JP2020171240A - Flow cell for detecting gas component and gas component detector - Google Patents

Abstract

To provide a downsized flow cell for detecting gas component.SOLUTION: A flow cell for detecting gas component comprises: a solution flow path 100 through which solution containing coenzyme flows which has a first flow path 110 which extends in a first direction +A and through which solution flows in the first direction, and a second flow path 120 which extends in a second direction -A different from the first direction and through which solution flown out of the first flow path flows in the second direction; a gas flow path 200 through which gas sample flows; and a first enzyme holding membrane which holds an enzyme being a catalyst of reaction between coenzyme and the gas sample, and partitions the first flow path and the gas flow path, in which the inside of the second flow path constitutes an excitation region ER in which excitation light exciting coenzyme contained in solution flowing through the second flow path is irradiated to excite coenzyme.SELECTED DRAWING: Figure 2A

Description

The present invention relates to a flow cell for detecting a gas component and a gas component detecting device.

A detection device is known that detects a specific substance contained in a gas sample by detecting a decrease in coenzymes associated with an enzymatic reaction.
Here, in Patent Document 1, as such a detection device, for example, by utilizing the fact that NADH, which is a coenzyme, decreases with the reaction of ketones such as acetone and substrates such as nonenal, it is used as a gas sample. A detection device for detecting a contained substrate is disclosed. Specifically, the detection device disclosed in Patent Document 1 has an enzyme holding film that holds an enzyme so as to be in contact with both a solution flow path through which a solution containing a coenzyme flows and a gas flow path through which a gas sample flows. are doing. Then, this detection device irradiates the region of the solution flow path in which the enzyme retention film is arranged with excitation light, and detects the fluorescence emitted by the coenzyme that receives the excitation light.

JP-A-2016-220573

By the way, it is desirable that the detection device as described above is small in size in consideration of the space for mounting the detection device when it is mounted on a moving body such as an automobile. Along with this, it is desirable that the gas component detection flow cell provided in the above-mentioned detection device is also small.
However, the detection device disclosed in Patent Document 1 has a limit in miniaturization due to its configuration.

As an example of the problem to be solved by the present invention, miniaturization of the flow cell for detecting a gas component can be mentioned.

The invention according to claim 1
A solution flow path through which a solution containing a coenzyme flows, the first flow path extending in the first direction and the solution flowing in the first direction and the first flow path extending in a second direction different from the first direction. A solution flow path having a second flow path through which the solution flowing out of the flow path flows in the second direction,
The gas flow path through which the gas sample flows and
A first enzyme-retaining membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the first flow path from the gas flow path.
With
The inside of the second flow path constitutes an excitation region that excites the coenzyme by being irradiated with excitation light that excites the coenzyme contained in the solution flowing through the second flow path.
This is a flow cell for detecting gas components.

It is the schematic of the gas component detection apparatus of 1st Embodiment. It is a vertical sectional view of the flow cell for detecting a gas component of 1st Embodiment. It is a cross-sectional view of the flow cell for detecting a gas component of 1st Embodiment. It is a model diagram of the catalytic reaction which occurs inside the flow cell for detecting a gas component of 1st Embodiment. It is a vertical sectional view of the flow cell for detecting a gas component of the 2nd Embodiment. It is sectional drawing of the flow cell for detecting a gas component of 2nd Embodiment. It is a vertical sectional view of the gas component detection flow cell of the 3rd Embodiment. It is sectional drawing of the flow cell for detecting a gas component of 3rd Embodiment. It is a vertical sectional view of the flow cell for detecting a gas component of 4th Embodiment. It is a vertical sectional view of the flow cell for detecting a gas component of 5th Embodiment. It is a cross-sectional view of the flow cell for detecting a gas component of 5th Embodiment. It is a vertical sectional view of the flow cell for detecting a gas component of the sixth embodiment.

≪Overview≫
Hereinafter, a plurality of embodiments (first to sixth embodiments) which are examples of the present invention will be described in the order of description thereof. In all the drawings to be referred to, components having the same function are designated by the same reference numerals, and the description thereof will be omitted as appropriate in the specification.

<< First Embodiment >>
First, the first embodiment will be described with reference to FIGS. 1 and 2A and 2B. First, the configuration and function of the gas component detection device 10 (see FIG. 1) of the present embodiment will be described. Next, the gas component detection operation of the present embodiment will be described. Next, the effect of this embodiment will be described.

<Structure and function of the gas component detection device of the first embodiment>
FIG. 1 is a schematic view of the gas component detection device 10 of the present embodiment. The gas component detection device 10 of the present embodiment includes a light irradiation device 20 (an example of an irradiation device), a light detection device 30 (an example of a detection device), and a gas component detection flow cell 40 (hereinafter referred to as a flow cell 40). , The processing device CU is provided. Then, the gas component detection device 10 irradiates the flow cell 40 with excitation light from the light irradiation device 20, and the light detection device 30 detects the fluorescence emitted by the coenzyme inside the flow cell 40 to detect the fluorescence of the flow cell 40. It has a function of detecting a substrate contained in a gas sample flowing through a gas flow path 200.

Here, the substrate contained in the gas sample of the present embodiment contains a ketone group. Further, as the coenzyme, one that is excited by excitation light and emits fluorescence before or after the reaction with the substrate is used.

When NADH or NADPH is used as the coenzyme, for example, alanine dehydrogenase, alcohol dehydrogenase, aldehyde dehydrogenase, isocitrate dehydrogenase, uridine-5'-diphospho-glucose dehydrogenase, Galactose dehydrogenase, formate dehydrogenase, glyceraldehyde-3-phosphate dehydrogenase, glycerol dehydrogenase, glycerol-3-phosphate dehydrogenase, glucose dehydrogenase, glucose-6-phosphate dehydrogenase Enzymes, glutamate dehydrogenase, cholesterol dehydrogenase, sarcosine dehydrogenase, sorbitol dehydrogenase, carbonate dehydrogenase, lactic acid dehydrogenase, 3-hydroxybutyric acid dehydrogenase, pyruvate dehydrogenase, fructose dehydrogenase , 6-Phosphogluconic acid dehydrogenase, formaldehyde dehydrogenase, mannitol dehydrogenase, malic acid dehydrogenase, leucine dehydrogenase, etc., in particular, using NADH or NADPH as an electron donor. An enzyme that reduces ketones (acetone, 2-butanone, 2-pentanone, etc.) or enone (nonenal, ethyl vinyl ketone, etc.), more specifically, secondary alcohol dehydrogenase (S-ADH) (secondary alcohol dehydration). It can be a primary alcohol (secondary alcohol dehydrogenase) EC: 1.1.1.x), an enone reductase (ER1) (enone reductase type 1, ER1), or the like.

[Light irradiation device]
As shown in FIG. 1, the light irradiation device 20 has a light source 22 and a lens system 24.
As an example, the light source 22 has a function of emitting ultraviolet light having a peak wavelength of 340 nm as excitation light. The light source 22 is, for example, an ultraviolet light emitting diode. However, the light source 22 is not limited to the ultraviolet light emitting diode, and may be, for example, an ultraviolet laser diode, a mercury lamp, or the like. The broken line OA with an arrow in FIG. 1 means the optical axis OA of the excitation light (and fluorescence described later) emitted by the light source 22.

The lens system 24 is arranged between the light source 22 and the flow cell 40, and has a function of condensing the excitation light emitted from the light source 22 toward the second flow path 120 of the flow cell 40. The lens system 24 includes a collimating lens 24A, a condenser lens 24B, and an excitation light bandpass filter 24C. The collimating lens 24A, the excitation light bandpass filter 24C, and the condenser lens 24B are arranged in this order from the light source 22 side to the flow cell 40 side.

The collimated lens 24A has a function of converting the excitation light emitted by the light source 22 into parallel light, and the condensing lens 24B has a function of condensing the excitation light made parallel by the collimated lens 24A toward the second flow path 120 of the flow cell 40. .. The excitation light bandpass filter 24C has a function of transmitting excitation light in a band including the wavelength of the excitation light excited by the coenzyme. The coenzyme used in this embodiment is, for example, NADH (reduced nicotinamide adenine dinucleotide) or NADPH (reduced nicotinamide adenine dinucleotide phosphate), and NADH absorbs ultraviolet rays having a wavelength of 340 nm. It has the property of emitting fluorescence. Therefore, the range of wavelengths transmitted by the excitation light bandpass filter 24C of the present embodiment is set to 330 nm to 350 nm. The chemical structure of the coenzyme changes reversibly before and after the reaction with the substrate.

Here, supplementing the meaning of "-" used in the present specification, for example, "330 nm to 350 nm" means "330 nm or more and 350 nm or less". And, as used in this specification, "~" means "more than the description part before" ~ "and less than the description part after" ~ "".

[Photodetector]
As shown in FIG. 1, the photodetector 30 has a detection unit 32 and a lens system 34. The light detection device 30 is arranged on the opposite side of the light irradiation device 20 with the flow cell 40 interposed therebetween.
The detection unit 32 is a detector that detects fluorescence, and may be, for example, a spectrophotometer, a photomultiplier tube, a photodiode detector, or the like, depending on the application and purpose.

The lens system 34 is arranged between the flow cell 40 and the detection unit 32, and has a function of condensing the fluorescence emitted from the second flow path 120 of the flow cell 40 toward the detection unit 32. The lens system 34 has, for example, a collimating lens 34A, a condenser lens 34B, and a fluorescent bandpass filter 34C. The collimating lens 34A, the fluorescent bandpass filter 34C, and the condenser lens 34B are arranged in this order from the flow cell 40 side to the detection unit 32 side.

The collimated lens 34A has a function of making the fluorescence parallel light, and the condensing lens 34B has a function of condensing the fluorescence made into parallel light by the collimated lens 34A toward the detection unit 32. The fluorescent bandpass filter 34C has a function of transmitting fluorescence in a band including the wavelength of fluorescence emitted by the coenzyme. The wavelength of fluorescence emitted by excitation of NADH, which is a coenzyme, is 440 nm to 510 nm, and more specifically, around 491 nm. Therefore, the range of wavelengths transmitted by the fluorescent bandpass filter 34C of the present embodiment is set to 440 nm to 510 nm.

[Flow cell for detecting gas components]
FIG. 2A is a vertical cross-sectional view of the flow cell 40 of the present embodiment, and FIG. 2B is a cross-sectional view of the flow cell 40 of the present embodiment. Specifically, FIG. 2A is a sectional view taken along line 2A-2A of FIG. 2B, and FIG. 2B is a sectional view taken along line 2B-2B of FIG. 2A.
The flow cell 40 of the present embodiment has a second cylinder that holds a solution flow path 100 through which a solution containing a coenzyme flows, a gas flow path 200 through which a gas sample flows, and an enzyme that catalyzes the reaction between the coenzyme and the gas sample. It has a body 622 (an example of a first enzyme retention membrane) and has a function of reacting a gas sample with a solution. Further, the flow cell 40 of the present embodiment has a function of forming an excitation region ER that excites a coenzyme by irradiating a solution that has reacted with a gas sample with excitation light from the outside (the above-mentioned light irradiation device 20).

As shown in FIGS. 2A and 2B, the flow cell 40 has a columnar shape in appearance as an example. As shown in FIGS. 1 and 2A and 2B, the flow cell 40 includes a first cylinder 50, a second cylinder 60, a third cylinder 70, an inflow portion IN1, an outflow portion OT1, and an intake portion IN2. It is provided with an exhaust unit OT2. Note that the flow cell 40 of FIGS. 2A and 2B illustrates a state in which its axis overlaps the optical axis OA. In the following description, the side of the flow cell 40 where the light irradiation device 20 is arranged is defined as one end side of the flow cell 40, and the side where the photodetector 30 is arranged is defined as the other end side of the flow cell 40. Further, in the following description, when simply described as "one end side", it means "one end side of the flow cell 40", and when simply describing "the other end side", it means "the other end side of the flow cell 40". It shall be.

The first cylinder 50 is a bottomed cylinder having a cylinder body 52 and a bottom plate 54. The bottom plate 54 is connected to the tubular body 52 at one end of the tubular body 52. The outflow portion OT1 is connected to one end of the tubular body 52 on one end side. The first cylinder 50 is made of a light-transmitting material. Specifically, the first cylinder 50 is made of a material that transmits light having a wavelength of 330 nm to 510 nm and is difficult to autofluorescent, for example, an acrylic resin such as polymethylmethacrylate resin (PMMA).

The second cylinder 60 is a bottomed cylinder having a cylinder body 62 and a bottom plate 64. The bottom plate 64 is connected to the tubular body 62 at the other end of the tubular body 62. The cylinder 62 has a diameter larger than that of the cylinder 52 of the first cylinder 50. The second cylinder 60 is arranged on the other end side of the outflow portion OT1 in a state where its own shaft is overlapped with the shaft of the cylinder body 52.
The tubular body 62 has a first tubular body 621 arranged on one end side and a second tubular body 622 arranged on the other end side. The other end of the second tubular body 622 protrudes to the other end side of the tubular body 52.
As an example, the first cylinder 621 is made of the same material as the first cylinder 50.
The second tubular body 622 is an enzyme-retaining membrane in which a secondary alcohol dehydrogenase is immobilized on a porous substrate having gas permeability. Here, as an example, the porous base material is made of polytetrafluoroethylene, polydimethylsiloxane, polypropylene, polyethylene, polymethylmethacrylate, polystyrene, polyvinylidene fluoride, polyether sulfone, cellulose mixed ester, cellulose acetate and the like. ing.
The inflow portion IN1 is connected to the end of the first cylinder 621 (one end side of the second cylinder 60).

The third cylinder 70 is a cylinder having a cylinder body 72 and a pair of bottom plates 74 penetrating the center. The third cylinder 70 is arranged so as to surround the second cylinder 60 from the outside in the radial direction in a state where its own shaft is overlapped with the shaft of the cylinder 52. As an example, the third cylinder 70 is made of the same material as the first cylinder 50.
The cylinder body 72 has a larger diameter than the cylinder body 62 of the second cylinder 60. The length (from one end to the other end) of the cylinder 72 is set to be the same length as the second cylinder 622 of the second cylinder 60 as an example. Further, the outer peripheral edges of the pair of bottom plates 74 are connected to both ends of the tubular body 72, respectively. The inner peripheral edges of the pair of bottom plates 74 are connected to both ends of the second cylinder 622 of the second cylinder 60, respectively.
As described above, the third cylinder 70 forms a closed space with the second cylinder 622, the cylinder 72, and the pair of bottom plates 74 on the radial outer side of the first cylinder 50 and the second cylinder 60. There is.
The intake portion IN2 and the exhaust portion OT2 are connected to two different parts of the cylinder 72 (see FIG. 2B).

[Relationship between each component of the flow cell and the solution flow path and gas flow path]
As described above, the flow cell 40 has been described separately for the first cylinder 50, the second cylinder 60 and the third cylinder 70, the inflow portion IN1 and the outflow portion OT1, and the intake portion IN2 and the exhaust portion OT2. The closed space formed by the components of is defined as follows.

(Solution flow path)
A solution containing a coenzyme flows in a closed space extending from the inflow portion IN1 to the outflow portion OT1. In this embodiment, the closed space is defined as the solution flow path 100.
Here, in the solution flow path 100, the closed space surrounded by the cylinder body 52 of the first cylinder 50 and the cylinder body 62 of the second cylinder 60 is defined as the first flow path 110. The first flow path 110 extends in a direction from one end side to the other end side in the axial direction of the flow cell 40 (an example of the first direction, the + A direction in FIG. 2A), and is a flow path through which the solution flows in the + A direction. ing.

Further, the closed space inside the cylinder body 52 of the first cylinder 50 in the solution flow path 100 is defined as the second flow path 120. The second flow path 120 extends from the other end side in the axial direction of the flow cell 40 toward one end side (an example of the second direction, the −A direction in FIG. 2A), and flows out from the first flow path 110. The flow path is such that the solution flows in the −A direction. That is, the −A direction is different from the + A direction.

As described above (or as shown in FIG. 1), the light irradiation device 20 is arranged on one end side of the flow cell 40, and the light detection device 30 is arranged on the other end side. Then, in the present embodiment, the excitation light emitted from the light irradiation device 20 is irradiated to the inside of the second flow path 120. Therefore, the inside of the second flow path 120 constitutes an excitation region ER that excites the coenzyme by being irradiated with excitation light that excites the coenzyme contained in the solution flowing through the second flow path 120.

(Gas flow path)
Further, a gas sample flows in a closed space extending from the intake unit IN2 to the exhaust unit OT2. In this embodiment, the closed space is defined as a gas flow path 200. Then, according to the definition of the gas flow path 200, the following can be said in relation to other constituent requirements of the flow cell 40.
For example, the gas flow path 200 covers the first flow path 110 and the second flow path 120 from the outside in the radial direction. From another point of view, the first flow path 110 and the second flow path 120 are covered with the gas flow path 200. Further, the second tubular body 622 holds an enzyme that catalyzes the reaction between the coenzyme and the gas sample, and has a function of separating the first flow path 110 and the gas flow path 200.

[Processing device]
The processing device CU includes a light irradiation device 20, a light detection device 30, a solution supply system connected to the inflow section IN1 of the flow cell 40 (not shown), a solution outflow system connected to the outflow section OT1 (not shown), and an intake section. It has a function of controlling the intake system (not shown) connected to IN2 and the exhaust system (not shown) connected to the exhaust unit OT2. The specific function of the processing device CU will be described in the description of the gas component detection operation by the gas component detection device 10 described later. Further, the processing device CU may have a function of analyzing the concentration of the substrate contained in the gas sample flowing through the gas flow path 200 of the flow cell 40 based on the amount of fluorescence detected by the light detection device 30.

The above is a description of the configuration and function of the gas component detection device 10 of the present embodiment.

<Gas component detection operation by the gas component detection device of the first embodiment>
Next, the gas component detection operation by the gas component detection device of the present embodiment will be described with reference to the drawings.
First, the processing device CU includes a light irradiation device 20, a light detection device 30, a solution supply system connected to the inflow section IN1 of the flow cell 40, a solution outflow system connected to the outflow section OT1, and an intake air connected to the intake section IN2. The exhaust system connected to the system and the exhaust unit OT2 is operated (see FIG. 1).
Along with this, the solution flows from the solution supply system into the solution flow path 100 via the inflow portion IN1. Further, the gas sample is taken into the gas flow path 200 from the intake system via the intake unit IN2. (See Fig. 2)
The solution flowing from the inflow portion IN1 flows in the first flow path 110 in the + A direction. In this case, the phenomenon (catalytic reaction) shown in FIG. 3 described later occurs.
Next, the solution that has flowed through the first flow path 110 flows into the second flow path 120. Here, the inside of the second flow path 120 is irradiated with the excitation light emitted from the light irradiation device 20. Along with this, fluorescence is generated from the solution flowing in the −A direction inside the second flow path 120. The generated fluorescence is detected by the photodetector 30.
Further, the solution flowing through the second flow path 120 is discharged to the solution outflow system via the outflow portion OT1 (is discharged from the solution flow path 100). Further, the gas sample that has moved in the gas flow path 200 is exhausted to the exhaust system via the exhaust unit OT2.

Here, the phenomenon that occurs in the solution flowing through the first flow path 110 and the second flow path 120 will be described with reference to FIG. FIG. 3 is a model diagram of a catalytic reaction occurring inside the flow cell 40 of the present embodiment.
The following catalytic reaction occurs between the solution inside the first flow path 110 and the gas sample inside the gas flow path 200 via the second tubular body 622 (first enzyme holding membrane). That is, the gas sample containing the substrate aldehyde or ketone and the buffer solution (solution) in which the coenzyme NADH (or NADPH) is dissolved are in a state via the second cylinder 622. As described above, the second tubular body 622 is an enzyme-retaining membrane in which alcohol dehydrogenase is immobilized on a porous substrate having gas permeability. Therefore, the substrate and the coenzyme permeate the inside of the second cylinder 622. As a result, the presence of the substrate and coenzyme in the immediate vicinity of the enzyme causes the reverse reaction by the alcohol dehydrogenase to proceed, and NADH (or NADPH) is oxidized and changed to NAD + (or NADP +), resulting in NADH (or NADPH). Or the concentration of NADPH) decreases.
In this case, NADH (or NADPH) has a property of emitting fluorescence by excitation with ultraviolet rays having a wavelength near 340 nm (fluorescence), whereas NAD + (or NADP +) has a property of not being excited and emitting fluorescence (non-fluorescence). .. Therefore, when the solution flowing through the second flow path 120 is irradiated with excitation light having a peak wavelength of 340 nm from the light irradiation device 20 after flowing through the first flow path 110, NADH is excited and emits fluorescence in the vicinity of 490 nm. Since this amount of fluorescence correlates with the concentration of aldehyde or ketone, the concentration of aldehyde or ketone can be calculated by measuring the change in the amount of fluorescence. When the substrate is alcohols, the base mass is calculated from the increase in NADH concentration.

The above is the description of the gas component detection operation by the gas component detection device 10 of the present embodiment.

<Effect of the first embodiment>
Next, the effects of the present embodiment (first to fifth effects) will be described with reference to the drawings.

[First effect]
As shown in FIGS. 2A and 2B, the solution flow path 100 of the present embodiment has a first flow path 110 for causing a catalytic reaction between a gas sample and a solution, and a gas and a catalytic reaction in the first flow path 110. The solution is irradiated with excitation light and is separated from the second flow path 120 constituting the excitation region ER. The component of the second flow path 120 does not include the second tubular body 622 (first enzyme retention membrane).
In the case of the present embodiment, even if a pressure change occurs inside the gas flow path 200 or the inside of the solution flow path 100 for some reason, the second flow path 120 does not deform (or is difficult to deform). Therefore, the volume of the excited region ER tends to be kept constant (or almost constant). Further, in the case of the present embodiment, the transmittance of the solution in the second cylinder 622 (first enzyme holding membrane) may change, but the first flow path 110 having the second cylinder 622 as a wall is an excited region. Not an ER.
Therefore, in the case of the present embodiment, the amount of fluorescence in the excited region ER can be easily detected more accurately.

[Second effect]
As shown in FIGS. 2A and 2B, the solution flow path 100 of the present embodiment extends in a direction different from that of the first flow path 110 and the first flow path 110, and constitutes an excitation region ER. It has a flow path 120. That is, the second flow path 120 is not arranged on the extension of the first flow path 110 in the extending direction. The direction in which the solution inside the second flow path 120 flows (−A direction) is opposite to the direction in which the solution inside the first flow path 110 flows (+ A direction), and the second flow path 120 is the first. It is adjacent to the flow path 110. That is, the first flow path 110 and the second flow path 120 overlap in the radial direction of the flow cell 40. In other words, the first flow path 110 covers the second flow path 120 from the outside in the radial direction.
Therefore, in the case of this embodiment, the flow cell 40 can be miniaturized.

[Third effect]
The first flow path 110 (the entire outer circumference of the flow path 110) of the present embodiment is covered with the gas flow path 200 as shown in FIGS. 2A and 2B. The first flow path 110 and the gas flow path 200 are separated by a second tubular body 622 which is a tubular wall. That is, the first flow path 110 and the gas flow path 200 are separated by the first enzyme retention membrane.
From the above, in the case of the present embodiment, the gas sample and the solution can be efficiently catalytically reacted. Along with this, in the case of the present embodiment, the amount of change in the amount of fluorescence (fluorescence output) inside the second flow path 120 (excitation region ER) can be increased. From another point of view, in the case of the present embodiment, the flow cell 40 can be miniaturized and the amount of change in the amount of fluorescence (fluorescence output) inside the second flow path 120 (excitation region ER) can be increased.

[Fourth effect]
In the case of this embodiment, as shown in FIGS. 2A and 2B, the component of the second flow path 120 constituting the excited region ER does not include the second tubular body 622 (first enzyme holding membrane).
Therefore, in the case of the present embodiment, there is no (or unlikely) restriction on the optical properties (particularly transmittance, reflectance, autofluorescence) of the first enzyme-retaining film. Along with this, for example, the degree of freedom in designing the configuration of the first enzyme retention membrane can be expanded. For example, the first enzyme retaining membrane can have a multilayer structure (not shown).

[Fifth effect]
In the case of the present embodiment, as shown in FIGS. 2A and 2B, the second flow path 120 constituting the excitation region ER is arranged on the opposite side of the gas flow path 200 with the first flow path 110 interposed therebetween. .. That is, in the case of this embodiment, the excitation region ER is not adjacent to the gas flow path 200.
Therefore, in the case of the present embodiment, for example, even if dew condensation or the like occurs inside the gas flow path 200, the dew condensation or the like is unlikely to affect the fluorescence in the excited region ER. Along with this, in the case of the present embodiment, for example, the amount of fluorescence in the excited region ER can be easily detected even when the measurement operation of a relatively high-humidity gas sample is performed.

The above is the description of the effect of this embodiment. Further, the above is the description of the first embodiment.

<< Second Embodiment >>
Next, the second embodiment will be described with reference to FIGS. 4A and 4B. Hereinafter, parts different from the first embodiment of the present embodiment will be described. When the same components as the components of the first embodiment are used as the components of the present embodiment, the names, symbols, and the like of the components will be described using the same components as those of the first embodiment.

<Structure and function of the gas component detection device of the second embodiment>
FIG. 4A is a vertical sectional view of the gas component detecting flow cell 40A (hereinafter referred to as flow cell 40A) of the present embodiment, and FIG. 4B is a horizontal sectional view of the flow cell 40A of the present embodiment. Specifically, FIG. 4A is a sectional view taken along line 4A-4A of FIG. 4B, and FIG. 4B is a sectional view taken along line 4B-4B of FIG. 4A.
The gas component detection device 10A of the present embodiment is different from the gas component detection device 10 of the first embodiment only in that the flow cell 40A of the present embodiment is used instead of the flow cell 40 of the first embodiment.

First, the solution flow path 100A of the present embodiment has a third flow path 130. The third flow path 130 is a closed space surrounding the outer peripheral surface of the gas flow path 200 in the solution flow path 100A, and is a direction from one end side to the other end side in the axial direction of the flow cell 40A (an example of the first direction). , In the + A direction of FIG. 4A), and the solution flowing out to the first flow path 110 flows in the + A direction. Further, the flow cell 40A includes an enzyme holding membrane (a cylinder 72A described later) that holds an enzyme that catalyzes the reaction between the coenzyme and the gas sample and separates the third flow path 130 and the gas flow path 200.

From another point of view, the flow cell 40A of the present embodiment flows into the first cylinder 50, the second cylinder 60, the third cylinder 70, and the fourth cylinder 80, as shown in FIGS. 4A and 4B. A unit IN1, an outflow unit OT1, an intake unit IN2, and an exhaust unit OT2 are provided.
As described above, the cylinder body 72A (an example of the second oxygen retention membrane) of the third cylinder 70 is an oxygen retention membrane. The fourth cylinder 80 forms a third flow path 130 in a gap with the third cylinder 70 while covering the third cylinder 70 from the outside in the radial direction. The inflow portion IN1 is connected to the other end of the fourth cylinder 80 on the other end side.

<Gas component detection operation by the gas component detection device of the second embodiment>
The gas component detection operation of the present embodiment is the same as that of the first embodiment except that the solution flowing into the first flow path 110 is the solution after flowing through the third flow path 130 in the −A direction. Is.

<Effect of the second embodiment>
In the case of the present embodiment, the solution flowing into the second flow path 120, which is the excitation region ER, flows through the third flow path 130. Further, the third flow path 130 is separated from the gas flow path 200 by a tubular body 72A formed of an oxygen retaining film. With the above configuration, in the case of the present embodiment, the solution flowing into the second flow path 120 is catalytically reacted with the gas sample for a longer time than in the case of the first embodiment.
Therefore, according to the present embodiment, the amount of change in the amount of fluorescence (fluorescence output) inside the second flow path 120 (excitation region ER) can be increased as compared with the case of the first embodiment. From another point of view, in the case of the present embodiment, the flow cell 40 can be miniaturized and the amount of change in the amount of fluorescence (fluorescence output) inside the second flow path 120 (excitation region ER) can be increased.
Other effects of this embodiment are the same as those of the first embodiment.

The above is the description of the second embodiment.

<< Third Embodiment >>
Next, the third embodiment will be described with reference to FIGS. 5A and 5B. Hereinafter, parts different from the first and second embodiments of the present embodiment will be described. When the same components as those of the first and second embodiments are used as the components of the present embodiment, the names, symbols, etc. of the components are the same as those of the first and second embodiments. It will be described using.

<Structure and function of the gas component detection device of the third embodiment>
FIG. 5A is a vertical sectional view of the gas component detection flow cell 40B of the present embodiment (hereinafter, referred to as a flow cell 40B), and FIG. 5B is a horizontal sectional view of the flow cell 40B of the present embodiment. Specifically, FIG. 5A is a sectional view taken along line 5A-5A of FIG. 5B, and FIG. 5B is a sectional view taken along line 5B-5B of FIG. 5A.
The gas component detection devices 10B of the present embodiment are the gas component detection devices 10 and 10A of the first and second embodiments only in that the flow cell 40B of the present embodiment is used instead of the flow cell 40 of the first embodiment. different.

Comparing FIG. 5A with FIG. 4A in the case of the second embodiment, the flow cell 40B of the present embodiment looks like a part of the flow cell 40A of the second embodiment. That is, the flow cell 40B of the present embodiment looks like the flow cell 40A of the second embodiment does not have the first flow path 110 and the third flow path 130 with the axis interposed therebetween. However, when FIG. 5B is compared with FIG. 4B, that is, in a vertical cross section, the flow cell 40A of the second embodiment has a shape substantially point-symmetrical with respect to the axis, whereas the flow cell 40B of the present embodiment has a shape that is substantially point-symmetrical. It has a shape that extends in the direction perpendicular to its cross section.

Therefore, the first cylinder 50, the cylinder body 52, and the bottom plate 54 of the second embodiment correspond to the first wall 50B, the vertical wall 52B, and the bottom plate 54B of the present embodiment. Further, the second cylinder 60 and the second cylinder 622 of the second embodiment correspond to the second wall 60B and the second wall member 622B (an example of the first enzyme holding membrane) of the present embodiment, respectively. Further, the third cylinder 70 and the cylinder 72A of the second embodiment correspond to the third wall 70B and the third wall member 72B (an example of the second enzyme holding membrane) of the present embodiment, respectively. Further, the fourth cylinder 80 of the second embodiment corresponds to the fourth wall 80B of the present embodiment. As a result, as shown in FIGS. 5A and 5B, the flow cell 40B of the present embodiment has a solution flow path 100B having a first flow path 110, a second flow path 120, and a third flow path 130, and a gas flow. It has a road 200B.

<Gas component detection operation by the gas component detection device of the third embodiment>
The gas component detection operation of the present embodiment is the same as that of the second embodiment.

<Effect of the third embodiment>
The effect of this embodiment is the same as that of the first and second embodiments.

The above is the description of the third embodiment.

<< Fourth Embodiment >>
Next, the fourth embodiment will be described with reference to FIG. Hereinafter, parts different from the first to third embodiments of the present embodiment will be described. When the same components as those of the first to third embodiments are used as the components of the present embodiment, the names, symbols, etc. of the components are the same as those of the first to third embodiments. It will be described using.

<Configuration and Function of Gas Component Detection Device of the Fourth Embodiment>
FIG. 6 is a vertical cross-sectional view of the gas component detection flow cell 40C (hereinafter referred to as a flow cell 40C) of the present embodiment. Specifically, FIG. 6 is a vertical cross-sectional view cut on a cut surface (not shown) including the optical axis OA. Only in that the gas component detection device 10C of the present embodiment is the flow cell 40C of the present embodiment instead of the flow cell 40 of the first embodiment, the gas component detection devices 10 and 10A of the first to third embodiments, Different from 10B.

Comparing FIG. 6 with FIG. 2A in the case of the first embodiment, the flow cell 40C of the present embodiment appears to be a part of the flow cell 40 of the first embodiment. That is, the flow cell 40C of the present embodiment is arranged in a state in which the flow cell 40 of the first embodiment is tilted by about 90 °. In addition, in the flow cell 40C of the present embodiment, the other end of the gas flow path 200 of the flow cell 40 of the first embodiment is offset toward one end. Then, in the flow cell 40C of the present embodiment, the light irradiation device 20 and the photodetector 30 are arranged on one end side and the other end side of the position where the other end of the gas flow path 200 is offset and opened, respectively. Here, in the case of the present embodiment, the flow path covered by the first flow path 110 corresponding to the second flow path 120 of the first embodiment is referred to as the fourth flow path 120C. Further, the solution that has flowed through the first flow path 110 is once delivered, and further, a connecting flow path for delivering the solution to the fourth flow path 120C is connected to the connecting flow path 140C (another example of the second flow path). To do. The direction in which the solution flows inside the connecting flow path 140C is different from the + A direction and the −A direction, and in the case of the present embodiment, the direction is about 90 ° with respect to the + A direction. That is, the flow direction of the solution flowing through the connecting flow path 140C is a direction that intersects the + A direction and the −A direction.
As described above, the optical axis OA is oriented along the direction in which the solution flows inside the connecting flow path 140C, and the connecting flow path 140C is adjacent to the first flow path 110 and the fourth flow path 120C. ..

The flow cell 40 of the first embodiment (see FIGS. 2A and 2B) has a shape substantially point-symmetrical with respect to the axis, whereas the flow cell 40C of the present embodiment extends in a direction perpendicular to the cross section. (Vertical cross section is omitted).

Therefore, the first cylinder 50, the cylinder body 52, and the bottom plate 54 (see FIG. 2A) of the first embodiment correspond to the first wall 50C, the vertical wall 52C, and the bottom plate 54C of the present embodiment, respectively. Further, the second cylinder 60 and the second cylinder 622 of the first embodiment correspond to the second wall 60C and the second wall member 622C (an example of the first enzyme holding membrane) of the present embodiment, respectively. Further, the third cylinder 70 and the cylinder 72 of the first embodiment correspond to the third wall 70C and the third wall member 72C of the present embodiment, respectively. As a result, in the flow cell 40C of the present embodiment, as described above (as shown in FIG. 6), the solution flow path 100 having the first flow path 110, the connecting flow path 140C and the fourth flow path 120C, and the gas. It is provided with a flow path 200.

<Gas component detection operation by the gas component detection device of the fourth embodiment>
The gas component detection operation of this embodiment is the same as that of the first embodiment.

<Effect of Fourth Embodiment>
The effect of this embodiment is the same as that of the first to third embodiments.

The above is the description of the fourth embodiment.

<< Fifth Embodiment >>
Next, the fifth embodiment will be described with reference to FIGS. 7A and 7B. Hereinafter, parts different from the first to fourth embodiments of the present embodiment will be described. When the same components as those of the first to fourth embodiments are used as the components of the present embodiment, the names, codes, etc. of the components are the same as those of the first to fourth embodiments. It will be described using.

<Structure and function of the gas component detection device of the fifth embodiment>
FIG. 7A is a vertical cross-sectional view of the gas component detection flow cell 40D (hereinafter referred to as flow cell 40D) of the present embodiment, and FIG. 7B is a cross-sectional view of the flow cell 40D of the present embodiment. Specifically, FIG. 7A is a sectional view taken along line 7A-7A of FIG. 7B, and FIG. 7B is a sectional view taken along line 7B-7B of FIG. 7A. Only in that the gas component detection device 10D of the present embodiment is the flow cell 40D of the present embodiment instead of the flow cell 40 of the first embodiment, the gas component detection devices 10 and 10A of the first to fourth embodiments, Different from 10B and 10C.

Comparing FIG. 7A with FIG. 2A in the case of the first embodiment, the flow cell 40D of the present embodiment deforms the first flow path 110 of the flow cell 40 of the first embodiment. As shown in FIG. 2A, the first flow path 110 of the first embodiment is a gap between the cylinder 52 of the first cylinder 50 and the second cylinder 622 of the second cylinder 60. On the other hand, the first flow path 110D of the present embodiment is arranged in the gap between the tubular body 52, the second tubular body 622, and the tubular body 52 and the second tubular body 622, as shown in FIG. 7A. It is composed of a spiral wall 110D1 centered on an axis. Therefore, in the case of the present embodiment, the solution inside the first flow path 110D flows in the + A direction while being rotated around the axis by the spiral wall 110D1.

<Gas component detection operation by the gas component detection device of the fifth embodiment>
The gas component detection operation of this embodiment is the same as that of the first embodiment.

<Effect of the fifth embodiment>
In this embodiment, the moving distance of the solution flowing through the first flow path 110D is longer than that in the case of the first embodiment. Therefore, in the case of the present embodiment, the amount of change in the amount of fluorescence (fluorescence output) inside the second flow path 120 (excitation region ER) can be increased as compared with the case of the first embodiment.
Other effects of this embodiment are the same as those of the first to fourth embodiments.

The above is the description of the fifth embodiment.

<< 6th Embodiment >>
Next, the sixth embodiment will be described with reference to FIG. Hereinafter, parts different from the first to fifth embodiments of the present embodiment will be described. When the same components as those of the first to fifth embodiments are used as the components of the present embodiment, the names, symbols, etc. of the components are the same as those of the first to fifth embodiments. It will be described using.

<Structure and Function of Gas Component Detection Device of the Sixth Embodiment>
FIG. 8 is a vertical cross-sectional view of the gas component detection flow cell 40E (hereinafter referred to as a flow cell 40E) of the present embodiment. Specifically, FIG. 8 is a vertical cross-sectional view cut on a cut surface (not shown) including the optical axis OA. Only in that the gas component detection device 10E of the present embodiment is the flow cell 40E of the present embodiment instead of the flow cell 40 of the first embodiment, the gas component detection devices 10 and 10A of the first to fifth embodiments, It is different from 10B, 10C and 10D.

Comparing FIG. 8 with FIG. 2A in the case of the first embodiment, the flow cell 40E of the present embodiment is coated with the shielding material SH on a portion other than both ends of the second flow path 120. The transmittance of the excitation light in the portion of the flow cell 40E coated with the shielding material SH is set to 1% or less.

<Gas component detection operation by the gas component detection device of the sixth embodiment>
The gas component detection operation of this embodiment is the same as that of the first embodiment.

<Effect of the sixth embodiment>
In the present embodiment, as compared with the first embodiment, it is difficult for light from the outside to enter from a portion other than both ends of the second flow path 120. Therefore, in this embodiment, the S / N ratio at the time of fluorescence detection in the excited region ER can be increased as compared with the first embodiment.
Therefore, this embodiment can improve the detection accuracy of the fluorescence output as compared with the first embodiment.
Other effects of this embodiment are the same as those of the first to fifth embodiments.

In the flow cell 40E of the present embodiment, it is said that the shielding material SH is applied to a portion other than both ends of the second flow path 120, but the portion to which the shielding material SH is applied is the second flow path 120. It may be a part other than both ends of the above and at least a part of the solution flow path 100 and the gas flow path 200. Even in the case of this modification, the detection accuracy of the fluorescence output can be improved as compared with the first embodiment.
Further, in the present embodiment, it is assumed that the shielding material SH is applied to the flow cell 40E. However, if the transmittance of the external light can be reduced, that is, the transmittance of the external light can be reduced, the same effect may be realized by a method other than the coating of the shielding material SH. For example, a part of the flow cell 40E may be formed of a material having a transmittance of excitation light of 1% or less.

As described above, each embodiment of the present invention has been described as an example, but the present invention is not limited to each embodiment.

For example, one embodiment of each embodiment may be combined with the components of another embodiment. For example, the spiral wall 110D1 of the fifth embodiment may be combined with the sixth embodiment. Further, the shielding material SH of the sixth embodiment may be combined with the second embodiment.

Further, the light irradiation device 20 and the light detection device 30 included in the gas component detection device 10 of the first embodiment are arranged on one end side and the other end side of the flow cell 40, respectively, so that the excitation light to the excitation region ER is emitted. It was explained that the irradiation and the detection of fluorescence from the excited region ER are performed (see FIG. 1). However, if the excitation region ER can be irradiated with the excitation light and the fluorescence from the excitation region ER can be detected, the light irradiation device 20 and the light detection device 30 do not have to be arranged on one end side and the other end side of the flow cell 40, respectively. .. For example, the light irradiation device 20 and the light detection device 30 may be arranged on either one end side or the other end side of the flow cell 40.

10 Gas component detection device 10A Gas component detection device 10B Gas component detection device 10C Gas component detection device 10D Gas component detection device 10E Gas component detection device 20 Light irradiation device (example of irradiation device)
30 Photodetector (an example of a detector)
40 Flow cell for detecting gas component 40A Flow cell for detecting gas component 40B Flow cell for detecting gas component 40C Flow cell for detecting gas component 40D Flow cell for detecting gas component 40E Flow cell for detecting gas component 100 Solution flow path 100A Solution flow path 110 First flow path 110D 1st flow path 120 2nd flow path 120C 4th flow path 130 3rd flow path 140C Connecting flow path (another example of the 2nd flow path)
200 Gas flow path 200B Gas flow path ER Excitation region OA Optical axis SH Shielding material + A 1st direction-A 2nd direction

Claims (11)

A solution flow path through which a solution containing a coenzyme flows, the first flow path extending in the first direction and the solution flowing in the first direction and the first flow path extending in a second direction different from the first direction. A solution flow path having a second flow path through which the solution flowing out of the flow path flows in the second direction,
The gas flow path through which the gas sample flows and
A first enzyme-retaining membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the first flow path from the gas flow path.
With
The inside of the second flow path constitutes an excitation region that excites the coenzyme by being irradiated with excitation light that excites the coenzyme contained in the solution flowing through the second flow path.
Flow cell for detecting gas components. The first flow path is covered with the gas flow path.
The flow cell for detecting a gas component according to claim 1. The solution flow path extends in the first direction on the opposite side of the gas flow path with the gas flow path in between, and the solution flowing into the first flow path is in the direction opposite to the first direction. It has a third flow path that flows
A second enzyme-retaining membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the third flow path from the gas flow path is provided.
The flow cell for detecting a gas component according to claim 1 or 2. The second direction is the opposite direction of the first direction.
The second flow path is adjacent to the first flow path.
The flow cell for detecting a gas component according to any one of claims 1 to 3. The second direction is a direction that intersects the first direction.
The solution flow path extends in the first direction, is adjacent to the first flow path, and has a fourth flow path in which a solution flowing from the second flow path flows in a direction opposite to the first direction. ,
The flow cell for detecting a gas component according to any one of claims 1 to 3. At least a part of the solution flow path and the gas flow path, other than both ends of the second flow path, has a transmittance of 1% or less of the excitation light.
The flow cell for detecting a gas component according to any one of claims 1 to 5. The first flow path is provided with a spiral groove about an axis along the first direction.
In the first flow path, the solution that moves while being guided by the spiral groove flows in the first direction.
The flow cell for detecting a gas component according to any one of claims 1 to 6. A partially omitted version of claim 1. A solution flow path through which a solution containing a coenzyme flows, a first flow path extending in the first direction and a second flow path extending in a second direction different from the first direction. A solution channel with a path and
The gas flow path through which the gas sample flows and
A first enzyme-holding membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the first flow path from the gas flow path.
With
The inside of the second flow path constitutes an excitation region that excites the coenzyme by being irradiated with excitation light that excites the coenzyme contained in the solution flowing through the second flow path.
Flow cell for detecting gas components. A solution flow path through which a solution containing a coenzyme flows, which extends in the first direction and extends in the first flow path in which the solution flows in the first direction and in the first direction or a second direction different from the first direction. A solution flow path having a second flow path in which the solution existing and flowing out from the first flow path flows in the first direction or the second direction, and
The gas flow path through which the gas sample flows and
A first enzyme-retaining membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the first flow path from the gas flow path.
With
The first flow path is covered with the gas flow path.
Flow cell for detecting gas components. The gas flow path through which the gas sample flows and
A solution flow path through which a solution containing a coenzyme flows, which extends in the first direction and flows in the first direction, the first direction, or a second direction different from the first direction. The second flow path in which the solution existing and flowing out from the first flow path flows in the first direction or the second direction, and the first flow path on the opposite side of the gas flow path. A solution flow path having a third flow path in which a solution extending in one direction and flowing into the first flow path flows in a direction opposite to the first direction.
A first enzyme-retaining membrane that holds an enzyme that catalyzes the reaction between a coenzyme and a gas sample and separates the first flow path from the gas flow path.
A second enzyme-holding membrane that holds an enzyme that catalyzes the reaction between the coenzyme and the gas sample and separates the third flow path from the gas flow path.
A flow cell for detecting gas components. The flow cell for detecting a gas component according to any one of claims 1 to 10,
An irradiation device that irradiates the excitation region or the inside of the second flow path with excitation light that excites a coenzyme.
A detection device that detects the fluorescence emitted by the coenzyme irradiated with the excitation light inside the excitation region or the second flow path, and
A gas component detector comprising.

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