CN109283154A - The detection system and method for volatile organic matter molecule in a kind of exhaled gas - Google Patents

The detection system and method for volatile organic matter molecule in a kind of exhaled gas Download PDF

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CN109283154A
CN109283154A CN201811298889.0A CN201811298889A CN109283154A CN 109283154 A CN109283154 A CN 109283154A CN 201811298889 A CN201811298889 A CN 201811298889A CN 109283154 A CN109283154 A CN 109283154A
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gas
chamber
gasmetry
alveolar
organic matter
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CN109283154B (en
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娄存广
刘秀玲
荆聪蕊
侯凯旋
祝伟仝
吕林洋
王鑫
张建涛
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Hebei University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3581Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
    • G01N21/3586Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation

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Abstract

The present invention provides the detection system and method for volatile organic matter molecule in a kind of exhaled gas, the detection system includes the gentle bulk measurement system of alveolar gas separating system;The alveolar gas separating system includes declining to swing chamber, pulse laser, photodetector and signal processing and control system;The gas measurement system includes gasmetry chamber, transmitter, detector, Terahertz lens and signal processing system.The present invention utilizes near infrared light cavity ring-down spectroscopy measuring system, realize the online real-time separation of dead space gas and alveolar air, endogenous VOCs concentration is higher by two to three times than the concentration in the exhaled gas sample for being mixed with dead space gas in alveolar air, and alveolar air can more reflect human physiological metabolism's situation, thus be excluded that the interference of dead space gas or other invalid gases, characteristic molecular measurement accuracy is helped to improve, system detection sensitivity is greatly promoted.

Description

The detection system and method for volatile organic matter molecule in a kind of exhaled gas
Technical field
The present invention relates to gas detection technology fields, and in particular to the inspection of volatile organic matter molecule in a kind of exhaled gas Examining system and method.
Background technique
The certain metabolins and chemical substance of body or blood flow carry out blood circulation system and systemic pulmonary circulation in alveolar Exchange, causes exhaled gas component and concentration to can reflect body metabolism function and morbid state, waving in characteristics of contaminated respiratory droplets gas The measurement of hair property chemical substance (VOCs) is suitable in healthy population carrying out tendency patient as a kind of Non-invasive detection technology Screening, therefore receive more and more attention.It has been generally acknowledged that the levels of the analyte of measurement and the degree of potential disease Between exist association.For example, the ethyl alcohol and acetone in exhaled gas are related with intracorporal glucose metabolism, it can reflect testee's Blood glucose level.However, feature VOCs concentration is generally in ppm magnitude and hereinafter, gas componant is complicated and on having in exhaled gas As many as hundred kinds, in addition to there are also free radicals for stable molecule, and meanwhile it is larger by environmental gas interference, measurement accuracy is affected, at present Common laser spectrometry is difficult to distinguish these disturbing molecules.In addition, disease marker content is extremely low, type is more, compels The detection method of highly sensitive, strong specificity and high s/n ratio will be developed by being essential.
Studies have shown that the relevant VOCs molecule of disease and group have fixed rotational frequency, especially acetone, acetaldehyde, H2S isopolarity molecule shows distinct " fingerprint " characteristic in terahertz wave band, has stronger absorption.And in exhaled gas Account for the CO of larger proportion2It is not absorbed Deng in terahertz wave band, greatly reduces interference, avoid the bands of a spectrum overlapping of infrared spectroscopy Problem, so that molecule identification is more easier.But using tera-hertz spectra detection, there are still trace gas molecules types merely More, concentration is low, and spectral signature identifies more difficult, the low disadvantage of detection sensitivity.Therefore, it is dense how to improve VOCs in detection gas Degree excludes other factors interference, and the highly sensitive detection for obtaining marker becomes focus on research direction.
Summary of the invention
One of the objects of the present invention is to provide a kind of detection systems of volatile organic matter molecule in exhaled gas, with solution Certainly existing apparatus spectral signature identifies more difficult, the low problem of detection sensitivity.
The second object of the present invention is to provide a kind of detection method of volatile organic matter molecule in exhaled gas.
An object of the present invention is achieved through the following technical solutions: volatile organic matter point in a kind of exhaled gas The detection system of son, including the gentle bulk measurement system of alveolar gas separating system;
The alveolar gas separating system includes:
Decline and swing chamber, be airtight cavity, the both ends of cavity are high reflectivity mirror, be equipped on the cavity for exhaled gas into The inflatable mouth entered, the first gas outlet, the second gas outlet for alveolar air discharge and the pressure monitoring mouth that are discharged for dead space gas, It is equipped with check valve at the inflatable mouth, the first gas outlet and the second gas outlet, it is equal at the first gas outlet and the second gas outlet Equipped with vacuum pump;
Pulse laser, for swinging chamber emission pulse laser to declining;
Photodetector, for detect through decline swing chamber after the exponential decay curve that changes over time of light signal strength;And
Signal processing and control system become at any time for obtaining carbon dioxide in gas concentration according to the synchronous operation of ring-down time The waveform diagram of change, and corresponding vacuum pump is controlled according to gas concentration lwevel information, dead space gas is discharged, alveolar air is pumped into gas Measuring system;
The gas measurement system includes:
Gasmetry chamber is airtight cavity, and the both ends of cavity are Terahertz window, and the air inlet imported for alveolar air is equipped on cavity Mouthful, the exhaust outlet for excessive gas to be discharged and the air pressure detection mouth being connected with air gauge, be equipped with gasmetry is intracavitary Active adsorbing material, for adsorbing the volatile organic matter molecule under test gas;
Transmitter, for generating and emitting THz wave to gasmetry chamber;
Detector, for receiving the THz wave across gasmetry chamber;
Terahertz lens, including the first Terahertz lens and the second Terahertz lens, the first Terahertz lens be set to transmitter and It is intracavitary for THz wave to be focused on gasmetry between gasmetry device;Second Terahertz lens are set to gasmetry chamber Between detector, the THz wave for passing through gasmetry chamber converges to detector;And
Signal processing system, for detection gas terahertz time-domain spectroscopy and frequency domain spectra be analyzed and processed.
In the alveolar gas separating system, is swung in the pulse laser and declining and be equipped with optoisolator between chamber, described Pressure monitoring mouth is equipped with gas pressure sensor, and blow gun and filter are equipped at the inflatable mouth, and described decline swings chamber for diameter For 5cm, length is the cylindrical stainless steel cavity of 20cm.
In the alveolar gas separating system, the pulse laser is the single mode pulse laser of output wavelength 1573nm, Pulse recurrence frequency 100Hz ~ 1KHz is continuously adjustable, 2 ~ 3ns of pulsewidth.
In the gas measurement system, Terahertz window selects HDPE material, and the exhaust outlet is equipped with vacuum pump.
In the gas measurement system, the adsorbent material is graphene oxide paper, Au- graphene oxide, foamy graphite Alkene, PdO WO3One of nano material or tin oxide-reduced graphene nano film material.
The second object of the present invention is to what is be achieved: the detection side of volatile organic matter molecule in a kind of exhaled gas Method, comprising the following steps:
A, the detection system of volatile organic matter molecule in exhaled gas is set, and the detection system includes alveolar gas separating system And gas measurement system;
The alveolar gas separating system includes:
It declines and swings chamber, be airtight cavity, the both ends of cavity are the reflecting mirror of reflectivity > 99.9%, are equipped on the cavity for exhalation Inflatable mouth, the first gas outlet for the discharge of dead space gas, the second gas outlet for alveolar air discharge and the pressure prison that gas enters Mouth is surveyed, check valve is equipped at the inflatable mouth, the first gas outlet and the second gas outlet, in the first gas outlet and the second outlet Vacuum pump is equipped at mouthful;
Pulse laser, for swinging chamber emission pulse laser to declining;
Photodetector, for detect through decline swing chamber after the exponential decay curve that changes over time of light signal strength;And
Signal processing and control system become at any time for obtaining carbon dioxide in gas concentration according to the synchronous operation of ring-down time The waveform diagram of change, and corresponding vacuum pump is controlled according to gas concentration lwevel information, dead space gas is discharged, alveolar air is pumped into gas Measuring system;
The gas measurement system includes:
Gasmetry chamber is airtight cavity, and the both ends of cavity are Terahertz window, and the air inlet imported for alveolar air is equipped on cavity Mouthful, the exhaust outlet for excessive gas to be discharged and the air pressure detection mouth being connected with air gauge, be equipped with gasmetry is intracavitary Active adsorbing material, for adsorbing the volatile organic matter molecule under test gas;
Transmitter, for generating and emitting THz wave to gasmetry chamber;
Detector, for receiving the THz wave across gasmetry chamber;
Terahertz lens, including the first Terahertz lens and the second Terahertz lens, the first Terahertz lens be set to transmitter and It is intracavitary for THz wave to be focused on gasmetry between gasmetry device;Second Terahertz lens are set to gasmetry chamber Between detector, the THz wave for passing through gasmetry chamber converges to detector;And
Signal processing system, for detection gas terahertz time-domain spectroscopy and frequency domain spectra be analyzed and processed;
B, start detection system, will decline and swing chamber and be evacuated to vacuum, pulmonary gases incoming call is declined by inflatable mouth and swings chamber by subject, online Real-time detection, which enters to decline, swings the ring-down time of chamber gas;
C, signal processing and control system obtain carbon dioxide in gas concentration changes with time according to the synchronous operation of ring-down time Waveform diagram, and determined to enter the stage locating for gas automatically according to waveform diagram, then by controlling corresponding vacuum pump, by dead space gas It is intracavitary to be pumped into gasmetry by discharge for alveolar air;
D, the intracavitary active adsorbing material of gasmetry adsorbs the volatile organic matter molecule in alveolar air, passes through air pressure The table pressure intracavitary to gasmetry is monitored, and excessive gas is discharged by exhaust outlet, then uses radiation of visible light gasmetry Chamber enables active adsorbing material to adsorb more volatile organic matter molecules;
E, transmitter is generated and transmitted by THz wave, and THz wave converges to detector after passing through gasmetry chamber, finally obtains The terahertz time-domain spectroscopy and frequency domain spectra of gas are simultaneously analyzed and processed.
In step a, is swung in the pulse laser and declining and be equipped with optoisolator between chamber, be equipped in the pressure monitoring mouth Pressure sensor, is equipped with blow gun and filter at the inflatable mouth, and described to decline that swing chamber be diameter be 5cm, and length is 20cm's Cylindrical stainless steel cavity, the pulse laser are the single mode pulse laser of output wavelength 1573nm, pulse recurrence frequency 100Hz ~ 1KHz is continuously adjustable, 2 ~ 3ns of pulsewidth;The Terahertz window selects HDPE material, and the exhaust outlet is equipped with vacuum pump, institute Stating adsorbent material is graphene oxide paper, Au- graphene oxide, foamy graphite alkene, PdO WO3Nano material or tin oxide-are also One of former graphene nano thin-film material.
It needs to measure the absorption conduct swung the ring-down time that chamber is filled with after nitrogen, and calculate nitrogen that declines in step b, before measurement Background deduction;In measurement process, monitoring declines and swings cavity pressure, and keeps declining that swing the atmospheric pressure value of chamber be the target value set.
In step c, the absorption coefficient of under test gas is obtained by following formula;
(I)
In formula (I), α indicates absorption coefficient, τ0Indicate that ring-down time when vacuum, τ indicate ring-down time when incoming call gas, c It indicates the light velocity, gas concentration lwevel A=α/M is then calculated according to molecule molar absorption coefficient M.
In step d, the visible light is the continuous laser of 200 ~ 900nm of wavelength, and 10 ~ 300mw of power is continuously adjustable.
Compared with prior art, the invention has the following beneficial effects:
(1) this system utilizes near infrared light cavity ring-down spectroscopy measuring system, realizes the online real-time separation of dead space gas and alveolar air, Endogenous VOCs concentration is higher by two to three times than the concentration in the exhaled gas sample for being mixed with dead space gas in alveolar air, therefore Dead space gas or the interference of other invalid gases are excluded, characteristic molecular measurement accuracy is helped to improve.
(2) by Single wavelength cavity attenuation and vibration technique, s grades of response times of μ, ppb magnitude measurement accuracy may be implemented.
(3) the gas concentration lwevel information obtained according to optical cavity ring-down spectrum analysis, can accurate judgement subject's expiratory air Then the different phase of body passes through the convenient automatic collection and separation control for swinging the realization of the structures such as chamber to alveolar air that decline of special designing System.
(4) by using active adsorbing material, especially Au- graphene oxide, PdO WO3Nano material and tin oxide- Reduced graphene nano film material substantially increases the concentration effect of trace characteristic gas organic molecule, further increases Detection sensitivity, meanwhile, further eliminate the influence of interference gas.
(5) terahertz time-domain spectroscopy detection technique can directly extract the absorption of sample from the time-domain spectroscopy signal of sample The physical messages such as coefficient and refractive index, have many advantages, such as that signal-to-noise ratio is high, dynamic range is big, the spectral region that can detecte it is wide.
Detailed description of the invention
Fig. 1 is detection method flow chart.
Fig. 2 is the structural schematic diagram of alveolar gas separating system.
Fig. 3 is the structural schematic diagram of the gas measurement system based on terahertz light spectral technology.
Fig. 4 is the changes of concentrations of carbon dioxide waveform diagram of human body normal cycle of respiration.
Fig. 5 is that whether there is or not the time-domain and frequency-domain control curve figures of HDPE material Terahertz window.
In figure: 1, declining and swing chamber;2, high reflectivity mirror;3, inflatable mouth;4, the first gas outlet;5, the second gas outlet;6, Pressure monitoring mouth;7, pulse laser;8, optoisolator;9, photodetector;10, signal processing and control system;11, gas Measure chamber;12, Terahertz window;13, air inlet;14, exhaust outlet;15, air pressure detection mouth;16, active adsorbing material;17, emit Device;18, detector;19, the first Terahertz lens;20, the second Terahertz lens.
Specific embodiment
Embodiment 1
As shown in Figures 1 to 5, in exhaled gas of the present invention volatile organic matter molecule detection system, including alveolar air separation System and gas measurement system.Wherein, alveolar gas separating system includes:
It declines and swings chamber 1, be diameter be 5cm, length is the cylindrical stainless steel airtight cavity of 20cm, and the both ends of cavity are high reflectance Usual R > 99.9% of reflecting mirror 2(), go out on cavity equipped with the inflatable mouth 3 entered for exhaled gas, for the first of the discharge of dead space gas Port 4, the second gas outlet 5 for alveolar air discharge and pressure monitoring mouth 6, go out in inflatable mouth 3, the first gas outlet 4 and second It is equipped with check valve at port 5, is equipped with vacuum pump at the first gas outlet 4 and the second gas outlet 5;At the inflatable mouth 3 Equipped with disposable blow gun and filter;It is equipped with gas pressure sensor in pressure monitoring mouth 6, pressure sensor connects single-chip microcontroller, Single-chip microcontroller controls relay and an extract system, when the intracorporal air pressure of chamber reaches set target value, passes through pressure Sensor spreads out of electric signal, controls relay closure by single-chip microcontroller into single-chip microcontroller, rotates motor, extract system fortune It goes, the atmospheric pressure value inside holding chamber is the target value set, the pumping when the target value of setting is not achieved in intracavitary air pressure System does not work.
Pulse laser 7 is the quasi- single mode of single solid-state small size of output wavelength 1573nm set on the left side for swinging chamber 1 of declining Pulse laser, the pulse recurrence frequency KHz of 100 Hz ~ 1 are continuously adjustable, 2 ~ 3ns of pulsewidth, for swashing to declining to swing chamber 1 and emit pulse Light;It is swung in pulse laser and declining and is equipped with optoisolator 8 between chamber, using the light of the nonreciprocity principle based on Faraday rotation Isolator is a kind of passive device for only Unidirectional light being allowed to pass through, the reflected light of high reflective mirror can be carried out well every From causing to damage to avoid reflected light feed-in laser.
Photodetector 9, set on the right side for swinging chamber 1 of declining, the light signal strength after swinging chamber that declines for detection transmission becomes at any time The exponential decay curve of change.
Signal processing and control system 10, for obtaining carbon dioxide in gas concentration according to the synchronous operation of ring-down time, And corresponding vacuum pump is controlled according to gas concentration lwevel information, dead space gas is discharged, alveolar air is pumped into gas measurement system.
Gas measurement system includes:
Gasmetry chamber 11 is airtight cavity, and the both ends of cavity are Terahertz window 12, and Terahertz window 12 selects HDPE material, Cavity is equipped with the air inlet 13 imported for alveolar air, the exhaust outlet 14 for excessive gas to be discharged and is connected with air gauge Air pressure detection mouth 15, the exhaust outlet 13 be equipped with vacuum pump.Active adsorbing material 16 is equipped with gasmetry is intracavitary, for inhaling Volatile organic matter molecule in attached gas.
Active adsorbing material 16 is graphene oxide paper, Au- graphene oxide, foamy graphite alkene, PdO WO3Nano material Or one of tin oxide-reduced graphene nano film material.PdO‒WO3Nano material is prepared by infusion process, synthesis Process is as follows: weighing the WO being sintered through 300 DEG C3Powder 1g injects 100 mL of deionized water, and 30min is stirred under room temperature, and urine is added Element (purity 99%) 0.0564g, is slowly heated to 90 DEG C.Palladium chloride (purity 99.99%) powder 0.0233g is added, continues to stir Mix cooling and standings after 4h.After supercentrifuge separates, solution is dried and takes out PdO WO3Powder sample, through 500 DEG C of sintering 2h The PdO that palladium mass fraction is 1.0% is made and loads WO3Powder of nanometric particles (1.0% PdO WO3).Then re-compacted at film-form It can use.
Tin oxide-reduced graphene nano thin-film preparation, what which mainly used is that redox graphene is molten Liquid and stannic chloride pentahydrate powder.24mg stannic chloride pentahydrate and 1.5ml redox graphene solution are blended in 20ml and gone Aqueous solution, is then transferred in reaction kettle by ultrasonic vibration 1h in ionized water, and reaction kettle is placed in heater box at 120 DEG C and is heated 12h.Reaction reaction was completed kettle is cooling, and product high speed centrifugation 15min is collected white precipitate, the precipitating deionization that will be collected into Water cleans repeatedly obtains tin oxide-reduced graphene suspension afterwards several times, is finally putting into constant temperature drying 5-8h in heater box, obtains Complete tin oxide-reduced graphene film.
Transmitter 17 is set on the left of gasmetry chamber, for being generated and transmitted by THz wave.
Detector 18 is set on the right side of gasmetry chamber, for receiving the THz wave across gasmetry chamber.
Terahertz lens, including the first Terahertz lens 19 and the second Terahertz lens 20, the first Terahertz lens 19 are set It is intracavitary for THz wave to be focused on gasmetry between the gentle fluid measurer of transmitter;Second Terahertz lens 20 are set Between gasmetry chamber and detector, the THz wave for passing through gasmetry chamber converges to detector.
Signal processing system, for detection gas terahertz time-domain spectroscopy and frequency domain spectra be analyzed and processed.
Embodiment 2
The separation of alveolar air
Firstly, opening the check valve of inflatable mouth 3, subject, which is breathed pulmonary gases by disposable blow gun, swings chamber 1, pulse into declining Laser 7 emits light source, and pulse recurrence frequency 1KHz, 2 ~ 3ns of pulsewidth, output wavelength 1573nm, this is enhancing Fingerprint Selectivity key core technologies, exist by the gas concentration lwevel that signal processing and 10 pairs of control system enter gases Line real-time monitoring judges the stage that characteristics of contaminated respiratory droplets gas is according to the display of the waveform diagram of carbon dioxide, and then control is opened corresponding Check valve realize alveolar air separation.
Wherein, the control intracavity gas by being formed with pressure sensor, single-chip microcontroller, relay and an extract system Pressure output equipment.When intracavitary air pressure reaches set target value, gas pressure sensor transmission electric signal enters list Piece machine is controlled relay closure by single-chip microcontroller, rotates motor, extract system operation, and the atmospheric pressure value inside holding chamber is The target value set, when the target value of setting is not achieved in intracavitary air pressure, the output system does not work.
This measuring principle is based on background deduction method.High pure nitrogen is measured before the start of the measurement enter to decline swing declining for chamber and swing Time, measurement are averaged afterwards three times, the absorption of nitrogen are calculated, as background.Then sample measurement is carried out.Measurement is exhaled every time After inhaling sample, sample is extracted out cavity with vacuum pump, to prevent from remaining, also needs to be cleaned using high pure nitrogen.
According to cavity-type BPM basic principle, after the sample absorbance for calculating each measurement, background deduction method need to be used, is obtained Tested carbon dioxide (CO2) actual absorption.Calculate according to the ring-down time of the gas of measurement and determines tested carbon dioxide (CO2) concentration.
When pulse laser is after optoisolator enters the optical resonator being made of two high reflective mirrors, ignore diffraction and Scattering loss, light vibrate back and forth between two hysteroscopes, every round trip, just have sub-fraction light through mirror surface and leave light Chamber, the multiple light signal strength through after chamber that photodetector detects change over time as exponential decay curve, according to
(I)
Operation obtains gas actual absorption factor alpha, and according to molecule molar absorption coefficient M be calculated gas concentration lwevel A=α/ M.In formula, τ0Respectively represented with τ measure it is intracavitary for vacuum and incoming call gas when ring-down time.Meanwhile reflectance ratio of high reflected mirror is got over Height, light path is longer, and measurement accuracy is higher.Measurement chamber is flowed slowly into when characteristics of contaminated respiratory droplets gas passes through conduit, is absorbed according to exhaled gas The time trend of coefficient, as shown in figure 4, whether can determine whether the arrival of alveolar air.
Gas molecule enrichment and measurement
The alveolar air isolated is pumped into gasmetry chamber 11 by air inlet, human body is adsorbed using active adsorbing material 16 and exhales Organic gas in gas out carries out real-time monitoring, extra gas to the air pressure in gasmetry chamber 11 by air gauge It can be discharged from exhaust outlet 14, use up irradiation gasmetry chamber 11, active adsorbing material 16 is enable to adsorb more VOCs molecules. The THz wave that transmitter 17 emits is saturating to the center of gasmetry chamber, then through the second Terahertz through the first Terahertz lens focus Mirror receives the THz wave across gasmetry chamber by detector 18, detects the terahertz time-domain spectrum and frequency domain spectra of gas, The spectrum of adsorbed gas is analyzed.
Wherein, Terahertz window 12 is used to THz wave with the HDPE material compared with high pass rate, as shown in figure 5, by Terahertz time-domain waveform slightly postpones after HDPE window, and frequency-domain waveform amplitude has lesser decline, but frequency-domain waveform shape has no Variation, illustrates HDPE to the preferable permeability of THz wave and flat frequency response characteristic.

Claims (9)

1. the detection system of volatile organic matter molecule in a kind of exhaled gas, which is characterized in that including alveolar gas separating system And gas measurement system;
The alveolar gas separating system includes:
Decline and swing chamber, be airtight cavity, the both ends of cavity are high reflectivity mirror, be equipped on the cavity for exhaled gas into The inflatable mouth entered, the first gas outlet, the second gas outlet for alveolar air discharge and the pressure monitoring mouth that are discharged for dead space gas, It is equipped with check valve at the inflatable mouth, the first gas outlet and the second gas outlet, it is equal at the first gas outlet and the second gas outlet Equipped with vacuum pump;
Pulse laser, for swinging chamber emission pulse laser to declining;
Photodetector, for detect through decline swing chamber after the exponential decay curve that changes over time of light signal strength;And
Signal processing and control system become at any time for obtaining carbon dioxide in gas concentration according to the synchronous operation of ring-down time The waveform diagram of change, and corresponding vacuum pump is controlled according to gas concentration lwevel information, dead space gas is discharged, alveolar air is pumped into gas Measuring system;
The gas measurement system includes:
Gasmetry chamber is airtight cavity, and the both ends of cavity are Terahertz window, and the air inlet imported for alveolar air is equipped on cavity Mouthful, the exhaust outlet for excessive gas to be discharged and the air pressure detection mouth being connected with air gauge, be equipped with gasmetry is intracavitary Active adsorbing material, for adsorbing the volatile organic matter molecule under test gas;
Transmitter, for generating and emitting THz wave to gasmetry chamber;
Detector, for receiving the THz wave across gasmetry chamber;
Terahertz lens, including the first Terahertz lens and the second Terahertz lens, the first Terahertz lens be set to transmitter and It is intracavitary for THz wave to be focused on gasmetry between gasmetry device;Second Terahertz lens are set to gasmetry chamber Between detector, the THz wave for passing through gasmetry chamber converges to detector;And
Signal processing system, for detection gas terahertz time-domain spectroscopy and frequency domain spectra be analyzed and processed.
2. the detection system of volatile organic matter molecule in exhaled gas according to claim 1, which is characterized in that described In alveolar gas separating system, is swung in the pulse laser and declining and be equipped with optoisolator between chamber, set in the pressure monitoring mouth There is gas pressure sensor, be equipped with blow gun and filter at the inflatable mouth, described to decline that swing chamber be diameter be 5cm, and length is The cylindrical stainless steel cavity of 20cm.
3. the detection system of volatile organic matter molecule in exhaled gas according to claim 1, which is characterized in that described In alveolar gas separating system, the pulse laser is the single mode pulse laser of output wavelength 1573nm, pulse recurrence frequency 100Hz ~ 1KHz is continuously adjustable, 2 ~ 3ns of pulsewidth.
4. the detection system of volatile organic matter molecule in exhaled gas according to claim 1, which is characterized in that described In gas measurement system, Terahertz window selects HDPE material, and the exhaust outlet is equipped with vacuum pump.
5. the detection system of volatile organic matter molecule in exhaled gas according to claim 1, which is characterized in that described In gas measurement system, the adsorbent material is graphene oxide paper, Au- graphene oxide, foamy graphite alkene, PdO WO3It receives Rice one of material or tin oxide-reduced graphene nano film material.
6. the detection method of volatile organic matter molecule in a kind of exhaled gas, which comprises the following steps:
A, the detection system of volatile organic matter molecule in exhaled gas is set, and the detection system includes alveolar gas separating system And gas measurement system;
The alveolar gas separating system includes:
It declines and swings chamber, be airtight cavity, the both ends of cavity are the reflecting mirror of reflectivity > 99.9%, are equipped on the cavity for exhalation Inflatable mouth, the first gas outlet for the discharge of dead space gas, the second gas outlet for alveolar air discharge and the pressure prison that gas enters Mouth is surveyed, check valve is equipped at the inflatable mouth, the first gas outlet and the second gas outlet, in the first gas outlet and the second outlet Vacuum pump is equipped at mouthful;
Pulse laser, for swinging chamber emission pulse laser to declining;
Photodetector, for detect through decline swing chamber after the exponential decay curve that changes over time of light signal strength;And
Signal processing and control system become at any time for obtaining carbon dioxide in gas concentration according to the synchronous operation of ring-down time The waveform diagram of change, and corresponding vacuum pump is controlled according to gas concentration lwevel information, dead space gas is discharged, alveolar air is pumped into gas Measuring system;
The gas measurement system includes:
Gasmetry chamber is airtight cavity, and the both ends of cavity are Terahertz window, and the air inlet imported for alveolar air is equipped on cavity Mouthful, the exhaust outlet for excessive gas to be discharged and the air pressure detection mouth being connected with air gauge, be equipped with gasmetry is intracavitary Active adsorbing material, for adsorbing the volatile organic matter molecule under test gas;
Transmitter, for generating and emitting THz wave to gasmetry chamber;
Detector, for receiving the THz wave across gasmetry chamber;
Terahertz lens, including the first Terahertz lens and the second Terahertz lens, the first Terahertz lens be set to transmitter and It is intracavitary for THz wave to be focused on gasmetry between gasmetry device;Second Terahertz lens are set to gasmetry chamber Between detector, the THz wave for passing through gasmetry chamber converges to detector;And
Signal processing system, for detection gas terahertz time-domain spectroscopy and frequency domain spectra be analyzed and processed;
B, start detection system, will decline and swing chamber and be evacuated to vacuum, pulmonary gases incoming call is declined by inflatable mouth and swings chamber by subject, online Real-time detection, which enters to decline, swings the ring-down time of chamber gas;
C, signal processing and control system obtain carbon dioxide in gas concentration changes with time according to the synchronous operation of ring-down time Waveform diagram, and determined to enter the stage locating for gas automatically according to waveform diagram, then by controlling corresponding vacuum pump, by dead space gas It is intracavitary to be pumped into gasmetry by discharge for alveolar air;
D, the intracavitary active adsorbing material of gasmetry adsorbs the volatile organic matter molecule in alveolar air, passes through air pressure The table pressure intracavitary to gasmetry is monitored, and excessive gas is discharged by exhaust outlet, then uses radiation of visible light gasmetry Chamber enables active adsorbing material to adsorb more volatile organic matter molecules;
E, transmitter is generated and transmitted by THz wave, and THz wave converges to detector after passing through gasmetry chamber, finally obtains The terahertz time-domain spectroscopy and frequency domain spectra of gas are simultaneously analyzed and processed.
7. the detection method of volatile organic matter molecule in exhaled gas according to claim 6, which is characterized in that step It in a, is swung in the pulse laser and declining and is equipped with optoisolator between chamber, be equipped with pressure sensor in the pressure monitoring mouth, It is equipped with blow gun and filter at the inflatable mouth, described to decline that swing chamber be diameter be 5cm, and length is the cylindrical stainless steel of 20cm Cavity, the pulse laser are the single mode pulse laser of output wavelength 1573nm, and pulse recurrence frequency 100Hz ~ 1KHz connects Continue adjustable, 2 ~ 3ns of pulsewidth;The Terahertz window selects HDPE material, and the exhaust outlet is equipped with vacuum pump, and the adsorbent material is Graphene oxide paper, Au- graphene oxide, foamy graphite alkene, PdO WO3Nano material or tin oxide-reduced graphene nanometer One of thin-film material.
8. the detection method of volatile organic matter molecule in exhaled gas according to claim 6, which is characterized in that step It needs measurement to decline in b, before measurement and swings the ring-down time that chamber is filled with after nitrogen, and calculate the absorption of nitrogen as background deduction;? In measurement process, monitoring declines and swings cavity pressure, and keeps declining that swing the atmospheric pressure value of chamber be the target value set.
9. the detection method of volatile organic matter molecule in exhaled gas according to claim 6, which is characterized in that step In d, the visible light is the continuous laser of 200 ~ 900nm of wavelength, and 10 ~ 300mw of power is continuously adjustable.
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