JPH09138225A - Exhalation analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an exhalation analyzer by which even a low-concentration component in an exhalation can be analyzed and which can be used as a nonconcentration type by a method wherein a concentrated-sample introduction part or the like in which an exhalation sample adsorbed to the inside of a collection pipe is desorbed is installed. SOLUTION: A collection pipe 18 is mounted on, and attached to, a concentrated- sample introduction part 20 so as to be heated, a secondary concentration pipe 202 is cooled, a carrier-gas flow passage 281 is selected by a flow-passage changeover part 30, and a carrier gas C is passed to the secondary concentration pipe 202 from the collection pipe 18. Then, an exhalation sample A is desorbed from the collection pipe 18, and it is concentrated so as to be adsorbed to the secondary concentration pipe 202. Then, the secondary concentration pipe 202 is heated, and, e.g. a splendid valve 302 is closed. Then, the exhalation sample A flows together with the carrier gas C so as to pass a precolumn 141, a main column 142 and a detector 16. Respective components which are contained in the exhalation sample A are separated by the precolumn 141 and the main column 142, they are detected by the detector 16 so as to have a difference in terms of time, and they are analyzed quantitatively and qualitatively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a breath analyzer for analyzing components contained in exhaled breath using gas chromatography in the medical field, health industry, drunk driving enforcement, drug investigation, etc.

[0002]

2. Description of the Related Art Conventionally, as described in, for example, Japanese Unexamined Patent Publication (Kokai) No. 6-58919, a breath analyzer for collecting and analyzing the breath of a subject has been developed. Breath analyzers are, for example, breath analysis for clinical tests in the medical field and monitoring of patient condition, measurement of work environment and indoor environment in the industrial field, drunk driving control and drug control in the police field, and firefighting field. It is used in a wide range of fields such as fire cause investigation and health care in the health industry field.

[0003] This breath analyzer uses gas chromatography. The breath analyzer is attached to the main body of the breath analyzer and has an outer peripheral portion covered with a heater. Two carrier gas flow paths respectively connected via a four-way electromagnetic valve, an air cylinder connected to the four-way electromagnetic valve, and a sample measuring section provided in a part of each carrier gas flow path. I have.

[0004] On the downstream side of each sample measuring section, a breathing introduction pump (suction pump) connected via a three-way electromagnetic valve and an exhaust pipe is provided. Further, it is provided with two separation columns and the like, which are connected to the above-mentioned respective three-way electromagnetic valves in parallel and independently of each other.

When the exhaled breath is collected from the subject and analyzed, when the subject exhales the exhaled air into the exhalation sampling tube, the exhaled breath exhaled to the exhalation sampling tube is delivered by the exhalation introducing pump. While being discharged to the outside of the device, a part of the exhaled breath fills each sample measuring unit as an exhaled breath sample. Next, when carrier gas is sent from the air cylinder to each sample measuring unit, the exhaled breath sample filled in each measuring unit is sent to each separation column, and then each exhaled breath sample is different due to the difference in retention time of each component gas. To be separated. Thereafter, the breath analysis is performed by a predetermined calculation process.

[0006]

For example, in the case of diabetes, arteriosclerosis, etc., the concentration of pentane in the breath is increased by lipid peroxidation, but the concentration is at most pg / mL. However, in a conventional breath analyzer, for example, since the limit of a component that can be analyzed is on the order of ng / mL, pg of pentane or the like is used.
There is a problem that low-concentration components on the order of / mL cannot be analyzed.

In order to solve this problem, the present inventor has
A new breath analyzer that concentrates breath samples (hereinafter,
It is called "concentrated type". ) Figured out. However, this new breath analyzer is structurally unusable as a conventional direct injection type (hereinafter referred to as "non-concentrating type"). Therefore, two types of breath analyzers are required, which causes a new problem that the size and the price are increased as a whole.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a breath analyzer which can analyze even a low concentration component contained in the exhaled breath in a small amount and can be used as a conventional non-concentrated type. .

[0009]

A breath analyzer according to claim 1, wherein a pre-column and a main column for passing a breath sample to separate components contained in the breath sample are separated by the pre-column and the main column. A detector that detects the components, a collection tube that adsorbs the exhaled breath sample inside, a concentrated sample introduction part that desorbs the exhaled breath sample adsorbed in the collection tube, and exhaled breath that exhales breath into the inside. A collection tube, a sample loop for adsorbing exhaled air as an exhaled breath sample, a pump for sucking the exhaled air in the exhaled breath sampling tube through the sample loop to fill the exhaled breath sample in the sample loop, and the concentrated sample introduction A first carrier gas flow path that allows the exhaled breath sample desorbed in the column to pass through the precolumn and the main column by a carrier gas; A second carrier gas flow passage for allowing the breath sample filled in the pull loop to pass through the main column by a carrier gas, and a third carrier gas flow passage for purging the breath sample remaining in the pre-column by a carrier gas, A flow path switching unit that can switch to one of the first or second and third carrier gas flow paths.

When used as a concentrated type, the first carrier gas channel is selected by the channel switching unit. The breath sample concentrated and collected in the collection tube is desorbed at the concentrated sample introduction part and passes through the precolumn and the main column together with the carrier gas. The concentration of the breath sample with respect to the carrier gas is much higher than when the non-concentrated breath component is flowed together with the carrier gas. That is, the detector can obtain a detection value with a high peak. Therefore, even low-concentration components that are slightly contained in the breath can be sufficiently analyzed.

When used as a non-concentrated type, the exhaled breath in the exhalation sampling tube is pumped through the sample loop to fill the sample loop with the exhaled breath sample.
Then, the flow path switching unit selects the second carrier gas flow path. The breath sample filled in the sample loop is
Pass through the main column with carrier gas.

The main column, the detector, and the pipes around them are common parts used in both the concentrated type and the non-concentrated type.

The breath analysis device according to claim 2 is characterized in that:
In the exhalation analyzer described above, an exhalation suction flow path for sucking the exhalation in the exhalation sampling tube with the pump through the sample loop is provided, and the flow path switching unit includes the exhalation suction flow path and the first carrier gas. It is possible to switch to either the flow passage or the second and third carrier gas flow passages.

It is possible to carry out all the steps of the concentrated type and the non-concentrated type only by switching between the exhaled breath suction channel and the first carrier gas channel and the second and third carrier gas channels. Become.

The breath analysis apparatus according to claim 3 is the method according to claim 1.
In the breath analyzer according to the description, the concentrated sample introduction unit,
First heating means for heating the collection tube to desorb the exhaled breath sample adsorbed in the collection tube, a secondary concentrating tube for adsorbing the exhaled breath sample therein, and desorption of the collection tube Cooling means for adsorbing the exhaled breath sample in the secondary concentrating tube and second heating means for heating the secondary concentrating tube to desorb the exhaled breath sample adsorbed in the secondary concentrating tube. It is what

The breath sample concentrated and collected in the collection tube is further concentrated and adsorbed to the secondary concentration tube. Therefore,
By passing this exhaled sample through the main column with the carrier gas, it becomes possible to analyze a lower concentration component.

[0017]

1 and 2 are configuration diagrams showing an embodiment of an exhalation analyzer according to the present invention. FIG. 1 shows a state in which an exhalation suction passage and a first carrier gas passage are switched. FIG. 2 shows a state in which the second carrier gas flow path is switched to. Hereinafter, description will be made mainly with reference to these drawings.

The breath analyzer 12 according to the present invention includes a pre-column 141 and a main column 142 for passing the breath sample A to separate the components contained in the breath sample A, and a component separated by the pre-column 141 and the main column 142. A detector 16 for detecting, a collection tube 18 in which the exhaled breath sample A is adsorbed, a concentrated sample introduction section 20 for desorbing the exhaled breath sample A adsorbed in the collection tube 18, and an exhaled breath A ′. The exhaled breath sampling tube 22 blown inside, the sample loop 24 for adsorbing the exhaled breath A ′ as the exhaled breath sample A, and the sample loop 24 by sucking the exhaled breath A ′ in the exhaled breath sampling tube 22 through the sample loop 24 A pump 26 for filling the exhaled breath sample A with the exhaled air, and an exhaled air suction flow passage 280 for sucking the exhaled air A ′ in the exhaled air sampling tube 22 with the pump 26 through the sample loop 24, The exhaled breath sample A desorbed in the concentrated sample introduction part 20 is pre-column 1 by the carrier gas C ₁ .
41 and a first carrier gas flow passage 281 for passing through the main column 142, and a second carrier gas flow passage 282 for passing the breath sample A filled in the sample loop 24 through the main column 142 by the carrier gas C ₂ . ,
A third carrier gas channel 283 for purging the exhaled breath sample A remaining in the pre-column 141 with the carrier gas C ₃ .
And a channel switching unit 30 that can switch to either one of the exhalation suction channel 280, the carrier gas channel 281, and the carrier gas channels 282, 283.

The pre-column 141 is for removing unnecessary components, and has a property of easily holding polar components such as water and acetone.

The concentrated sample introduction section 20 includes a collection tube support 201 for supporting the collection tube 18, a secondary concentration tube 202 for adsorbing the exhaled breath sample A therein, and a secondary concentration tube 202 for supporting the secondary concentration tube 202. Concentrator support 203. The collection tube support 201 has a built-in first heating means (not shown) for desorbing the exhaled breath sample A adsorbed in the collection tube 18. The secondary concentrating tube support 203 has a cooling means (not shown) for adsorbing the exhaled breath sample A desorbed from the collecting tube 18 in the secondary concentrating tube 202, and the secondary concentrating tube 202 is heated to be secondary A second heating means (not shown) for desorbing the exhaled breath sample A adsorbed in the concentrating tube 202 is incorporated.
For example, the first and second heating means are electric heaters, and the cooling means is a container containing liquid nitrogen.

As the secondary concentrating tube 202, a capillary tube having an inner diameter of 0.5 to 1.0 mm is used, but it is desirable that the material and characteristics of the main column 142 are the same. In addition, the secondary concentration tube 2
Since No. 02 uses a liquid phase of an adsorbent coated, the efficiency of secondary concentration is higher than that of a raw tube without coating. The secondary concentration tube 202 and the secondary concentration tube support 203 may be omitted when the concentration rate of the collection tube 18 is high.

The exhalation sampling tube 22 has an exhalation outlet 221 and an exhalation inlet 222. The subject attaches the disposable mouthpiece 223 to the exhalation inlet 222, puts his mouth on the mouthpiece 223, and exhales A ′ into the exhalation sampling tube 22.
Blow in. The exhalation sampling tube 22 is fixed by the exhalation sampling tube support member 23. Exhalation tube support 2
A third heating unit (not shown) for heating the exhaled air A ′ and the like is incorporated in the unit 3.

The flow path switching unit 30 is composed of a sampling valve 301, electromagnetic valves 302 and 304, and control means 303 for controlling energization of the solenoids of the sampling valve 301 and the electromagnetic valves 302 and 304. The control means 303 may be any one such as a manual switch, a relay and a timer, a microcomputer and its program. A gas cylinder 321 filled with carrier gas C is connected to the flow path switching unit 30 via a pressure reducing valve 322. As carrier gas C, air, hydrogen,
Nitrogen, helium, argon and the like are generally used.

The sampling valve 301 is, for example, a rotary valve having ten ports 1 to 10. FIG. 3 is a schematic cross-sectional view showing an example of the sampling valve 183. In FIG. 3, the sampling valve 301
Is composed of a fixed body 301A having ports 1 to 10, a rotating body 301B having communication tubes a to e, and an actuator (not shown) such as a solenoid for rotating the rotating body 301B. FIG. 3 [1] shows the exhalation suction flow path 280.
And a state in which the carrier gas flow channel 281 is switched to,
FIG. 3 [2] shows a state in which the carrier gas flow paths 282 and 283 are switched to.

A pipe 341 connected to one end of the pre-column 141 is connected to the port 1. The port 2 has a pipe 342 connected to one end of the main column 142.
Is connected. Sample loop 24 on port 3
A pipe 343 connected to one end of is connected. A pipe 344 connected to the pump 26 is connected to the port 4. A pipe 345 connected to the exhalation sampling tube 22 is connected to the port 5. A pipe 346 connected to the other end of the sample loop 24 is connected to the port 6. The carrier gas C ₂ is supplied to the port 7 with a solenoid valve 302.
A pipe 347 to be introduced through is connected. A pipe 348 for discharging the carrier gas C ₃ that has passed through the concentrated sample introduction unit 20 and the pre-column 141 is connected to the port 8. A pipe 349 connected to the other end of the pre-column 141 is connected to the port 9. The carrier gas C ₁ , which has passed through the concentrated sample introduction part 20, is supplied to the port 10.
A pipe 340 for introducing C ₃ through the filter 204 is connected. The pre-column 141, the main column 142, the sampling valve 301, and the pipes 341, ... Surrounding them are housed in a thermostat (not shown) kept constant at 100 ° C., for example.

The detector 16 may detect any of mass, heat conduction, ionic current and the like.

Next, the operation of the breath analyzer 12 will be described.

[Concentration type operation 1 (analysis)]

First, the exhaled breath sample A is adsorbed to the collection tube 18 by using the exhaled breath concentration and collection device 80 shown in FIG. The breath concentration / collection device 80 collects the Tedlar bag 82 filled with the breath A ′, the collection pipe 18 communicating with the inside of the Tedlar bag 82, and the collection pipe 18 for the breath A ′ inside the Tedlar bag 82.
A pump 84 for suctioning through the collection tube 18, an integrated flow meter 86 for measuring an integrated flow rate f of the expired air A ′ passing through the collection tube 18, a pressure gauge 88 for measuring a pressure p of the expired air A ′ in the Tedlar bag 82, and a pressure gauge. A main control unit 90 that stops the pump 84 when the pressure p of the exhaled air A ′ measured at 88 becomes a fixed value p _F or less, a thermostat 92 that keeps the temperature T of the collection tube 18 constant, and a trap The water absorption filter 94 provided in the flow path of the exhaled air A ′ between the collecting tube 18 and the pump 84 is provided. Tedlar bag 82, T-tube 881 of pressure gauge 88,
The collection tube 18, the water absorption filter 94, the pump 84, and the integrating flowmeter 86 are connected by flexible tubes 95a to 95e, respectively.

The collection tube 18 is filled with an adsorbent 181 for adsorbing the exhaled breath sample A. Tedlar bag 82
Has an exhalation discharge port 821 and an exhalation blowout port 822. Although not particularly shown, the exhalation outlet 821 and the exhalation inlet 822 are provided with stop valves that can be opened and closed manually. In advance, the subject attaches the disposable mouthpiece 823 to the breath inlet 822 and
3 and the exhalation A ′ is blown into the Tedlar bag 82. The integrating flow meter 86 is a general gas flow meter such as a mass flow meter. The pressure gauge 88 uses, for example, a piezoelectric effect that generates a voltage when a pressure is applied to a piezoelectric element, and outputs an electric signal corresponding to the pressure p of the exhalation A ′ to the main control unit 90. The main control unit 90 includes, for example, a microcomputer including a CPU, a ROM, a RAM, an input / output interface, and the like, and a computer program stored in the ROM or the like. The operation of the main control unit 90, drives the pump 84 with stops when the pressure p of exhalation A 'output from the pressure gauge 88 becomes equal to or less than a predetermined value p _F, buzzer for informing not shown, the lamp It is programmed to be. According to experiments, the pressure p during suction is, for example, 400 mmHg, and the pressure p at the end of suction (that is, a constant value p _F ) is, for example, 420 mmHg. The incubator 92 includes a heating / cooling unit 96 and a temperature control unit 9
7 is comprised. The heating / cooling unit 96 has an upper side 98.
And the lower side 99, and the upper side 98 and the lower side 99 sandwich the collection tube 18. Therefore, the collection tube 18 can be easily attached to and detached from the heating / cooling unit 96. The upper side 98 is composed of a heat insulating material 981, a heat transfer material 982, and the like. The lower side 99 is composed of a heat insulating material 991, a heat transfer material 992, a Peltier element 993, a radiation fin 994, and the like. The heat transfer materials 982 and 992 and the radiation fins 994 are
Made of aluminum. A thermocouple 971 is embedded inside the heat transfer material 992. The thermocouple 971 is a heat transfer material 9
The voltage 92 corresponding to the temperature T of the collection tube 18 is output to the temperature controller 97. The temperature control unit 97 is, for example, C
It is composed of a microcomputer including a PU, a ROM, a RAM, an input / output interface, a computer program for temperature control stored in the ROM, and a DC voltage power supply. The operation of the temperature control unit 97 is to energize the Peltier element 993 so that the temperature T of the collection tube 18 output from the thermocouple 971 becomes a constant value T _C.
When the fixed value T _C is equal to or higher than room temperature, a simple electric heater or the like may be used instead of the Peltier element 993. The moisture absorbing filter 94 is filled with a moisture absorbing material 941 such as silica gel or calcium carbonate.

When the pump 86 is operated, the exhaled air A'is sucked from the Tedlar bag 82 through the collection tube 18. As a result, the exhaled breath component A is concentrated and collected by the adsorbent 181 in the collection tube 18. At this time, the pressure p during suction is measured by the pressure gauge 88, and the integrated flow rate f is measured by the integrated flow meter 86. If Tedlar bag 82 is emptied, the pressure p reaches a predetermined value p _F, the main control unit 90 is a pump 8
4 is stopped. Since the integrated flow rate f at the end of suction is output from the integrated flow meter 86 to the main control unit 90, the collection tube 18
The amount of expiration A 'concentrated in the water is also known.

Subsequently, the collection tube 18 is connected to the concentrated sample introduction section 20.
And heat the collecting tube 18 to, for example, 250 ° C. and cool the secondary concentrating tube 202 to, for example, −130 to −180 ° C.
In addition, the carrier gas passage 2 is formed by the passage switching unit 30.
81 (FIG. 1) is selected to collect the carrier gas C in the collection tube 18
To the secondary concentrator 202. Then, the exhaled breath sample A is desorbed from the collection tube 18, further concentrated, and adsorbed to the secondary concentration tube 202.

When the adsorption of the exhaled breath sample A to the secondary concentrating tube 202 is completed, the secondary concentrating tube 202 is heated to 190 ° C., for example. At this time, in order to save the carrier gas C, the solenoid valve 30
Since 2 is closed, the carrier gas C ₁ is supplied to the solenoid valve 304 → concentrated sample introducing section 20 → filter 204 → port 10 → port 9 → precolumn 141 → port 1 → port 2 → main column 142 → detector 16 → Discharge and flow.
The exhaled breath sample A also flows together with the carrier gas C and passes through the pre-column 141, the main column 142 and the detector 16. Each of the components contained in the exhaled breath sample A has a pre-column 141.
And separated by the main column 142, they are detected by the detector 16 with a time difference. In the detector 16, qualitative analysis is performed by the volume (holding capacity) of the carrier gas C from the injection of the exhaled breath sample A until the separation zone of each component appears or the time (holding time), and the peak area or peak height is determined. Therefore, quantitative analysis is performed.

According to the breath analyzer 12, since the breath sample A concentrated by the concentrated sample introducing unit 20 is used, even a low concentration component such as pentane containing only pg / mL order in the breath is sufficient. Can be analyzed.

[Concentration type operation 2 (backflush and analysis)]

The carrier gas flow path 283 (FIG. 2) is selected by the flow path switching unit 30 to flow the carrier gas C ₃ . At this time, the solenoid valve 304 is opened, so that the carrier gas C ₃ is supplied from the solenoid valve 304 → concentrated sample introducing section 20 → filter 204 → port 10 → port 1 → precolumn 141.
By flowing in the order of → port 9 → port 8 → discharging, the precolumn 141 and the like can be purged.

At this time, the carrier gas passage 282 (FIG. 2) may be selected by opening the solenoid valve 302. In this case, the carrier gas C ₂ is the solenoid valve 302 →
Port 7 → Port 6 → Sample loop 24 → Port 3 →
It flows in the order of port 2 → main column 142 → detector 16 → discharge. Therefore, since the exhaled breath sample A remaining in the main column 142 also flows together with the carrier gas C ₂ , the analysis can be continued as necessary and the main column 14 can be continued.
2 etc. can be purged. In this case, it is premised that the sample loop 24 is not filled with the breath sample A.

[Non-concentrating operation 1 (exhalation suction)]

First, the exhalation sampling tube 22 is heated to, for example, 40 ° C., and the exhalation suction channel 280 is set by the channel switching unit 30.
Select (Fig. 1). When the subject blows the exhaled air A ′ into the exhaled air sampling tube 22, the pump 26 correspondingly operates for a predetermined time. At this time, the exhaled breath A ′ is the exhaled breath collection tube 2
The flow is 2 → port 5 → port 6 → sample loop 24 → port 3 → port 4 → pump 26 → discharging. As a result, the breath A ′ is filled in the sample loop 24 as the breath sample A.

[Non-concentrated operation 2 (analysis)]

The carrier gas flow path 282 (FIG. 2) is selected by the flow path switching unit 30 to flow the carrier gas C.
At this time, the solenoid valve 302 is opened, so that the carrier gas C ₂ is transferred from the solenoid valve 302 → port 7 → port 6 → sample loop 24 → port 3 → port 2 → main column 142.
-> Detector 16-> discharge and flow. The exhaled breath sample A filled in the sample loop 24 also flows together with the carrier gas C ₂ .
It passes through the main column 142 and the detector 16. The respective components contained in the exhaled breath sample A are separated by the main column 142 and thus detected by the detector 16 with a time difference. The detector 16 performs a predetermined analysis as described above.

FIG. 5 is a waveform diagram showing an example of the concentration-type analysis result of the breath analyzer 12. FIG. 6 is an explanatory diagram showing an example of the backflush. Hereinafter, description will be given with reference to FIGS. 1 to 6.

The concentrated type can also detect low-concentration high-boiling components (such as hexane) which cannot be detected by the non-concentrated type.
However, a normal high boiling point component has a long residence time in the pre-column 141 and the main column 142 (retention time is slow). Therefore, the time required for analysis is, for example, 15 minutes in the non-concentrated type, but it takes 1 hour or more in the concentrated type. In the example of FIG. 5, pentane P is detected in about 6 minutes and hexane H is detected in about 30 minutes after starting the analysis. Therefore, even if only pentane P needs to be detected, it is necessary to continue the analysis for a long time in order to discharge hexane H. Also,
Passing a high-boiling-point component such as hexane H through the main column 142 and the detector 16 also causes contamination and deterioration of these components.

Therefore, in order to shorten the analysis time and prevent contamination and deterioration, backflushing is performed. First, when the carrier gas C ₁ starts to flow through the precolumn 141 and the main column 142, pentane P and hexane H, which are the components of the breath sample A, enter the precolumn 141 (FIG. 6 [1]). Pentane P is less likely to be retained in the precolumn 141 than hexane H, so the precolumn 141 is first
(Fig. 6 [2]). Time passes, Pentane P
However, even though the column has progressed considerably through the main column 142, hexane H is still in the precolumn 141 (FIG. 6 [3]). If the carrier gas C ₁ is kept flowing as it is, it takes a long time for the hexane H to leave the main column 142. Therefore, the pre-column 141 and the main column 142 are separated, a carrier gas C _{3 in the} direction opposite to the carrier gas C ₁ is flown through the pre-column 141, and a carrier gas C ₂ in the same direction as the carrier gas C ₁ is passed through the main column 142. Shed. As a result, pentane P exits the main column 142 and is detected, and hexane H is also purged from the pre-column 141 (FIG. 6 [4]). Therefore, the analysis time is significantly reduced. In the example of FIG. 5, the analysis can be completed in about 8 minutes.
Hexane H is used in the main column 142 and the detector 16
Since it does not flow to the inside, these pollutions and deteriorations are prevented.

Needless to say, the above embodiment is merely an example and does not limit the present invention. For example,
The sampling valve 301 may switch the flow path by switching the solenoid valve. The breath analysis apparatus 12 may be fully automated by providing the control means 303 with a function of controlling the detector 16, the concentrated sample introduction unit 20, the breath collection tube support 23, the pump 26, and the like. Each port 1-10, pre-column 141, main column 142, exhalation sampling tube 22, sample loop 24,
The pump 26 and the solenoid valve 302 may be connected in any combination as long as the functions of the exhalation suction passage 280 and the carrier gas passages 281 and 280 can be realized.

[0046]

According to the breath analysis device of the first to third aspects, the breath sample concentrated and collected in the collection tube is desorbed at the concentrated sample introduction part, and the breath sample is pre-columned and main by the carrier gas. Since it is passed through the column, even low-concentration components such as pentane, which are contained in the exhaled air in a small amount, can be sufficiently analyzed. Moreover, the exhaled breath sample desorbed in the concentrated sample introduction part is passed by the carrier gas to the pre-column and the main column, and the exhaled breath sample filled in the sample loop is passed to the main column by the carrier gas. A second carrier gas flow path, a third carrier gas flow path for purging the exhaled sample remaining in the precolumn with a carrier gas, and either the first carrier gas flow path or the second and third carrier gas flow paths. By providing the flow path switching unit that can be switched to either one side, it can be used as a concentrated type and a non-concentrated type while sharing the main column, the detector and the like. Therefore, downsizing and cost reduction of the entire device can be achieved. Furthermore, the third carrier gas flow path allows unnecessary high-boiling components to be quickly discharged without passing through the main column and detector, significantly reducing the analysis time and contaminating the main column and detector. It can also prevent deterioration.

According to the exhalation analyzer of the second aspect, an exhalation suction passage for sucking the exhalation in the exhalation sampling tube by the pump through the sample loop is provided, and the exhalation suction passage and the first carrier gas passage are provided. , The second and third carrier gas flow passages, and the second and third carrier gas flow passages can be switched to one of the second and third carrier gas flow passages. All the steps of the concentrated type and the non-concentrated type can be executed only by switching to the gas flow path, so that operability and convenience can be improved.

According to the breath analysis device of the third aspect, the breath sample concentrated and collected in the collection tube is further concentrated and adsorbed on the secondary concentration tube, and the breath sample is pre-columned and main column by the carrier gas. Since it is allowed to pass through, it is possible to sufficiently analyze even lower concentration components.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing an embodiment of an exhalation analyzer according to the present invention, showing a state of switching to an exhalation suction passage and a first carrier gas passage.

FIG. 2 is a configuration diagram showing an embodiment of an exhalation analyzer according to the present invention, showing a state in which switching is made to a second carrier gas flow path and a second carrier gas flow path.

FIG. 3 is a schematic cross-sectional view showing an example of a sampling valve in the breath analysis device of FIGS. 1 and 2, and FIG.
Shows the state where the breath suction passage and the first carrier gas passage are switched, and FIG. 3 [2] shows the state where the second and third carrier gas passages are switched.

FIG. 4 is a cross-sectional configuration diagram illustrating an example of a breath concentration and collection device.

5 is a waveform chart showing an example of analysis results when used as a concentrated type in the breath analyzer of FIG.

6 is an explanatory diagram showing an example of backflush in the breath analyzer of FIG. 1, and time elapses in the order of FIG. 6 [1] to [4].

[Explanation of symbols]

12 Breath Analyzer 141 Pre-column 141 Main Column 16 Detector 18 Collection Tube 20 Concentrated Sample Introduction Section 202 Secondary Concentration Tube 22 Expiration Collection Tube 24 Sample Loop 26 Pump 280 Exhalation Suction Flow Channel 281 First Carrier Gas Flow Channel 282 No. Second carrier gas channel 282 Third carrier gas channel 30 Channel switching unit A'Expiration A Exhaled sample C Carrier gas C ₁ Carrier gas flowing through the first carrier gas channel C ₂ Second carrier gas channel Carrier gas flowing through C ₃ Carrier gas flowing through the third carrier gas channel

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G01N 30/46 G01N 30/46 A 30/88 30/88 E

Claims (3)

[Claims] 1. A pre-column and a main column which pass an exhaled breath sample to separate components contained in the exhaled breath sample,
A detector for detecting the components separated by the precolumn and the main column, a collection tube for adsorbing the exhaled breath sample inside, and a concentrated sample introduction section for desorbing the exhaled breath sample adsorbed in the collection tube , An exhalation sampling tube with exhaled air blown thereinto, a sample loop for adsorbing the exhaled air as an exhaled sample inside, and exhalation in the exhalation sampling tube through the sample loop to suck the exhaled sample into the sample loop. A pump to be filled, a first carrier gas flow path for passing the exhaled sample desorbed in the concentrated sample introduction part to the precolumn and the main column by a carrier gas, and the exhaled sample filled in the sample loop as a carrier. A second carrier gas flow path that allows gas to pass through the main column and the exhalation test remaining in the precolumn. And a third carrier gas flow path for purging by the carrier gas, said first or second and third breath analyzer that includes a one or the other to be switchable flow path switching unit of the carrier gas flow path. 2. An exhalation suction flow path for sucking the exhaled air in the exhalation sampling tube by the pump through the sample loop is provided, and the flow path switching unit includes the exhalation suction flow path and the first carrier gas flow path. And the second and third carrier gas flow paths can be switched to either one. 3. The enriched sample introduction part includes first heating means for heating the collection tube to desorb the exhaled breath sample adsorbed in the collection tube, and adsorbing the exhaled breath sample therein. A secondary concentrating tube, a cooling means for adsorbing the exhaled breath sample desorbed from the collection tube into the secondary concentrating tube, and a breath sample adsorbed in the secondary concentrating tube by heating the secondary concentrating tube The exhalation analyzer according to claim 1, further comprising a second heating means for desorbing the gas.