JP3172126U - Analyzing equipment for gases containing trace components - Google Patents

Abstract

Disclosed is an apparatus for analyzing an extremely small amount of a volatile component that quantifies the total amount of an extremely small amount of components that are in gas-liquid equilibrium. A sample bottle containing a viscous liquid such as blood for maintaining a constant temperature, a vibration device for applying vibration for keeping the sample bottle at a constant temperature, and all gas components on the liquid for analysis Collecting trace components introduced by a conduit for passing a gas amount of 2 times or more, preferably 6 times or more of the volume of gas at the top of the sample bottle, and a conduit from the top of the sample bottle to the outside. It consists of a concentrating device. [Selection] Figure 1

Description

  The present invention is for quantifying the total amount of trace components in gas-liquid equilibrium, and more particularly, relates to a quantitative device for trace components in a gas body in gas-liquid equilibrium.

Conventionally, in order to quantify a very small amount of components in a liquid, it has been practiced to collect a liquid and quantify a part thereof by a liquid chromatograph or a gas chromatograph. If it is a viscous substance such as blood, a dangerous substance, and a compound that easily coagulates, it is a substance, and it is not easy to inject it into the previous chromatograph in a normal state.
For quantitative determination of trace compounds, a method of taking out a gas body using a microsyringe and injecting it into a gas chromatograph, or a method of collecting a trace gas component by attaching an adsorbent to the outside of a syringe needle and then injecting it into the gas chromatograph Has been taken. However, in this method, since a part of the gas body vaporized by vapor-liquid equilibrium is collected, the measurement sensitivity is insufficient, and labor is required to determine the measurement standard for performing the quantification. It was. Also, the operation for collection required an equilibrium time such as 30 minutes. In order to solve these problems, in order to collect the entire gas portion with a gas syringe, it is necessary to employ a sample bottle that contracts in order to prevent external gas contamination when collecting the gas. Sample bottles are not yet in practical use.

  Furthermore, a system for monitoring the blood level of an endogenous compound by detecting a marker that is the endogenous compound itself or a marker that arises from the endogenous compound, such as odor, when the patient exhales is disclosed in Japanese Patent Publication 2009. 519467, which is a method of sampling a patient's expired breath, at least one proportional to the corresponding concentration of at least one endogenous compound in the patient. Analyzing the breath concentration of one endogenous compound marker using sensor technology, calculating the concentration of the endogenous compound marker in the patient's breath, and calculating the endogenous compound marker in the patient's breath Calculate the corresponding concentration of the endogenous compound in the patient based on the measured concentration Comprising a method for monitoring the endogenous compound in a patient, it is due to four stages. This achieves the above object, but there is no disclosure as an analyzer for a gas containing a trace amount component of the present invention.

  Also provided is a measuring device capable of measuring the concentration in the venous anesthetic exhaled breath and determining the blood concentration. Japanese Laid-Open Patent Publication No. 2008-3046 (Patent Document 2) proposes a sampling line that collects exhaled breath from a subject P to which intravenous anesthetic is administered, heats the breath to a predetermined temperature, and keeps the primary ion from the primary ion supply device A reaction device having a drift tube that introduces exhaled air from a sampling line and generates reaction product ions of a venous anesthetic component and primary ions, and ion selection that selects ions of a specific mass from the primary ions and product ions Chamber, an electron multiplier that counts the number of selected primary ions and product ions per unit time, and a predetermined calculation based on the counted number of primary ions and product ions per unit time A control arithmetic unit that calculates an expiratory concentration by an equation and calculates the blood concentration based on a known correlation value between the expiratory concentration and the blood concentration; An output device for outputting that calculation results, those that include a. As can be clearly seen, the concentration in the breath can be measured, but the device is extremely complex and is expected to be an expensive device, and the requirements of the present invention are not shown.

  In addition, a low-concentration ethanol liquid sample is placed in a sealed container as a headspace, leaving a gas phase portion, and a solid-phase microextraction fiber is inserted into the gas phase portion so that the ethanol in the sample solution has an adsorption time of about 1 hour. Japanese Patent Application Laid-Open No. 2011-43329 proposes a method for obtaining ethanol adsorbed by adsorption. This technology adsorbs a part of the ethanol in the gas part, and it is difficult to quickly adsorb to the adsorbent, and a method for collecting all the chemical substances in the gas phase of this project is shown. It has not been.

Japanese Patent Publication No. 2009-519467 JP 2008-3046 A JP 2011-43329 A

The present invention has been devised in view of the above-described conventional apparatus, and the present invention is capable of quantifying a trace amount component in a liquid by subjecting the gas vaporized by vapor-liquid equilibration to analysis. It is possible.
That is, a viscous liquid such as blood is placed in a test bottle, and vibration is applied to maintain a constant temperature. Next, all the gas components on the liquid are subjected to analysis. As an operation for this purpose, a gas amount of 2 times or more, preferably 6 times or more of the volume of the gas body in the upper part of the sample bottle is passed through the upper part of the sample bottle and led to a cooling and concentrating device provided in another location. , Collect trace components. By such an operation, a gas containing a very small amount of components is subjected to almost total analysis.

The present invention makes it possible to determine a very small amount of a component in a liquid by subjecting the gas vaporized by vapor-liquid equilibration to the analysis.
That is, a viscous liquid such as blood is placed in a test bottle, and vibration is applied to maintain a constant temperature. Next, all the gas components on the liquid are subjected to analysis. As an operation for this purpose, a gas amount of 2 times or more, preferably 6 times or more of the volume of the gas body in the upper part of the sample bottle is passed through the upper part of the sample bottle and led to a cooling and concentrating device provided in another location. , Collect trace components. By such an operation, a gas containing a very small amount of components is subjected to almost total analysis.

An embodiment will be described with reference to the drawings. FIG. 1 is a configuration diagram of an analyzer for a gas containing a trace amount component according to the present invention. FIG. 2 is a configuration diagram showing a usage state of the device of the present invention.
An embodiment of the present invention will be described with reference to the drawings. 0.25 ml of blood is placed in 4 ml of a sample bottle. The sample bottle is kept at a temperature of 25 degrees and vibration is applied for 1 minute. A gas stream is passed through the sample bottle for 10 seconds for 10 seconds, and then the sample volatile component gas is cooled and concentrated. The sample gas component is then injected into the gas chromatograph by switching the cock. FIG. 3 is a quantitative graph of acetone and ethanol contained in whole blood.
All of these operations are performed by an automated program. The gas stream that has passed through the sample bottle is three times the volume of the space above the liquid in the sample bottle.
By this procedure, trace gas components acetone and ethanol in blood were measured.
Although it can be applied to viscous liquids as a sample, it can also be applied to the determination of trace components in liquids such as water that are easy to handle.

  FIG. 2 shows an outline of the system when the configuration diagram of FIG. 1 is implemented, and FIG. 2 showing a specific usage state will be described. In the configuration diagram of the usage state of FIG. It lights up when the power is turned on. Reference numeral 2 denotes a reset switch for stopping the operation of the apparatus. Reference numeral 3 denotes a valve opening switch, which can open the electromagnetic valve manually. Reference numeral 4 denotes a vibration switch, which can manually vibrate the vibration container. Reference numeral 5 denotes a start switch for automatically operating the apparatus. Reference numeral 6 denotes a sample connection connector for connecting a gas line before measurement. Reference numeral 7 denotes a vibration adjustment dial for adjusting the vibration intensity of the vibration container. Reference numeral 8 denotes a vibrating container which is vibrated manually or automatically so that the container is kept warm so as to maintain a constant temperature. Reference numeral 9 denotes a conduit which cooperates with the vibrating container 8 and the gas chromatograph 13 for injecting the sample.

The apparatus driving method will be described. The apparatus can be operated automatically or manually. Table 1 shows the operation items of the apparatus.
For automatic operation, press the start switch to start the operation. When operating manually, each part is driven while the switch is pressed.
In addition, operations other than temperature adjustment of the vibrating container can be stopped by pressing a reset switch.

  Next, details of the automatic operation will be described. When the automatic operation is performed, the start switch 5 of the gas chromatograph 10 and the start switch 5 of the present apparatus are simultaneously pressed. The operation after the start switch 5 is pressed will be described below. When the vibrating container vibrates, this is performed for 70 seconds after the switch is pressed. The valve is opened and closed. This is opened 60 seconds after the switch is pressed, and gas is supplied to the sample bottle. The valve closes after 70 seconds.

  Further, the vibration adjustment will be described. The vibration intensity of the vibration container can be adjusted by turning the vibration adjustment dial.

  The overall operation method will be described. As a preparation, as a preparation of the apparatus, the gas chromatograph 13 and the entire gas sampling apparatus are turned on and stabilized for 30 minutes. Next, as a sample preparation, 0.05 to 1.0 ml of the sample is put in a sample bottle. The sample bottle should be at room temperature. A sample bottle is connected to the gas supply line, and a sample bottle cap with two gas lines is connected to the sample bottle containing the sample. This completes the preparation.

Next, the measurement will be described. The measurement is performed in the following order.
1. Place the sample bottle in a vibrating container and keep it accurate for 1 minute. (The vibrating container is kept at 50 ° C, and keep the sample at this temperature.)
2. Press the start button of all gas sampling devices and gas chromatograph devices at the same time.
3. Click the measurement start button of the measurement software on the PC to start data acquisition.
4). Measurement ends in 6 minutes from the start of measurement.
After the measurement is completed, click the measurement end button on the software, and then click the save button to save the measurement result as an image (png format) and data (CSV format).

  When the measurement is completed, the sample bottle containing the sample can be removed from the vibrating container 8 after 70 seconds from the measurement (after the vibration of the vibrating container is stopped). It is also possible to remove the cap from the sample bottle. At this time, the gas line is not removed from the gas connector of the total gas supply device during the measurement. The gas line is removed after the measurement is completed.

  An example of measurement of acetone and ethanol contained in blood is shown in FIG. As shown in FIGS. 1 and 2, the measurement procedure is performed by transferring 0.25 ml of human whole blood stored in a sealed container to the sample bottle 9 as a liquid sample 20. A tertiary butanol solution is then added as an internal standard. Next, the sample bottle 9 is attached to the sample bottle cylinder 21 maintained at a constant temperature by adjusting the temperature, and the temperature is kept at 23 degrees to apply vibration to the sample bottle 9. It is carried out for 70 seconds by the vibration adjustment dial 7 for vibration operation. When the vibration operation has passed for 60 seconds, gas is passed through the conduit 10 for introducing the sample bottle gas, and the gas in the sample bottle 9 is led from the sample bottle 11 through the gas conduit 14 to the sample cooling and concentration tube 22. Guide, cool and concentrate. At this time, it is guided by the suction pump 15. The sample cooling and concentration tube 22 in the cooling and concentration unit 23 is previously cooled to −50 ° C. or less by the liquid carbonic acid 26 through the liquid carbonic acid introduction tube 25. The conduit sample cooling concentration tube 22 and the cooling concentration unit 23 are protected by a protection cylinder 24 formed so as to cover the outer periphery thereof through a conduit 12 for introducing gas from the sample bottle 9 into a sample cooling concentration tube installed in the gas chromatograph 13. Has been. A conduit 25 guides the liquid carbonic acid 26 to the cooling and concentration unit 23. The operation of guiding the sample to the sample cooling and concentration tube 22 is performed for 10 seconds. Next, after the sample cooling and concentration tube 22 is heated to vaporize the sample, the six-way switching valve 19 is operated via the conduit 18, and the gasified sample gas is connected to the gas chromatograph via the conduit 16 and the conduit 17. To the graph 13 and analyzed separately. It was found that acetone in whole blood contained 0.03 mg / dl, and ethanol contained 0.057 mg / dl.

When 290 μl of an aqueous solution containing 3.4 × 10 ⁻⁵ % each of acetone and ethanol was put into a 4 ml sample bottle, gas flow to the sample bottle was conducted for 20 seconds and 28 ml was circulated, and the measurement was performed according to the above procedure. was gotten.

  When commercially available chocolate was put into a sample bottle and measured at a temperature of 50 ° C., the ethanol component was detected.

Effect of device

As described above, the present invention collects a part of a gas body vaporized by vapor-liquid equilibrium, so that measurement sensitivity is not insufficient, and a measurement standard for performing quantification is set. In addition, the collection operation does not require an equilibration time such as 30 minutes for the collection operation, and it is extremely efficient, and the determination of trace components in the liquid is vaporized by vapor-liquid equilibrium. By subjecting all of the gases to analysis, a very small amount can be determined.
This can be used for prevention of drunk driving because the measurement of the alcohol concentration in the blood is very simply performed.

It is a block diagram of the analyzer of the gas containing the trace amount component by this invention. It is a block diagram which shows the use condition of this invention apparatus. It is a quantitative graph of acetone and ethanol contained in whole blood.

DESCRIPTION OF SYMBOLS 1 ... Power lamp 2 ... Reset switch 3 ... Valve open switch 4 ... Vibration switch 5 ... Start switch 6 ... Sample connection connector 7 ... Vibration adjustment dial 8 ... Sample Bottle cylinder 9 ... sample bottle 10 ... conduit 11 for introducing sample bottle gas ... conduit 12 for introducing gas from the sample bottle ... conduit 13 ... gas chromatograph 14 ... gas conduit 15 ... · Suction pump 16 ··· Gas conduit 17 ··· Gas conduit 18 ··· Gas conduit 19 ··· 6-way switching valve 20 ··· Liquid sample 21 in sample bottle · · · Sample bottle cylinder 22 ··· Sample cooling and concentration tube 23 ··· Cooling and concentration unit 24 ··· Protection cylinder 25 ··· Liquid carbonic acid introduction tube 26 ··· Liquid carbonic acid 27 ··· Drying container

The present invention has been devised in view of the above-described conventional apparatus, and the present invention is capable of quantifying a trace amount component in a liquid by subjecting the gas vaporized by vapor-liquid equilibration to analysis. It is possible.
That is, a viscous liquid such as blood is placed in a sample bottle , and vibration is applied to maintain a constant temperature. Next, all the gas components on the liquid are subjected to analysis. The operation for this, more than twice the volume of the sample bottle top gas body, led preferably the amount of more than 6 times the gas is passed through a sample bottle top, to the cooling concentrating device provided elsewhere , Collect trace components. By such an operation, a gas containing a very small amount of components is subjected to almost total analysis.

The present invention makes it possible to determine a very small amount of a component in a liquid by subjecting the gas vaporized by vapor-liquid equilibration to the analysis.
That is, a viscous liquid such as blood is placed in a sample bottle , and vibration is applied to maintain a constant temperature. Next, all the gas components on the liquid are subjected to analysis. The operation for this, more than twice the volume of the sample bottle top gas body, led preferably the amount of more than 6 times the gas is passed through a sample bottle top, to the cooling concentrating device provided elsewhere , Collect trace components. By such an operation, a gas containing a very small amount of components is subjected to almost total analysis.

An embodiment will be described with reference to the drawings. FIG. 1 is a configuration diagram of an analyzer for a gas containing a trace amount component according to the present invention. FIG. 2 is a configuration diagram showing a usage state of the device of the present invention.
An embodiment of the present invention will be described with reference to the drawings. 0.25 ml of blood is placed in 4 ml of a sample bottle . The sample bottle is kept at a temperature of 25 degrees and a vibration is applied for 1 minute. A gas stream is passed through the sample bottle for 14 seconds for 10 seconds, and then the sample volatile component gas is cooled and concentrated. The sample gas component is then injected into the gas chromatograph by switching the cock. FIG. 3 is a quantitative graph of acetone and ethanol contained in whole blood.
All of these operations are performed by an automated program. The gas stream that has passed through the sample bottle is three times the volume of the space above the liquid in the sample bottle.
By this procedure, trace gas components acetone and ethanol in blood were measured.
Although it can be applied to viscous liquids as a sample, it can also be applied to the determination of trace components in liquids such as water that are easy to handle.

An example of measurement of acetone and ethanol contained in blood is shown in FIG. As shown in FIGS. 1 and 2, the measurement procedure is performed by transferring 0.25 ml of human whole blood stored in a sealed container to the sample bottle 9 as a liquid sample 20. A tertiary butanol solution is then added as an internal standard. Next, the sample bottle 9 is attached to the sample bottle cylinder 21 maintained at a constant temperature by adjusting the temperature, and the temperature is kept at 23 degrees to apply vibration to the sample bottle 9. It is carried out for 70 seconds by the vibration adjustment dial 7 for vibration operation. When the vibration operation has passed 60 seconds, leads to the gas from the conduit 10 to guide the gas into the sample bottle in a sample bottle 9, then it leads to the gas by venting the gas in the sample bottle 9 from the sample bottle gas to external conduit 11 through the gas conduit 14 to the sample cooling and concentration tube 22 for cooling and concentration. At this time, it is guided by the suction pump 15. The sample cooling and concentration tube 22 in the cooling and concentration unit 23 is previously cooled to −50 ° C. or less by the liquid carbonic acid 26 through the liquid carbonic acid introduction tube 25. The conduit sample cooling concentration tube 22 and the cooling concentration unit 23 are protected by a protection cylinder 24 formed so as to cover the outer periphery thereof through a conduit 12 for introducing gas from the sample bottle 9 into a sample cooling concentration tube installed in the gas chromatograph 13. Has been. A conduit 25 guides the liquid carbonic acid 26 to the cooling and concentration unit 23. The operation of guiding the sample to the sample cooling and concentration tube 22 is performed for 10 seconds. Next, after the sample cooling and concentration tube 22 is heated to vaporize the sample, the six-way switching valve 19 is operated via the conduit 18, and the gasified sample gas is connected to the gas chromatograph via the conduit 16 and the conduit 17. To the graph 13 and analyzed separately. It was found that acetone in whole blood contained 0.03 mg / dl, and ethanol contained 0.057 mg / dl.

It is a block diagram of the analyzer of the gas containing the trace amount component by this invention. It is a block diagram which shows the use condition of this invention apparatus. It is a quantitative graph of acetone and ethanol contained in whole blood.

DESCRIPTION OF SYMBOLS 1 ... Power lamp 2 ... Reset switch 3 ... Valve open switch 4 ... Vibration switch 5 ... Start switch 6 ... Sample connection connector 7 ... Vibration adjustment dial
DESCRIPTION OF SYMBOLS 8 ... Vibration apparatus 9 ... Sample bottle 10 ... Conduit which guides sample bottle gas 11 ... Conduit which guides gas from a sample bottle 12 ... Conduit 13 ... Gas chromatograph 14 ... Gas conduit DESCRIPTION OF SYMBOLS 15 ... Suction pump 16 ... Gas conduit 17 ... Gas conduit 18 ... Gas conduit 19 ... Six-way switching valve 20 ... Liquid sample 21 in a sample bottle ... Sample tube 22 ... Sample cooling concentration tube 23 ... Cooling concentration unit 24 ... Protection cylinder 25 ... Liquid carbonic acid introduction tube 26 ... Liquid carbonic acid 27 ... Drying container

Claims (1)

  To provide a test bottle containing a viscous liquid such as blood for maintaining a constant temperature, a heat retaining device for keeping the test bottle at a constant temperature, a vibration device for applying vibration, and all gas components on the liquid for analysis , Contained in a liquid comprising a conduit for passing a gas volume of 2 times or more, preferably 6 times or more of the volume of the gas body at the top of the sample bottle, and a concentrating device for collecting a trace amount component by the conduit An analyzer for trace volatile components.