JPH09166587A - Expiration analyzing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To sufficiently analyze even a low concentration component such as a trace quantity of pentane in expiration by disrobing an exhalation sample, concentrated and collected in a collecting pipe, at a concentrated sample lead-in part, and making this exhalation sample pass a first pre-column and a main column by carrier gas. SOLUTION: Using an expiration concentrating collecting device 80, an expiration sample A is adsorbed in a collecting pipe 26. The collecting pipe 26 is mounted in a concentrated sample lead-in part 28. The collecting pipe 26 is heated, while a secondary concentrating pipe 282 is cooled, and a carrier gas passage 361 is selected by a passage switching part 38 so as to make carrier gas C pass from the collecting pipe 26 to the secondary concentrating pipe 282. The sample A is thereby desorbed from the collecting pipe 26, further concentrated and adsorbed into the secondary concentrating pipe 282. When the secondary concentrating pipe 282 is heated, since a solenoid valve 385 is closed, carrier gas C1 passes a solenoid valve 384, the lead-in part 28, ports 3, 4, a first per-column 221, ports 7, 8, a main column 223 and a detector 24. The respective components of the sample A are separated by columns 221, 223 so a to be detected by a detector 24 with time difference.

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, which comprises first and second pre-columns and a main column for passing a breath sample to separate components contained in the breath sample, and these first and second pre-columns. A detector that detects the components separated by the first and second pre-columns and the main column, a collection tube that adsorbs the exhaled breath sample inside, and a concentration that desorbs the exhaled breath sample adsorbed in this collection tube A sample introduction unit, an exhalation sampling tube with exhaled air blown thereinto, a sample loop for adsorbing exhaled air as an exhaled sample inside, and exhalation in the exhalation sampling tube being sucked through the sample loop into the sample loop. A pump for filling the exhaled breath sample, and the exhaled breath sample desorbed in the concentrated sample introduction section is introduced into the first pre-column and the main column by a carrier gas. A first carrier gas passage for passing, a second carrier gas passage for passing the exhaled sample filled in the sample loop to the second precolumn and the main column by a carrier gas, and the first A third carrier gas flow path for purging the exhaled breath sample remaining in a pre-column with a carrier gas, a fourth carrier gas flow path for purging the exhaled breath sample remaining in the second pre-column with a carrier gas, and the fourth A flow path switching unit capable of switching to either one of the first and fourth carrier gas flow paths or the 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 first 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 exhaled breath sample filled in the sample loop passes through the second pre-column and the main column together with the 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 according to the above, an exhalation suction flow path for sucking the exhaled air in the exhalation sampling tube with the pump through the sample loop is attached, and the flow path switching unit includes the exhalation suction flow path and the first and fourth It is possible to switch to either one of the carrier gas passage of No. 2 and the second and third carrier gas passages.

All the steps of the concentrated type and the non-concentrated type can be executed only by switching between the exhaled breath suction channel and the first and fourth carrier gas channels and the second and third carrier gas channels. Is possible.

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 block diagrams showing an embodiment of an exhalation analyzer according to the present invention. FIG. 1 shows an exhalation suction passage and first and fourth carrier gas passages. The switched state is shown, and FIG. 2 shows the switched state to the second and third carrier gas flow paths. Hereinafter, description will be made mainly with reference to these drawings.

The breath analyzer 20 according to the present invention includes a first pre-column 221, a second pre-column 222 and a main column 223, which pass the breath sample A to separate the components contained in the breath sample A, and the pre-column 221. Detector 24 for detecting the components separated by 222 and main column 223, and collection tube 2 in which breath sample A is adsorbed inside
6, a concentrated sample introduction part 28 for desorbing the exhaled breath sample A adsorbed in the collection tube 26, an exhaled breath collection tube 30 with exhaled breath A ′ blown thereinto, and exhaled breath A ′ as the exhaled breath sample A. Sample loop 32 adsorbed inside and exhalation sampling tube 30
A pump 34 that fills the exhaled breath sample A into the sample loop 32 by sucking the exhaled breath A ′ in the sample loop 32, and an exhaled breath suction that sucks the exhaled breath A ′ in the exhalation sampling tube 30 through the sample loop 32 with the pump 34. The flow path 360 and the first carrier gas flow path 36 that allows the exhaled breath sample A desorbed in the concentrated sample introduction part 28 to pass through the pre-column 221 and the main column 223 by the carrier gas C ₁ .
1 and the second carrier gas flow path 36 that allows the exhaled breath sample A filled in the sample loop 32 to pass through the pre-column 222 and the main column 223 by the carrier gas C ₂ .
2, a third carrier gas channel 283 for purging the exhaled breath sample A remaining in the pre-column 221 with the carrier gas C ₃ , and a fourth carrier gas for purging the exhaled breath sample A remaining in the pre-column 222 with the carrier gas C ₄ . A flow channel 364, a breath suction flow channel 360, and a flow channel switching unit 38 that can switch to one of the carrier gas flow channels 361 and 364 and the carrier gas flow channels 362 and 363 are provided.

The pre-columns 221 and 222 have the characteristics that it is difficult to hold the components to be analyzed and it is easy to hold unnecessary components that are not to be analyzed. Pre-column 221,
The length of 222 is determined based on the retention of components, the elution time, and the like. Further, by making the characteristics of the pre-columns 221 and 222 different, it is possible to perform different purposes of analysis in the concentrated type and the non-concentrated type.

The concentrated sample introduction section 28 includes a collection tube support 281 for supporting the collection tube 26, a secondary concentration tube 282 for adsorbing the breath sample A therein, and a secondary concentration tube 282 for supporting the secondary concentration tube 282. Concentrator support 283. The collection tube support 281 incorporates a first heating means (not shown) for desorbing the exhaled breath sample A adsorbed in the collection tube 26. The secondary concentrating tube support 283 has a cooling means (not shown) for adsorbing the exhaled breath sample A desorbed from the collecting tube 26 to the inside of the secondary concentrating tube 282, and the secondary concentrating tube 282 is heated to be secondary. A second heating means (not shown) for desorbing the exhaled breath sample A adsorbed in the concentrating tube 282 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 pipe 282, a capillary pipe having an inner diameter of 0.5 to 1.0 mm is used, but it is preferable that the material and the characteristics of the main column 223 are the same. In addition, the secondary concentration tube 2
Since 82 uses the liquid phase of the adsorbent coated, the efficiency of the secondary concentration is higher than that of the uncoated raw tube. The secondary concentration tube 282 and the secondary concentration tube support 283 may be omitted when the concentration rate of the collection tube 26 is high.

The exhalation sampling tube 30 has an exhalation outlet 301 and an exhalation inlet 302. The subject attaches the disposable mouthpiece 303 to the exhalation inlet 302, puts his mouth on the mouthpiece 303, and exhales A ′ to the exhalation sampling tube 30.
Blow in. The exhalation sampling tube 30 is fixed by an exhalation sampling tube support 31. Breath collection tube support 3
A first heating means (not shown) for heating the exhaled air A ′ etc. is built in the apparatus 1.

The flow path switching section 38 includes a sampling valve 381, electromagnetic valves 382, 383, 384 and 385.
It is composed of a sampling valve 381 and a control unit 386 for controlling energization of solenoids of the solenoid valves 382 to 385. The control means 386 may be any one such as a manual switch, a relay and a timer, a microcomputer and its program. In the flow path switching unit 38, the gas cylinder 401 filled with the carrier gas C is provided with the pressure reducing valve 402.
Connected through. As the carrier gas C, air, hydrogen, nitrogen, helium, argon or the like is generally used.

The sampling valve 381 is, for example, a rotary valve having 16 ports 1 to 16.
FIG. 3 is a schematic sectional view showing an example of the sampling valve 381. In FIG. 3, a sampling valve 381
Is composed of a fixed body 381A having ports 1 to 16, a rotating body 381B having communication tubes a to h, and an actuator (not shown) such as a solenoid for rotating the rotating body 381B. FIG. 3 [1] shows the exhalation suction flow path 360.
And the carrier gas flow paths 361 and 364 are switched to each other, and FIG. 3B shows the carrier gas flow paths 362 and 363 switched to each other.

A pipe 421 for introducing the carrier gas C ₂ through the solenoid valve 383 is connected to the port 1.
A pipe 422 for discharging the carrier gas C ₅ that has passed through the concentrated sample introduction unit 28 is connected to the port 2. A pipe 423 for introducing the carrier gas C ₁ that has passed through the concentrated sample introduction unit 28 through a filter 284 is connected to the port 3. A pipe 424 connected to one end of the pre-column 221 is connected to the port 4. A pipe 425 for discharging the carrier gas C ₃ that has passed through the pre-column 221 is connected to the port 5. A pipe 4 for introducing carrier gas C ₃ through a solenoid valve 385 to the port 6.
26 is connected. Pre-column 22 on port 7
The pipe 427 connected to the other end of 1 is connected. The port 8 has a pipe 42 connected to the main column 223.
8 are connected. Pre-column 222 on port 9
A pipe 429 connected to one end of is connected. A pipe 430 for introducing the carrier gas C ₄ through the solenoid valve 382 is connected to the port 10. A pipe 431 for discharging the carrier gas C ₄ that has passed through the pre-column 222 is connected to the port 11. On port 12,
A pipe 432 connected to the other end of the pre-column 222 is connected. A pipe 433 connected to one end of the sample loop 32 is connected to the port 13. Port 1
A pipe 434 connected to the pump 34 is connected to the pipe 4. A pipe 435 connected to the exhalation sampling tube 30 is connected to the port 15. A pipe 436 connected to the other end of the sample loop 32 is connected to the port 16. The pre-columns 221 and 222, the main column 223, the sampling valve 381, and the pipes 421, ... Surrounding them are housed in a thermostat (not shown) kept at a constant temperature of 100 ° C., for example.

The detector 24 may detect any of mass, heat conduction, ionic current and the like.

Next, the operation of the breath analyzer 20 will be described.

[Concentration type operation 1 (adsorption of breath sample)]

First, the exhaled breath sample A is adsorbed to the collection tube 26 by using the exhaled air concentration and collection device 80 shown in FIG. The breath concentration collector 80 collects the Tedlar bag 82 filled with the breath A ′, the collection pipe 26 communicating with the inside of the Tedlar bag 82, and the collection pipe 26 of the breath A ′ inside the Tedlar bag 82.
A pump 84 for suctioning through, a cumulative flow meter 86 for measuring a cumulative flow rate f of the expiratory air A ′ passing through the collection tube 26, a pressure gauge 88 for measuring a pressure p of the expiratory 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 constant value p _F or less, a thermostat 92 that keeps the temperature T of the collection tube 26 constant, and a trap The water absorption filter 94 is provided in the flow path of the exhaled air A ′ between the collecting tube 26 and the pump 84. Tedlar bag 82, T-tube 881 of pressure gauge 88,
The collection tube 26, 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 26 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 collecting tube 26 is sandwiched between the upper side 98 and the lower side 99. Therefore, the collection tube 26 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 26 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 26 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 back 82 through the collection tube 26. As a result, the exhaled breath component A is concentrated and collected by the adsorbent 181 in the collection tube 26. 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 controller 90, the collection tube 26
The amount of expiration A 'concentrated in the water is also known.

Subsequently, the collection tube 26 is connected to the concentrated sample introduction section 28.
And heat the collecting tube 26 to, for example, 250 ° C. and cool the secondary concentrating tube 282 to, for example, −130 to −180 ° C.
In addition, the carrier gas passage 36 is formed by the passage switching unit 38.
1 (FIG. 1) is selected to allow the carrier gas C to pass from the collecting pipe 26 to the secondary concentrating pipe 282. Then, exhaled sample A
Desorbs the collecting tube 26, is further concentrated, and is adsorbed to the secondary concentrating tube 282.

[Concentration type operation 2 (analysis)]

When the adsorption of the exhaled breath sample A to the secondary concentrating tube 282 is completed, the secondary concentrating tube 282 is heated to 190 ° C., for example. At this time, in order to save the carrier gas C, the solenoid valve 38
Since 5 is closed, the carrier gas C ₁ is supplied from the solenoid valve 384 → concentrated sample introducing unit 28 → filter 284 → port 3 → port 4 → precolumn 221 → port 7 → port 8
→ Main column 223 → detector 24 → discharge. The exhaled breath sample A also flows together with the carrier gas C ₁ and passes through the pre-column 221, the main column 223 and the detector 24. Each component contained in the exhaled breath sample A has a pre-column 221.
And the main column 223 separates them, so that they are detected by the detector 24 with a time difference. In the detector 24, a qualitative analysis is performed by the volume (holding capacity) of the carrier gas C _{1 from} the time when the breath sample A is injected until the separation zone of each component comes out or the time (holding time), and the peak area or peak is obtained. Quantitative analysis is performed from the height.

According to the breath analysis device 12, since the breath sample A concentrated by the concentrated sample introducing section 28 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 3 (backflush and analysis)]

Then, the carrier gas flow path 363 (FIG. 2) is selected by the flow path switching unit 38 to select the carrier gas C ₃
Flow. At this time, the solenoid valve 385 is opened, so that the carrier gas C ₃ is transferred to the solenoid valve 385 → port 6 → port 7 →
The pre-column 221 can be purged by flowing through the pre-column 221 → port 4 → port 5 → discharging. If the solenoid valve 384 is opened, the carrier gas C
₅ is a solenoid valve 384 → concentrated sample introduction part 28 → filter 2
By the flow of 84 → port 3 → port 2 → discharge,
The collection tube 26 and the secondary concentration tube 282 can be purged.

At this time, the carrier gas passage 362 (FIG. 2) may be selected by opening the solenoid valve 383. In this case, the carrier gas C ₂ is the solenoid valve 383 →
Port 1 → Port 16 → Sample loop 32 → Port 1
3 → port 12 → pre-column 222 → port 9 → port 8 → main column 223 → detector 24 → discharge.
Therefore, the exhaled breath sample A remaining in the main column 223 also flows together with the carrier gas C ₂ , so that the analysis can be continued as necessary and the main column 223 and the like can be purged. In this case, it is premised that the sample loop 32 and the precolumn 222 are not filled with the breath sample A.

[Non-concentrating operation 1 (exhalation suction)]

First, the exhalation sampling tube 30 is heated to, for example, 40 ° C., and the exhalation suction passage 360 (FIG. 1) is selected by the passage switching unit 38. When the subject blows the exhaled air A ′ into the exhaled air sampling tube 30, the pump 34 correspondingly operates for a predetermined time. At this time, the exhalation A ′ is the exhalation sampling tube 30 → port 15 → port 16 → sample loop 32 → port 1
3 → port 14 → pump 34 → discharging. As a result, the breath A ′ is filled in the sample loop 32 as the breath sample A.

[Non-concentrated operation 2 (analysis)]

Subsequently, the carrier gas flow path 362 (FIG. 2) is selected by the flow path switching unit 38 to flow the carrier gas C. At this time, the solenoid valve 383 is opened, so that the carrier gas C ₂ is transferred to the solenoid valve 383 → port 1 → port 16 →
Sample loop 32 → port 13 → port 12 → pre-column 222 → port 9 → port 8 → main column 223
-> Detector 24-> Eject and flow. The exhaled breath sample A filled in the sample loop 32 also flows together with the carrier gas C ₂ .
Pre-column 222, main column 223 and detector 24
Pass through. Each component contained in the exhaled breath sample A is separated by the pre-column 222 and the main column 223, and thus detected by the detector 24 with a time difference.
The detector 24 performs a predetermined analysis as described above.

[Non-concentrated operation 3 (backflush and analysis)]

Subsequently, the carrier gas flow path 364 (FIG. 1) is selected by the flow path switching unit 38 to select the carrier gas C ₄
Flow. At this time, the solenoid valve 382 is opened, so that the carrier gas C ₄ is transferred to the solenoid valve 382 → port 10 → port 9
The pre-column 222 can be purged by the flow of → pre-column 222 → port 12 → port 11 → discharge.

At this time, the carrier gas passage 361 (FIG. 1) may be selected by opening the solenoid valve 384. In this case, the carrier gas C ₁ is the solenoid valve 384 →
The flow proceeds in the order of concentrated sample introduction unit 28 → filter 284 → port 3 → port 4 → precolumn 221, port 7 → port 8 → main column 223 → detector 24 → discharge. Therefore, the exhaled breath sample A remaining in the main column 223 also flows together with the carrier gas C ₁ , so that the analysis can be continued as necessary and the main column 223 and the like can be purged. In this case, it is premised that the collection tube 26, the secondary concentration tube 282, and the precolumn 221 are not filled with the breath sample A.

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.

For example, a high boiling point component such as hexane has a long residence time in the precolumns 221 and 222 and the main column 223 (retention time is slow). 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. In addition, the main column 223 and the detector 16
Passing a high-boiling point component such as hexane H into the mixture also causes contamination and deterioration of these components.

Therefore, in order to shorten the analysis time and prevent contamination and deterioration, backflushing is performed on the precolumns 221 and 222. First, the pre-column 221
Will be described. Carrier gas C ₁ is pre-column 22
1 and the main column 223 start flowing, breath sample A
Pentane P and hexane H, which are the components of
21 is entered (FIG. 6 [1]). Pentane P is hexane H
Since it is less likely to be retained by the pre-column 221, it passes through the pre-column 221 first (FIG. 6 [2]). Hexane H is still in the pre-column 221 even though the time has passed and the pentane P has advanced considerably through the main column 223 (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 223. Therefore, the pre-column 221 and the main column 223 are separated, a carrier gas C ₃ in the opposite direction to the carrier gas C ₁ is caused to flow through the pre-column 221, and a carrier gas C ₁ in the same direction as the carrier gas C ₁ is passed through the main column 223.
Flow ₂ As a result, the pentane P will be transferred to the main column 22.
3 is detected and hexane H is also purged from the precolumn 222 (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. Further, since hexane H does not flow to the main column 223 and the detector 24, contamination and deterioration of these are also prevented. For the pre-column 222, the pre-column 2
Since it is similar to the case of _No. 21, it may be considered by replacing it with precolumn 221 → 222, carrier gas C ₁ → C ₂ , carrier gas C ₃ → C ₄ , carrier gas C ₂ → C _{1 in} FIG.

Needless to say, the above embodiment is merely an example and does not limit the present invention. For example,
The sampling valve 381 may switch the flow path by switching the electromagnetic valve. The breath analysis apparatus 20 may be fully automated by providing the control means 386 with a function of controlling the detector 24, the concentrated sample introduction unit 28, the breath collection tube support 31, the pump 34, and the like.
Ports 1 to 16, pre-columns 221 and 222, main column 223, exhalation sampling tube 30, sample loop 3
2, the connection with the pump 34 and the solenoid valves 382-385,
Exhalation suction flow path 360 and carrier gas flow paths 361 to 36
Any combination may be used as long as the above-mentioned functions of No. 4 can be realized.

[0050]

According to the breath analysis apparatus of the first to third aspects, the breath sample concentrated and collected in the collection tube is desorbed in the concentrated sample introduction part, and the breath sample is first collected by the carrier gas. Since it is passed through the pre-column and the main 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 through the first precolumn and the main column by the carrier gas, and the exhaled breath sample filled in the sample loop is discharged by the carrier gas to the second side. Second carrier gas flow path to be passed through the pre-column and the main column, a third carrier gas flow path for purging the exhaled breath sample remaining in the first pre-column with carrier gas, and the exhaled breath sample remaining in the second pre-column A fourth carrier gas flow path for purging the carrier gas with a carrier gas, and a flow path switching unit capable of switching to either the first and fourth carrier gas flow paths or the second and third carrier gas flow paths. Since it is provided, 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, since the third and fourth carrier gas flow paths can quickly discharge unnecessary high-boiling components without passing through the main column and the detector, the analysis time can be significantly shortened and the main column and the detector can be shortened. It can also prevent the contamination and deterioration of.

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, the first and fourth carrier gases are provided. The flow passage and the second and third carrier gas flow passages can be switched to one of the flow passage switching units, so that the exhaled air suction flow passage, the first and fourth carrier gas flow passages, and All the steps of the concentrated type and the non-concentrated type can be performed only by switching to the second and third carrier gas flow paths, 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 first and fourth carrier gas passages.

FIG. 2 is a configuration diagram showing an embodiment of an exhalation analyzer according to the present invention, showing a state in which the second and third carrier gas flow paths are switched.

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 of switching to the exhalation suction flow channel and the first and fourth carrier gas channels, and FIG. 3 [2] shows the state of switching to the second and third carrier gas channels.

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]

20 Breath Analyzer 221 First Pre-column 222 Second Pre-column 223 Main Column 24 Detector 26 Collection Tube 28 Concentrated Sample Introducing Section 282 Secondary Concentration Tube 30 Exhalation Collection Tube 32 Sample Loop 34 Pump 360 Exhalation Suction Flow Path 361 First One carrier gas flow path 362 Second carrier gas flow path 363 Third carrier gas flow path 364 Fourth carrier gas flow path 38 Flow path switching unit A'Exhalation A Exhaled sample C Carrier gas C ₁ First carrier Carrier gas flowing through the gas channel C ₂ Carrier gas flowing through the second carrier gas channel C ₃ Carrier gas flowing through the third carrier gas channel C ₄ Carrier gas flowing through the fourth carrier gas channel

Claims (3)

[Claims] 1. A first and second pre-column and a main column for passing a breath sample to separate components contained in the breath sample, and components separated by the first and second pre-columns and the main column. A detector for detecting the exhaled air, a collection tube that adsorbs the exhaled breath sample inside, a concentrated sample introduction part that desorbs the exhaled breath sample adsorbed inside this collection tube, and exhaled breath sampling that exhaled breath into the inside A tube and a sample loop that adsorbs exhaled air as an exhaled breath sample inside,
A pump for charging the exhaled breath sample in the exhaled breath collection tube through the sample loop to fill the exhaled breath sample in the sample loop, and the exhaled breath sample desorbed in the concentrated sample introduction part by the carrier gas to the first precolumn and A first carrier gas channel to be passed through the main column, and a second carrier gas channel for passing the exhaled sample filled in the sample loop to the second precolumn and the main column by a carrier gas, A third carrier gas passage for purging the exhaled breath sample remaining in the first precolumn with a carrier gas, and a fourth carrier gas passage for purging the exhaled breath sample remaining in the second precolumn with a carrier gas. And the first and fourth carrier gas flow paths or the second and third carrier gas Breath analyzer and a switchable flow path switching unit either one on the road. 2. An exhalation suction flow path for sucking the exhaled air in the exhalation collection 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 and fourth carriers. The breath analyzer according to claim 1, which is switchable to either one of the gas channel and the second and third carrier gas channels. 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.