that can be used in the present invention to this.
  • the method for coating the receptor on the surface of the nanomechanical sensor body to form the receptor layer is not particularly limited, such as inkjet spotting, dip coating, spray coating, spin coating, casting, and coating using a doctor blade.
  • the surface of the sensor body is directly coated with the receptor material, but there is no intention of excluding other forms.
  • a mixture with other components such as a coating via a self-assembled monolayer and binders can also be used as the receptor layer.
  • the adhesion between the surface of the sensor body and the receptor material can be improved or strengthened.
  • the "sample gas” is a gas that may contain ammonia, and the origin of the gas is not limited.
  • the sample gas is a gas derived from an animal such as a human or livestock, and more specifically, a human-derived exhaled breath or skin gas.
  • the sample gas may be an exhaust gas discharged from an engine (internal combustion engine) of an automobile or the like.
  • a humidified sample gas in which the relative humidity of these sample gases is controlled is supplied to a nanomechanical sensor whose surface is coated with Poly (methyl vinyl ether-alt-maleic anhydride) as a material for a receptor layer.
  • detection of ammonia means at least one of detecting the presence or absence of ammonia in the sample gas and detecting or quantifying the content of ammonia in the sample gas.
  • a humidified sample gas in which the relative humidity of the sample gas is controlled is obtained by adding water vapor to the sample gas.
  • the method of adding water vapor to the sample gas is not particularly limited, but it can be performed, for example, by mixing a gas containing water vapor with the sample gas.
  • the relative humidity of the gas containing water vapor is not particularly limited, but may be, for example, 100% or any value less than 100%. Further, the relative humidity of the humidified sample gas is preferably controlled to 10% or more and 100% or less.
  • humidified sample gas and purge gas are alternately supplied to a nanomechanical sensor whose surface is coated with Poly (methyl vinyl ether-alt-maleic anhydride) as a material for the receptor layer, and the alternating supply thereof is performed. Based on the output signal of the nanomechanical sensor obtained by the above, the presence or absence of ammonia or the content of ammonia in the humidified sample gas is detected. As a result, the influence caused by the operation of the detection device and the like can be reduced, and the accuracy of the ammonia detection result can be further improved.
  • Poly methyl vinyl ether-alt-maleic anhydride
  • the "purge gas” refers to a gas supplied for the purpose of cleaning the surface of the receptor layer coated on the nanomechanical sensor body.
  • the composition of the purge gas is not particularly limited, but from the viewpoint of further improving the detection accuracy of ammonia in the humidified sample gas, the purge gas preferably contains water vapor, and the relative humidity of the purge gas and the relative humidity of the humidified sample gas are the same. Is more preferable.
  • the relative humidity of the purge gas and the relative humidity of the humidified sample gas By making the relative humidity of the purge gas and the relative humidity of the humidified sample gas the same, the influence of components other than ammonia on the detection result of ammonia can be reduced, and analysis such as extraction of feature amounts based on the detection result and ammonia The presence or absence of gas and / or the content of ammonia can be detected more easily and quickly.
  • the ammonia detector uses a gas pathway for introducing a sample gas that may contain ammonia and Poly (methyl vinyl ether-alt-maleic anhydride) as a receptor for stress or It has a nanomechanical sensor for detecting displacement and a means for mixing water vapor with the sample gas, and detects the presence or absence of ammonia or the content of ammonia in the sample gas according to the above-mentioned ammonia detection method.
  • a sample gas may contain ammonia and Poly (methyl vinyl ether-alt-maleic anhydride) as a receptor for stress or It has a nanomechanical sensor for detecting displacement and a means for mixing water vapor with the sample gas, and detects the presence or absence of ammonia or the content of ammonia in the sample gas according to the above-mentioned ammonia detection method.
  • the ammonia detector has a gas path into which the purge gas is introduced.
  • the ammonia detector has means for measuring the relative humidity of the sample gas and / or the purge gas.
  • the relative humidity of the sample gas and the purge gas may be measured by a relative humidity measuring means provided in the ammonia detection device.
  • the purge gas having the adjusted relative humidity may be supplied to the nanomechanical sensor by measuring the relative humidity of the humidified sample gas whose relative humidity is controlled in advance before supplying the nanomechanical sensor. ..
  • the relative humidity of the purge gas can be determined by including water vapor in the purge gas, and a means for including water vapor in the purge gas can be provided in the ammonia detection device.
  • the control of the amount of water vapor added during the measurement and the structure of the measuring device become simple (in particular, the sample gas is dried). It is convenient in that it contains only a small amount of water vapor) and the number of parameters under the measurement conditions is reduced. Furthermore, the ammonia detection sensitivity changes sensitively to a slight difference (but not limited to, for example, 1%) between the two relative humidities, and such a difference is larger than the presence or absence of ammonia in the detection signal. However, such changes can be compensated for by prior measurement or other methods. Therefore, it goes without saying that conditions such as making both relative humidity the same or fixing the difference between the two to a specific value are not essential matters for the present invention.
  • a piezoresistive surface stress sensor having a film-type structure was used as the nanomechanical sensor. Since the structure, operation and other features of the MSS are well known to those skilled in the art, further description thereof will be omitted, but Patent Document 1, Non-Patent Document 1 and the like should be referred to as necessary.
  • the MSS used here has a diameter of 300 ⁇ m of the film (a disc-shaped thin film portion coated with a receptor layer, which is supported by a narrow portion in which a piezoresistive element is embedded and is supported by a surrounding frame portion). Also, one having a film thickness of 5 ⁇ m was used.
  • Poly (methyl vinyl ether-alt-maleic anhydride) (product number 416320) obtained from Sigma-Aldrich Japan is dissolved in N, N-dimethylformamide to make a 1 g / L solution, and then the MSS body (sensor chip) is inkjetd. It was applied on top to make the film thickness about 1 ⁇ m. At that time, the sensor chip was heated to 80 ° C. in order to accelerate the drying of the coating liquid.
  • FIG. 1 is a conceptual diagram of an apparatus configuration in which an ammonia detection experiment was performed in this embodiment.
  • the sample ammonia is poly (methyl vinyl ether-alt-maleic anhydride) from a mass flow controller 3 (MFC1) to which an ammonia standard gas cylinder 1 (ammonia concentration: 100 ppm, nitrogen balance) is connected via a gas path. It is introduced into a sensor chamber (sealed chamber) 7 containing an MSS having a receptor layer coated with. Further, the gas paths from the two mass flow controllers 4 and 5 (MFC2 and MFC3) connected to the two nitrogen gas cylinders 2 are mass flow in front of (upstream side) the gas supply port to the sensor chamber 7.
  • MFC1 mass flow controller 3
  • the arrows schematically indicate the gas flow direction
  • the ammonia gas (black arrow) supplied from the ammonia standard gas cylinder 1 to the mass flow controller 3 (MFC1) is the two nitrogen gas cylinders 2.
  • injection that supplies a sample gas containing ammonia gas to the sensor chamber 7 and nitrogen gas (purge gas) that does not contain ammonia gas are supplied to the sensor chamber 7 to supply the receptor of the sensor body.
  • Ammonia was detected by performing a total of 4 cycles of switching the "purge” for washing the layer at 5-minute intervals.
  • the ratio of the flow rate of the mass flow controller 3 (MFC1) to the total flow rate of the mass flow controllers 4 and 5 (MFC2, MFC3) was adjusted to 1: 1 so that the ammonia concentration in the sample gas was 50 ppm.
  • the flow rates of the mass flow controllers 3, 4, and 5 are controlled to reduce the relative humidity (RH) of the sample gas and purge gas in injection and purge to 0% and 25. % And 50%.
  • RH relative humidity
  • the total flow rate of the mass flow controllers 3, 4, 5 (MFC1, MFC2, MFC3) in the injection and purge was set to 30 sccm.
  • FIG. 2 The results are shown in Fig. 2.
  • the horizontal axis of FIG. 2 is the time (minutes) from the start of the experiment, and the vertical axis is the MSS output signal (mV). However, the offset portion of each signal is subtracted so that the baseline of the signal becomes 0 mV. Since the 15 minutes from the start of the experiment is the preparation time for ensuring the stability of the operation of the MSS, the measurement results of the output signals during that period are omitted. The same applies to FIGS. 3 and 4 described later.
  • the output signal of the MSS was hardly confirmed by either the injection or the purge operation, but the relative humidity of the sample gas and the purge gas was high.
  • the MSS output signal was clearly confirmed. Specifically, when the injection was started at 15 minutes, the output signal strength increased, and when switching to purge at 20 minutes, the output signal strength decreased after spikes associated with the switching operation occurred. Further, when the injection was switched again at the time of 25 minutes, the output signal strength started to increase again, and thereafter, a highly reproducible signal waveform was obtained in response to the injection / purge switching operation. Further, when the relative humidity was 50%, a very large output signal was generated from the MSS as compared with the case where the relative humidity was 25%, and a signal strength of about 15 mV was obtained.
  • the noise level of MSS is 0.01 mV and the lower limit of detection is S.
  • / N 3 and the intensity of the sensor response is proportional to the sample concentration, these results indicate that ammonia can be detected in the extremely low concentration range of 0.1 ppm in calculation.
  • the flow rate of the sample gas in the experiment on which this calculation is based is 30 sccm, which has been verified so far in detecting low-concentration ammonia. There is no low flow rate.
  • the signal waveform is highly stable, a sample gas that may contain ammonia is supplied to a nanomechanical sensor having the same configuration as in this example, and the obtained signal strength and signal waveform are analyzed. Therefore, it is considered possible to identify that ammonia is contained.
  • ⁇ Comparative example 1> A receptor layer coated with Poly (methyl vinyl ether-alt-maleic anhydride) using trimethylamine gas, which is the same nitrogen-containing compound, instead of ammonia gas, using an experimental device having the same configuration as that of Example 1. Attempts were made to detect trimethylamine by MSS having. The concentration of trimethylamine in the sample gas was set to 50 ppm, and the relative humidity of the sample gas and the purge gas was adjusted to 0% and 25% by mixing the trimethylamine gas and the nitrogen gas under predetermined conditions as in Example 1. There are three ways of 50%.
  • the relative humidity of the sample gas and the purge gas is 0% and 25%.
  • the output signal of the MSS increased slightly as it increased to 50%, but no significant increase in signal strength as obtained in Example 1 was confirmed.
  • no commonality was observed in the signal waveforms obtained by switching injection / purge a total of four times. Therefore, it is not possible to extract any features from these signal intensities and signal waveforms, and it is almost impossible to identify whether or not the sample gas contains a sample (triethylamine in this case). Conceivable.
  • MSS having Poly (methyl vinyl ether-alt-maleic anhydride) as a receptor layer, among many kinds of gases to which the material of the sensor responds like the sensor disclosed in Patent Document 2.
  • the MSS itself with the receptor layer has extremely high selectivity for ammonia, even when in direct contact with the sample gas. It has been found that such high selectivity is exhibited as a signal waveform having high signal strength and excellent stability by using a humidified sample gas having a controlled relative humidity.
  • the MSS that is recognized to be capable of detecting a sample as obtained in Example 1 even when the same experiment is performed using a plurality of substances other than trimethylamine. Neither the output signal nor the significant increase in signal strength or stable signal waveform under humidified conditions was confirmed. In addition, since the same results were obtained in the same measurement performed at different dates and times, the detection of ammonia by MSS having Poly (methyl vinyl ether-alt-maleic anhydride) as a receptor layer has high reproducibility. It can be said to have.
  • Example 2 Next, using an experimental device having the same configuration as in Example 1, the relative humidity of the sample gas and the purge gas was set to 50%, and the ammonia concentration in the sample gas was set to 50 ppm, 30 ppm, and 10 ppm. Trimethylamine was detected by MSS having a receptor layer coated with methyl vinyl ether-alt-maleic anhydride. The flow rates of the mass flow controllers 3, 4, and 5 (MFC1, MFC2, MFC3) when the ammonia concentration is 30 ppm and 10 ppm are controlled as shown in Table 2 below, and the mass flow controllers 3 in injection and purge are controlled. The total flow rate of 4 and 5 (MFC1, MFC2, MFC3) was 30 sccm.
  • ammonia can be detected by MSS having a receptor layer coated with Poly (methyl vinyl ether-alt-maleic anhydride). It was suggested that it is possible even under the supply of the sample gas having a low flow rate as described above.
  • Poly methyl vinyl ether-alt-maleic anhydride
  • MSS methyl vinyl ether-alt-maleic anhydride
  • ammonia in a humidified sample gas having a controlled relative humidity can be detected with high selectivity and accuracy by a nanomechanical sensor having a receptor layer. It was. Since it was shown that ammonia can be detected even in the concentration range of 0.1 ppm or less, it has become possible to measure the concentration of ammonia in skin gas and exhaled breath with high sensitivity and high accuracy. It has the potential to be used extensively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pathology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Acoustics & Sound (AREA)
  • Food Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
PCT/JP2020/018649 2019-06-18 2020-05-08 ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置 Ceased WO2020255580A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20827748.3A EP3988913B1 (en) 2019-06-18 2020-05-08 Humidification-type high-sensitivity/high-selectivity ammonia detection method using nanomechanical sensor, and detection device thereof
JP2021527442A JP7262849B2 (ja) 2019-06-18 2020-05-08 ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置
US17/619,024 US12130270B2 (en) 2019-06-18 2020-05-08 Humidification type highly-sensitive/highly-selective ammonia detection method and detection device using nanomechanical sensor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-112434 2019-06-18
JP2019112434 2019-06-18

Publications (1)

Publication Number Publication Date
WO2020255580A1 true WO2020255580A1 (ja) 2020-12-24

Family

ID=74037235

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/018649 Ceased WO2020255580A1 (ja) 2019-06-18 2020-05-08 ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置

Country Status (5)

Country Link
US (1) US12130270B2 (https=)
EP (1) EP3988913B1 (https=)
JP (1) JP7262849B2 (https=)
TW (1) TWI797447B (https=)
WO (1) WO2020255580A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024131062A (ja) * 2023-03-15 2024-09-30 株式会社東芝 ガス検出システムおよびガス検出方法
JP2024134699A (ja) * 2023-03-22 2024-10-04 株式会社東芝 ケミカルセンサシステム

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040040841A1 (en) * 2002-09-04 2004-03-04 Anuncia Gonzalez-Martin Chemical sensors utilizing conducting polymer compositions
JP2009250896A (ja) * 2008-04-09 2009-10-29 National Institute Of Advanced Industrial & Technology アンモニア測定素子、アンモニア測定装置、アンモニアの測定方法、塩素測定素子、塩素測定装置及び塩素の測定方法
WO2011148774A1 (ja) 2010-05-24 2011-12-01 独立行政法人物質・材料研究機構 表面応力センサ
JP2016128776A (ja) 2015-01-09 2016-07-14 日本特殊陶業株式会社 アンモニア検出素子及びアンモニアセンサ
WO2018221283A1 (ja) 2017-05-31 2018-12-06 国立研究開発法人物質・材料研究機構 低吸湿性材料からなるナノメカニカルセンサ用受容体及びそれを受容体として使用するナノメカニカルセンサ
JP2019015675A (ja) * 2017-07-10 2019-01-31 富士通株式会社 ガスセンサ、ガスセンサシステム、及びガス検出方法
JP2019174268A (ja) * 2018-03-28 2019-10-10 日本電波工業株式会社 感知方法
JP2020003362A (ja) * 2018-06-28 2020-01-09 株式会社豊田中央研究所 アミン化合物検出素子及びその利用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630956A (en) * 1969-04-01 1971-12-28 Air Prod & Chem Method of producing gases with controlled concentrations of water vapor
US6123324A (en) * 1998-08-21 2000-09-26 Air Products And Chemicals, Inc. Process for humidifying a gas stream
KR20040054801A (ko) * 2001-11-26 2004-06-25 소니 인터내셔널(유로파) 게엠베하 실온에 근접한 온도에서 조작 및 제조되는, 1ｄ 반도체재료의 화학 감지 재료로서의 용도
US20050279987A1 (en) 2002-09-05 2005-12-22 Alexander Star Nanostructure sensor device with polymer recognition layer
US8152991B2 (en) * 2005-10-27 2012-04-10 Nanomix, Inc. Ammonia nanosensors, and environmental control system
KR100842247B1 (ko) * 2005-08-08 2008-06-30 한국전자통신연구원 전자후각 센서어레이, 이를 포함하는 센서시스템, 그센서어레이 제조방법 및 그 센서시스템을 이용한 분석방법
WO2008052104A2 (en) 2006-10-26 2008-05-02 Nanomix, Inc. Sensor having a thin-film inhibition layer, nitric oxide converter and monitor
JP6764281B2 (ja) * 2016-08-09 2020-09-30 太陽誘電株式会社 ガスセンサ
JP6873638B2 (ja) 2016-09-23 2021-05-19 太陽誘電株式会社 ガスセンサ及びガス検出方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040040841A1 (en) * 2002-09-04 2004-03-04 Anuncia Gonzalez-Martin Chemical sensors utilizing conducting polymer compositions
JP2009250896A (ja) * 2008-04-09 2009-10-29 National Institute Of Advanced Industrial & Technology アンモニア測定素子、アンモニア測定装置、アンモニアの測定方法、塩素測定素子、塩素測定装置及び塩素の測定方法
WO2011148774A1 (ja) 2010-05-24 2011-12-01 独立行政法人物質・材料研究機構 表面応力センサ
JP2016128776A (ja) 2015-01-09 2016-07-14 日本特殊陶業株式会社 アンモニア検出素子及びアンモニアセンサ
WO2018221283A1 (ja) 2017-05-31 2018-12-06 国立研究開発法人物質・材料研究機構 低吸湿性材料からなるナノメカニカルセンサ用受容体及びそれを受容体として使用するナノメカニカルセンサ
JP2019015675A (ja) * 2017-07-10 2019-01-31 富士通株式会社 ガスセンサ、ガスセンサシステム、及びガス検出方法
JP2019174268A (ja) * 2018-03-28 2019-10-10 日本電波工業株式会社 感知方法
JP2020003362A (ja) * 2018-06-28 2020-01-09 株式会社豊田中央研究所 アミン化合物検出素子及びその利用

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
B. J. C. MUTCH, E. W. BANISTER, MEDICINE & SCIENCE IN SPORTS & EXERCISE, vol. 15, no. 1, 1983, pages 41 - 50
B. TIMMER ET AL., SENS. ACTUATORS B, vol. 106, 2005, pages 477
G. YOSHIKAWAT. AKIYAMAS. GAUTSCHP. VETTIGERH. ROHRER: "Nanomechanical Membrane-type Surface Stress Sensor", NANO LETTERS, vol. 11, 2011, pages 1044 - 1048
JP ONGA AGGARWALD KRIEGER ET AL., AMERICAN JOURNAL OF MEDICINE, vol. 114, 2003, pages 188 - 193
LEE SEUNG-WOO, VOLATILE BIOMARKER ANALYSIS AND ADVANCED GAS-SENSING INSTRUMENTS, 2018, pages 189
M. BENDAHAN ET AL., SENS. AND ACTUATORS B, vol. 84, 2002, pages 6
P. SPANEL ET AL., J. BREATH RES., vol. 1, 2007
S. FURUKAWAY. SEKINE ET AL., J. CHROMATOGR. B, vol. 1053, 2017, pages 60
See also references of EP3988913A4
SHIRO IKEDA ET AL., KANAGAWA PREFECTURE MANUFACTURING TECHNOLOGY EXCHANGE MEETING, vol. 3101, 2014
SHOTA FURUKAWA ET AL., 2015 INDOOR ENVIRONMENT SOCIETY ACADEMIC MEETING SUMMARY, 2015, pages 198 - 199
SHU TSUBOI ET AL., FUJITSU, vol. 68, 2017, pages 59
Y. ZHENG ET AL., J. PHYS. CHEM. C, vol. 115, 2011, pages 2014

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024131062A (ja) * 2023-03-15 2024-09-30 株式会社東芝 ガス検出システムおよびガス検出方法
JP7840896B2 (ja) 2023-03-15 2026-04-06 株式会社東芝 ガス検出システムおよびガス検出方法
JP2024134699A (ja) * 2023-03-22 2024-10-04 株式会社東芝 ケミカルセンサシステム
JP7799649B2 (ja) 2023-03-22 2026-01-15 株式会社東芝 ケミカルセンサシステム

Also Published As

Publication number Publication date
EP3988913A1 (en) 2022-04-27
US20220291185A1 (en) 2022-09-15
JPWO2020255580A1 (https=) 2020-12-24
EP3988913B1 (en) 2024-10-09
EP3988913A4 (en) 2023-06-28
TWI797447B (zh) 2023-04-01
JP7262849B2 (ja) 2023-04-24
TW202107059A (zh) 2021-02-16
US12130270B2 (en) 2024-10-29

Similar Documents

Publication Publication Date Title
Wu et al. A wearable mask sensor based on polyaniline/CNT nanocomposites for monitoring ammonia gas and human breathing
Liu et al. Humidity-activated ammonia sensor with excellent selectivity for exhaled breath analysis
Ogimoto et al. Detection of ammonia in human breath using quartz crystal microbalance sensors with functionalized mesoporous SiO2 nanoparticle films
Kuzmych et al. Carbon nanotube sensors for exhaled breath components
Pandey et al. A review of sensor-based methods for monitoring hydrogen sulfide
Hu et al. Formaldehyde sensors based on nanofibrous polyethyleneimine/bacterial cellulose membranes coated quartz crystal microbalance
Chen et al. Detection of hexanal in humid circumstances using hydrophobic molecularly imprinted polymers composite
US9164080B2 (en) System and method for sensing NO
WO2010025600A1 (zh) 高灵敏度与高选择性气体传感器
JP2012112651A (ja) 化学物質検出装置
Kamel et al. Solid contact potentiometric sensors based on host-tailored molecularly imprinted polymers for creatine assessment
JP6961252B2 (ja) 低吸湿性材料からなるナノメカニカルセンサ用受容体及びそれを受容体として使用するナノメカニカルセンサ
JP7262849B2 (ja) ナノメカニカルセンサを用いた加湿型高感度・高選択性アンモニア検出方法及び検出装置
JP2001318069A (ja) 呼気ガス分析装置
Anh et al. A hydrogen peroxide sensor for exhaled breath measurement
Temel Real-time and selective recognition of erythromycin by self-assembly of calix [4] arene on QCM sensor
Liu et al. Electrochemical sensor based on molecularly imprinted film for high sensitivity detection of clenbuterol prepared using sol-gel method
Ghawanmeh et al. The recent progress on nanomaterial-based chemosensors for diagnosis of human exhaled breath: a review
Kiejzik et al. Exhaled Aldehydes and Ketones as Biomarkers of Lung Cancer and Diabetes: Review of Sensor Technologies for Early Disease Diagnosis
Zheng et al. Highly sensitive amperometric Pt–Nafion gas phase nitric oxide sensor: Performance and application in characterizing nitric oxide-releasing biomaterials
Zajda et al. Performance of Amperometric Platinized‐Nafion Based Gas Phase Sensor for Determining Nitric Oxide (NO) Levels in Exhaled Human Nasal Breath
US8663997B2 (en) Device and method for detecting trace gases characterized a mechanism which exhales a film of fluid to trap said gasses
Lee et al. Nanoassembled Thin-film-coated Quartz Crystal Microbalance Odor Sensors for Environmental and Human Breath Ammonia Assessments.
Chen et al. Decomposition and solubility of H2O2: implications in exhaled breath condensate
Palaniappan et al. Selective and enhanced nitric oxide detection using hemoprotein/silica hybrids

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20827748

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021527442

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020827748

Country of ref document: EP

Effective date: 20220118