CN103884673A - Online infrared spectroscopy monitoring system and method for hard drug taking condition - Google Patents

Online infrared spectroscopy monitoring system and method for hard drug taking condition Download PDF

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CN103884673A
CN103884673A CN201410126219.6A CN201410126219A CN103884673A CN 103884673 A CN103884673 A CN 103884673A CN 201410126219 A CN201410126219 A CN 201410126219A CN 103884673 A CN103884673 A CN 103884673A
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drugs
spectrum data
physical space
gas
industrial computer
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CN103884673B (en
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汤晓君
李玉军
朱凌建
赵安新
房甲敏
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Xian Jiaotong University
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Abstract

The invention discloses an online infrared spectroscopy monitoring system and method for a hard drug taking condition. The system comprises a plurality of electromagnetic directional valves, a Fourier transform infrared spectrometer, an air pump and an industrial personal computer, or comprises a plurality of air pumps, a Fourier transform infrared spectrometer and an industrial personal computer, or comprises a plurality of groups of optical fiber shunts and couplers, a Fourier transform infrared spectrometer and an industrial personal computer. The volatility of hard drugs and decomposed substances of the hard drugs and the infrared light absorption characteristic of volatile components are utilized, the on-line infrared spectrum gas analysis method of the Fourier transform infrared spectrometer is adopted to perform online analysis on components of the hard drugs, which are volatilized in the air, so that the hard drug taking condition in one or multiple physical spaces of a specific place such as KTV and hotels can be monitored in an online manner; if an abnormal condition is found, the industrial personal computer can inform the public security organization through an internet, and therefore, the system and the method can provide effective investigation means and evidences for drug control.

Description

A kind of drugs are sucked situation infrared spectrum on-line monitoring system and method
[technical field]
The composition on-line monitoring field that the present invention relates to drugs, particularly a kind of drugs are sucked situation infrared spectrum on-line monitoring system and method.
[background technology]
According to the United Nations's statistics, the annual drug trade volume in the whole world reaches more than 5,000 hundred million dollars, and turnover is also soaring in continuation, drugs can endanger people's life, upset the public, and can cause the unstable of country, therefore can say, drugs have become one of maximum public hazards of international community.Due to drug abuse and drug trafficking mostly in hotel, hotel, night the place such as shop carry out, therefore, to the monitoring in these places, be a kind of important means of virus investigation, the prohibition of drug.At present, there is no the instrument that can carry out on-line monitoring to these places, mainly monitor by the inspection of public security department.On the one hand, current ways of check has consumed a large amount of police strength; On the other hand, disturbed the normal business of hotel, hotel; The 3rd, the efficiency of virus investigation is very limited.Therefore, develop a kind of drugs and suck the on-line monitoring instrument of situation, by the composition of drugs volatile matter and analyte thereof in monitoring air, monitor in real time hotel, whether someone hotel take drugs, by greatly improving the dynamics of the virus investigation prohibition of drug, meanwhile, also reduce the demand of virus investigation police strength.Therefore, exploitation drugs on-line monitoring instrument, to safeguarding that civil order is with stable, the protection public is healthy significant.
At present, the check of drugs, mainly for kind, composition, structure, character and the content of research drugs, provides scientific basis and important clue for tracking down and try drug violation crime case.Drug testing mainly comprises visual testing, physical examination, chemical analysis, instrumental analysis etc.Visual testing is that color, smell, physical aspect and the proterties etc. to drugs are observed and compare, and drugs are tentatively judged; Physical examination is mainly that the physical property of drugs is tested as solubleness, fusing point, boiling point, draws the information relevant with process; Chemical analysis and instrument analytical method, it is mainly the chemical composition to drugs, as the compositions such as drug ingredient, additive composition, adulterated composition, impurity, solvent, metal carry out qualitative and quantitative analysis, thus the information of the aspect such as raw material, synthetic method and route, judgement drug source used in acquisition drugs processing building-up process.In addition drug testing also comprises biological specimen is tested as drugs prototype and metabolin thereof in saliva, urine, blood, hair, to determine whether suspect takes drugs and kind, the time etc. of consume illegal drugs.The sample of drug testing mainly comprises the drugs suspicious item of various forms, as the solid matters such as bulk, powder, injection, liquid etc.; Biological material, as drug addict's urine, blood, nail etc.After these samples are sampled, then adopt corresponding method to analyze.
The analysis of drugs is a complexity, highly difficult work, and its analytical technology adopting almost relates to all technology of analytical chemistry.At the initial stage of instrument analysis technology development, drug testing mainly adopts chemico-analytic method to complete, as chemical staining method.Along with the development and maturation of instrument analysis technology, Molecular Spectroscopy, as fluorometry (Fluorescence analysis), laser raman technology (Laser Raman Spectroscopy, LRS), FFIR (Fourier Transform Infrared, FTIR), chemoluminescence method (Chemoluminescence method) etc., chromatography, as thin-layered chromatography (Thin-layer chromatograph), high performance liquid chromatography (High Performance Liquid Chromatograph, HPLC), vapor-phase chromatography (Gas Chromatograph, GC) etc., combined gas chromatography mass spectrometry is (as GC-MS, HPLC-MS, GC-IMS, GC-HRMS etc.) and Capillary Electrophoresis (Capillary electrophoresis, etc. CE) instrument analytical method becomes the Main Means that drug testing is analyzed, and primary dcreening operation and preliminary experiment that chemical analysis rule is analyzed for drug testing as supplementary means.Conventional drugs of abuse method and feature thereof are as follows:
1) chemical staining method this be a kind of method for qualitative analysis, conventionally utilize drugs and some chemical reagent effect, produce the color of feature and determine its existence.This method simply, intuitively, easily operation, but need sample many, specificity is poor;
2) fluorometry fluorometry be carry out according to the molecular fluorescence spectrum of material qualitative, a kind of method of row quantitative test during with fluorescence intensity.Fluorometry is highly sensitive, can reach 10 -6.When use, will consider the influence factor of environment, different solvents, temperature, pH value and noise all can have impact to measurement result, but sometimes also can use under special circumstances these influence factors;
3) laser Raman spectrometry, in the time that monochromatic light is radiated in something, forms scattered light, and most of scattering light frequency is identical with incident light frequency, and this scattering is called Rayleigh scattering; In scattered light, can observe a fraction of frequency and be different from incident light frequency, this scattering is Raman scattering.The frequency of Raman scattering line and the difference of incident light frequency are called Raman frequency shift, and this frequency displacement can characterize the characteristic of different group vibrations in molecule, therefore can carry out qualitative and structure analysis to molecule by measuring.Whether Raman spectroscopy, except determining the molecular structure of various drugs, can be also that drugs detect to unknown article according to Raman Scattering Spectra;
4) chemiluminometry chemiluminescence is to provide excitation energy by chemical reaction, excites product molecule or other molecules that coexists to produce optical radiation.Chemiluminometry is exactly to detect and analyze different materials according to the difference of optical radiation.Chemiluminometry has luminous two kinds of liquid chemiluminescence and gas chemistry.Conventional chemiluminescent analyzer device has two kinds of discrete sampling formula and flow injection types.Experimental results show that chemiluminescence detection generally has higher sensitivity and accuracy than ultraviolet spectrometry and fluorometry, it has become a kind of important trace analysis method;
5) chromatography, chromatograph-mass spectrometer coupling method chromatograph are a kind of by kapillary, the composition of analysans are separated to carry out to the instrument of elemental analysis, are particularly suitable for organic quantitative test.Mass spectrometer is a kind of analytical instrument of identifying molecule, is particularly suitable for qualitative analysis.Two kinds of analytical instrument connect by special interface (molecular separator), and use the online rear operating parameter of computer controlled automatic, can become an entirety and analytical information is provided.Chromatograph-mass spectrometer coupling analytic approach can be carried out fast qualitative quantitative test to each component in COMPLEX MIXED matter sample, have qualitative accurately, the feature such as analysis speed is fast, easy and simple to handle.Chromatogram-the mass spectrometry using at present mainly contains GC/MS and HPLC/MS, and this method has now become drugs qualitative and quantitative analysis the most and one of working standard confirmation method.But chromatograph and mass spectrometer are relatively expensive, what two kinds of instruments formed is used in conjunction, and price is more high;
6) capillary electrophoresis Capillary Electrophoresis (CE), claims that again high performance capillary electrophoresis (HPCE) is one of the fastest analytical chemistry research field of development in recent years.With regard to drugs of abuse, between drugs component, possibility chemical property is widely different, also possibility molecular structure is very similar, and impurity, thinning agent wherein often exist with trace, and capillary electrophoresis technique separation efficiency is high, mass sensitivity is high, demand to sample and solvent is little, and can adopt multiple clastotype, realizes coupling with multiple detection method, analyst coverage is extensive, is therefore applicable to complicated drugs to carry out effective qualitative and quantitative analysis.Be applied at present the analyzing and testing of several frequently seen drugs example hydrochloric acid morphine, heroin, thebaine etc.In addition, compared with being applied to the other technologies of drug testing, CE has unique separating mechanism, can be used as the important method of drugs systematic analysis, mutually authenticate with additive method the description that jointly completes various drugs, set up fingerprint databases, and then infer strong technical support is provided for the source of drugs;
7) University of St Andrews of fourier transform infrared spectroscopy Britain and industry member cooperation, developed a kind of novel spectrometer that can the multiple poison gas composition of express-analysis in 1999, on market, occur.This instrument is through improved fourier-transform infrared spectrophotometer, by the Absorption of different poison gas wavelength is determined to poison gas kind.
From above-mentioned analysis, the detection to drugs at present, is to the drugs metabolin qualitative and quantitative analysis in various sample Chinese traditional medicine substances and biological sample mostly both at home and abroad.To the detection of metabolin, need to, to individuality or sample sampling, be the check afterwards of a kind of consume illegal drugs, rather than one be before the accident happened, or ongoing check, be therefore not suitable for on-line monitoring.To the analysis of drug ingredient, need equally sampling, censorship supervisor, do not test in the drugs of specific region and find.Therefore,, from existing drug testing instrument and method, still there is no the cheap drugs on-line monitoring instrument of energy at present.Conventional testing instruments substantially all relate to sampling, manual analysis supervisor.Some drug testing instrument prices are quite also expensive, complicated operation, for example chromatograph-mass spectrometer coupling method, chromatograph and mass spectrometer all belong to the instrument that price is higher, the price of separate unit instrument is up to hundreds thousand of Renminbi, and the operator of these instruments needs could realize correct analysis through strict training, therefore cannot meet the needs of automatic virus investigation.
[summary of the invention]
The object of the present invention is to provide a kind of drugs to suck situation infrared spectrum on-line monitoring system and method.It provides effective special reconnaissance means and virus investigation evidence for banning taking addictive drugs.
To achieve these goals, the first technical scheme arranged side by side that the present invention adopts is:
A kind of drugs are sucked situation infrared spectrum on-line monitoring system, comprise some solenoid directional control valves, Fourier transform infrared spectrometer, aspiration pump and industrial computer; Wherein, the air intake opening of some solenoid directional control valves is arranged in corresponding some monitored physical spaces, the gas outlet of some solenoid directional control valves is connected with the air chamber entrance of Fourier transform infrared spectrometer respectively, industrial computer is selected one of them solenoid directional control valve work within one time, aspiration pump is for the gas of monitored physical space being evacuated to the air chamber of Fourier transform infrared spectrometer, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer.
The method of sucking situation infrared spectrum on-line monitoring system based on above-mentioned drugs, comprises the following steps:
1) at one time, industrial computer is selected one of them solenoid directional control valve work, aspiration pump is evacuated to Fourier transform infrared spectrometer air chamber by this solenoid directional control valve by the air of a monitored physical space corresponding with this solenoid directional control valve and carries out on-line analysis, obtains absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another solenoid directional control valve work.
The second technical scheme arranged side by side that the present invention adopts is: a kind of drugs are sucked situation infrared spectrum on-line monitoring system, comprise some aspiration pumps, Fourier transform infrared spectrometer and industrial computer; Wherein, the air intake opening of some aspiration pumps is arranged in corresponding some monitored physical spaces, the gas outlet of some aspiration pumps is connected with the air chamber entrance of Fourier transform infrared spectrometer respectively, industrial computer is for selecting one of them aspiration pump work at one time, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer.
The method of sucking situation infrared spectrum on-line monitoring system based on above-mentioned drugs, comprises the following steps:
1) at one time, industrial computer is selected one of them aspiration pump work, the air that this aspiration pump is monitored physical space is evacuated to Fourier transform infrared spectrometer air chamber and carries out on-line analysis, obtains absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another aspiration pump work.
The third technical scheme arranged side by side that the present invention adopts is: a kind of drugs are sucked situation infrared spectrum on-line monitoring system, comprise some groups of fiber optic splitters and coupling mechanism, Fourier transform infrared spectrometer and industrial computer; Wherein, some groups of fiber optic splitters and coupling mechanism are arranged in corresponding some monitored physical spaces, and each group fiber optic splitter and coupling mechanism are coupled to Fourier transform infrared spectrometer light source by it at the absorbed interference light of corresponding monitored physical space, industrial computer is for selecting wherein one group of fiber optic splitter and coupling mechanism work at one time, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space and Optical transmission spectrum data transmission to industrial computer.
The method of sucking situation infrared spectrum on-line monitoring system based on above-mentioned drugs, comprises the following steps:
1) at one time, industrial computer is selected one group of fiber optic splitter and coupling mechanism work, this group fiber optic splitter and coupling mechanism are monitored the absorbed interference light of physical space and are coupled to Fourier transform infrared spectrometer light source and carry out on-line analysis, obtain absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another group fiber optic splitter and coupling mechanism work.
With respect to prior art, the present invention utilizes the volatility of drugs and the drugs analyte in absorption process, and the infrared extinction characteristic of effective constituent in volatile matter, adopt the method for infrared spectrum gas analysis to carry out on-line analysis to the aerial drug ingredient that volatilizees, carry out on-line monitoring with the drugs situation of sucking that realizes the particular place such as KTV, hotel, for the prohibition of drug provides effective investigation and virus investigation evidence.
[accompanying drawing explanation]
Fig. 1 is the schematic diagram that drugs of the present invention are sucked situation infrared spectrum on-line monitoring system;
Fig. 2 is that the light path of multiple physical space drugs on-line monitoring systems is switched schematic diagram;
Fig. 3 is heroinbase and heroin hydrochloride infrared absorpting light spectra;
Fig. 4 (a) is one-component 10% methane, 2% ethane, and 1% propane infrared absorpting light spectra, Fig. 4 (b) is the high wave number section of the middle infrared spectrum spectrogram of the combination gas of one-component 10% methane and 2% ethane;
Fig. 5 (a) is three spectrograms of the generation baseline distortion that obtains in the long-term on-line monitoring process of methane, ethane and propane gas;
Fig. 5 (b) is the spectrogram after three spectrogram baseline corrections in Fig. 5 (a);
Fig. 5 (c) is the initial spectrum figure of data1 in Fig. 5 (a), and baseline correction spectrogram, reconstruct spectrogram;
Fig. 5 (d) is the initial spectrum figure of data2 in Fig. 5 (a), and baseline correction spectrogram, reconstruct spectrogram;
Fig. 5 (e) is the initial spectrum figure of data3 in Fig. 5 (a), and baseline correction spectrogram, reconstruct spectrogram.
[embodiment]
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Referring to Fig. 1 and Fig. 2, a kind of drugs of the present invention are sucked situation infrared spectrum on-line monitoring system and method, this system comprises some solenoid directional control valves, Fourier transform infrared spectrometer, aspiration pump and industrial computer, or some aspiration pumps, Fourier transform infrared spectrometer and industrial computer, or some groups of fiber optic splitters and coupling mechanism, Fourier transform infrared spectrometer and industrial computer; Its method is utilized the volatility of drugs and the drugs analyte in absorption process, and the infrared extinction characteristic of effective constituent in volatile matter, adopt the method for infrared spectrum gas analysis to carry out on-line analysis to the aerial drug ingredient that volatilizees, carry out on-line monitoring with the drugs situation of sucking that realizes the particular place such as KTV, hotel, if note abnormalities, notify public security organ by internet, for the prohibition of drug provides effective investigation and virus investigation evidence.Drugs are sucked situation infrared spectrum on-line monitoring schematic diagram as shown in Figure 1.For the place with multiple physical spaces, as hotel, adopt a set of optical table of the three unities, one, each separate physical space light path/gas circuit, the mode that multiple light path/gas circuits are switched according to light path/gas circuit shares a set of optical table, then to each physical space air spectrum in scanning space one by one, determine whether that Poison sucks, to save system cost.Light path/gas circuit that drugs are sucked situation infrared spectrum on-line monitoring system is switched as shown in Figure 2.The drugs Online Transaction Processing switching for light path, first adopts optical fiber that light signal is delivered to each physical space, after the air of this physical space is to optical signal absorption, then light signal is transferred back to optical table with optical fiber; The test macro switching for gas circuit, adopts solenoid directional control valve to carry out gas circuit switching, and also has an extractor fan, to sample from the air of physical space, and is transported in the sample chamber of optical table.And the instrument that carries out drugs test for need movement only has a light path, a set of optical table, has a miniature air exhauster in gas circuit, by the sample air chamber of sample gas suction optical table, in order to spectral analysis.
The spectrum on line analysis of drugs is carried out according to the method for gas on-line analysis.First obtain standard specimen and the spectrogram thereof of drugs, then adopt the method for feature extraction, for every kind of drugs extract characteristic variable, and using these characteristic variables as input, with the kind of drugs, concentration is output, adopts partial least square method, neural network to set up its analytical model.In actual on-line analysis process, first carry out the correction of spectrum baseline, then according to the calculating formula calculated characteristics variate-value of characteristic variable, and according to set up model parameter, calculate the concentration of each component drugs gas.If the concentration of certain drugs gas componant reaches the concentration value of a certain setting, provide alarm signal.
Say further, it is to switch by light path that the drugs of multiple physical spaces of the present invention are sucked situation infrared spectrum on-line monitoring, or gas circuit is switched, adopt mode that each monitored physical space scans one by one to analyze by a Fourier transform infrared spectrometer, if gas circuit is switched, with aspiration pump, the gas of monitored physical space is evacuated to spectrometer air chamber, if light path is switched, arrive monitored physical space with optical fiber coupling spectrum instrument interference light, and absorbed interference light is coupled to spectrometer light source.
If it is gas circuit switch type that drugs are sucked situation infrared spectrum on-line monitoring system, each monitored physical space has a device for cleaning pipeline to cross solenoid valve to be connected with the air chamber of Fourier transform infrared spectrometer, in all gas circuits, only has a coupled solenoid valve state in opening, when system is in monitoring i physical space, need to be switched to i+1 physical space time, shutdown signal is sent to the solenoid valve being connected with i physical space pipeline, meanwhile, start signal is sent to the solenoid valve being connected with i+1 physical space pipeline, if drugs are sucked situation infrared spectrum, on-line monitoring system is optical-path-switching-type, each monitored physical space has two optical fiber to be connected with Fourier transform infrared spectrometer by fiber optic splitter/coupling mechanism, one for being transferred to monitored physical space by the light source interference light of coupling, another root is for being transferred to detector by the interference light after the volatile absorption of drugs and analyte thereof, system is by being sent to fiber optic splitter/coupling mechanism by switching signal, changing method is identical with gas circuit switching mode, whenever only have in the light path of a light path in Fourier transform infrared spectrometer.
Wherein, note abnormalities and refer to the possibility that monitors certain physical space and exist consume illegal drugs, its kind can comprise the drugs that current country is legal, notify public security organ to refer to by note, internet notice public security organ by internet, content comprises the kind of institute's consume illegal drugs, the place in place, comprises address, title, the room number of hotel/KTV.
Drugs of the present invention are sucked situation infrared spectrum on-line monitoring system and are made up of hardware and software two parts, and below in conjunction with accompanying drawing, the present invention is described in further detail.
1, hardware components
The hardware components that drugs are sucked situation infrared spectrum on-line monitoring system comprises connecting line, pipeline tap, industrial computer, Fourier transform infrared spectrometer composition, for optical fiber switch type monitoring system, also has fiber optic splitter/coupling mechanism, infrared optical fiber, and for gas circuit switch type monitoring system, also have multi-channel electromagnetic reversal valve, air pump.
Fourier transform infrared spectrometer is used for obtaining the absorption spectrum of drugs gas, can be the Tensor27 of Bruker company, and Tensor37 type can be also the Spectrum Two type of PE company, as long as 0.5cm can be provided -1above resolution, stable performance, the wave-number range upper limit can reach 6000cm -1above, lower limit is less than 600cm -1;
Connecting line can be glass tube, rubber tube, stainless-steel tube and other is not by the airtight connecting pipe of the tested gas attack of polycomponent.To with this embodiment, only otherwise corroded by organism, pipeline diameter is enough imbedded in wall connecting line, can bear 0.9~1.2 atmospheric pressure;
Industrial computer is used for obtaining the absorption spectrum of drugs gas from spectrometer, and realize the quantitative test of gas, and control the switching of optical fiber/gas circuit, as long as there is network interface, can carry out internet communication, can send binary signal, 500M internal memory, 1G dominant frequency is above, model is not limit, can be common industrial computer, can be also ordinary individual's desktop computer, can be even notebook computer;
Solenoid directional control valve can be multichannel, also can two-way.If the former, he itself has played pipeline tap, no longer needs pipeline tap, if the latter also needs pipeline tap.Solenoid directional control valve is subject to industrial computer control, the air of which physical space is pumped in the air chamber of Fourier transform infrared spectrometer determining, so which physical space is carried out to drugs monitoring;
Pipeline tap is used for connecting the air-transmitting pipeline of each physical space and the air delivering pipeline of Fourier transform infrared spectrometer air chamber;
Air pump is for the gas of each monitored physical space is pumped in Fourier transform infrared spectrometer air chamber, maintains the air pressure of air chamber in a certain definite scope simultaneously;
Optical fiber is used for transmitting optical signal, on the one hand, Fourier transform infrared spectrometer optical signal transmission, to the physical space that need to carry out drugs on-line monitoring, on the other hand, is received this light signal be transferred to the photodetector of inner leaf transformation infrared spectrometer.As long as optical fiber can transmit the infrared light of the above wavelength of 1 μ m, model is not done requirement;
As long as fiber optic splitter/coupling mechanism can be coupled to the interference light of Fourier transform infrared spectrometer in optical fiber, the infrared light after being absorbed can be coupled in optical fiber in monitored physical space.
2, software section
Software moves in industrial computer, and its function mainly comprises the control that air pump, light path/gas circuit are switched, drugs volatile matter, or the spectral analysis of educt gas, and the transmission of signal.
1) control of air pump
If it is gas circuit switch type that drugs are sucked situation infrared spectrum on-line monitoring system, air pump is housed.Air pump is used for the gas of each monitored physical space to be pumped in Fourier transform infrared spectrometer air chamber, maintains the air pressure of air chamber in a certain scope simultaneously.This pressure determines according to practical application, and the pressure that definite principle is pressure in air chamber when making sample gas in systems development process is consistent, and deviation is determined by user.Control algolithm can adopt pid control algorithm:
Δ=FS-F(1a)
C ( n ) = p P Δ ( n ) + p I Σ i = 0 n Δ ( i ) + [ Δ ( n ) - Δ ( n - 1 ) ]
C in formula (n) is current controlled quentity controlled variable; F is current test pressure value; F sfor maintaining the pressure reference value that can not affect the production of front end or safety; Δ (n), Δ (n-1) are respectively the difference of reference value and current pressure value and previous moment force value; p p, pI and p dbe respectively proportional component, integral element and differentiation element coefficient in PID control, they can obtain by pid control parameter control method.If drugs are sucked situation infrared spectrum, on-line monitoring system is optical-path-switching-type, there is no this step;
2) switching of light path/gas circuit
If it is gas circuit switch type that drugs are sucked situation infrared spectrum on-line monitoring system, in all gas circuits, only has one in opening.When system is in monitoring i physical space, need to be switched to i+1 physical space time, shutdown signal is sent to the solenoid valve being connected with i physical space pipeline, meanwhile, start signal is sent to the solenoid valve being connected with i+1 physical space pipeline.If drugs are sucked situation infrared spectrum, on-line monitoring system is optical-path-switching-type, switching signal is sent to fiber optic splitter/coupling mechanism, and changing method is identical with gas circuit switching mode;
3) spectral analysis of drugs volatile matter and educt gas composition and concentration
The spectral analysis of drugs volatile matter and educt gas composition and concentration is emphasis of the present invention.The present invention illustrates the spectroscopic analysis methods of drugs as an example of heroin example.For ease of explanation, only consider heroinbase and heroin hydrochloride.The abosrption spectrogram of heroinbase and heroin hydrochloride as shown in Figure 3.Conventional gas componant and the spectral analysis of concentration realize by analytical model, and the input of analytical model is the characteristic variable that some spectroscopic data forms through certain computing, and output is the concentration of object gas.Because the aerial content that volatilizees in drugs and analyte thereof is lower, therefore relative concentration is less, and it is saturated that its absorption spectrum can not be tending towards, and the non-linear of spectral line absorbance need not consider substantially, and characteristic variable can be as the analytical model of this drug ingredient.Because spectral instrument works long hours in process, spectrum easily distorts, and therefore also needs distortion identify and processing, obtaining reliably, analysis result accurately.Therefore, spectral analysis mainly comprises that the characteristic variable of each drug ingredient is extracted, spectrum distortion identification and processing two parts, and wherein first step completes in systems development process, and a rear step is the step that each spectral analysis all must complete.
(1) analytical model is set up
Sample gas spectrum obtains
Set up the analytical model of multicomponent gas, first will make certain demarcation sample.In this embodiment, need to analyze heroinbase and heroin hydrochloride, at given sample, be filled with in Fourier transform infrared spectrometer air chamber, first obtain its infrared absorption spectrum, then the sample gas gas chromatograph that takes a morsel from air chamber is analyzed, and obtains its concentration.
Characteristic variable is extracted
In characteristic variable leaching process, can extract the characteristic variable of a certain spectral line as certain gas, area that also can a certain section of spectrum, as characteristic variable, can also extract the combination of many spectral line values as the characteristic variable of gas with various.For different application scenarios, the extracting method difference of employing, selected characteristic variable is also different.For example, observe accompanying drawing 3 known, for the quantitative spectrochemical analysis of the combination gas of heroinbase and two kinds of gaseous state drugs of heroin hydrochloride, heroin hydrochloride is at 2630cm -1place has more by force, wider absorption peak, and heroinbase does not have, and on the contrary, heroinbase is at 3060cm -1there is a comparatively sharp-pointed absorption peak at place, but heroin hydrochloride do not have, and therefore, these two absorption peaks can be worked as the characteristic absorption peak that distinguishes these two kinds of drugs.Characteristic variable system of selection has forward selection procedures, Tikhonov method, least square method, principal component analysis (PCA) etc., for the sake of simplicity, adopts forward selection procedures here, and choosing wave number is 2630cm -1and 2135cm -1the difference of natural logarithm of two spectral line values as the characteristic variable of heroin hydrochloride:
v m=ln(val 2135)-ln(val 2630)(2a)
3060cm -1, 3000 cm -1and 3140cm -1the poor characteristic variable as heroinbase of natural logarithm of spectral line value:
v e=ln(val 3000)+ln(val 3140)-2×ln(val 3060)(2b)
V in formula mand v erepresent respectively the characteristic variable of heroin hydrochloride and heroinbase, ln (val n) represent the natural logarithm of the wave number spectral line value that is n.Here the forward selection procedures adopting is namely by observing accompanying drawing 3, and the characteristic variable that relatively difference of which two spectral line forms is higher to the remolding sensitivity of a certain gas, and lower to other gas sensitivity.Adopting natural logarithm is because spectral line value is spectral-transmission favtor, gets the linearity of the later characteristic variable forming of natural logarithm and relatively wants high.Getting spectral line poor is because the characteristic variable that this method forms is conducive to eliminate the impact that the translation of spectrum baseline brings as characteristic variable.If what the ordinate of spectrogram adopted is absorbance form, in formula (2), do not need to ask natural logarithm, directly by spectral line value;
(2) spectral analysis and spectrum distortion identification and processing
After spectrometer works long hours, because certain variation occurs for environmental parameter, spectrometer device characteristic, cause spectrum to produce certain distortion, this brings and has a strong impact on to analysis result.Spectrum distortion identification is to identify and process according to the distortion situation of spectrum, the impact bringing to analysis result to reduce as far as possible spectrum distortion with processing.Meanwhile, the identification of spectrum distortion must mutually combine with spectral analysis with processing, could obtain desirable result.In this application example, spectrum distortion is divided into baseline regular distortion and irregular distortion, for regular distortion, translation by spectrum realizes the correction of spectrum with rotation, and for irregular distortion, abandons this analysis, and point out mistake, or provide analysis result confidence level.If there is continuously irregular distortion, rescan background.In view of long-term drugs on-line monitoring experiment easily causes space-pollution, not general, it is example Mingguang City spectrum Distortion recognition and disposal route that the present embodiment adopts the on-line monitoring of methane, ethane and propane.The concentration obtaining is the spectrogram of 1% one-component gases methane, ethane and propane as shown in accompanying drawing 4 (a), one-component gas 10% methane, 1% ethane, 1% propane that obtain, and the combination gas spectrum of 10% methane and 2% ethane is as shown in accompanying drawing 4 (b).Corresponding with formula (2), the characteristic variable of methane, ethane and propane is respectively:
v m=ln(val 3022. 3)-ln(val 3016. 5)(3a)
v e=ln(val 3081.2)-ln(val 3029.2)(3b)
v p=ln(val 3028.0)-ln(val 3002.2)(3c)
The concentration calculation expression of methane, ethane and three kinds of gases of propane is respectively:
C 1=a 1v m+a 2v e+a 3v p(4a)
C 2=b 1v m+b 2v e+b 3v p(4b)
C 3=c 1v m+c 2v e+c 3v p(4c)
Three spectrogram data1, data2 as shown in accompanying drawing 5 (a) and data3 be Fourier transform infrared spectrometer to obtaining spectrum in the long-term on-line monitoring process of three component paraffin gas, its spectral analysis and spectrum distortion identification adopt respectively following steps to realize with processing:
Search in gas componant and non-sensitive district
Observe accompanying drawing 4 (a) known, near of locating in wave number 600,1100,2000,2500,3400 etc., methane, ethane and propane sensitivity very little, be referred to as non-sensitive district.Sensitivity S i for i kind gas in j non-sensitive district j, also available formula (5) is determined:
s ij=inv(Y i*Y i')*Y i*(1-V ij)'(5)
Y in formula irepresent the concentration value vector of i kind gas one-component sample; Y i' represent the transposition of vectorial Yi; V ij=[mean (v ij1), mean (v ij2) ..., mean (v ijN)] represent the spectral line mean vector in j non-sensitive district in i kind gas one-component sample spectrum, mean (v ijk) (k=1,2 ..., N) represent the average of some spectral lines in the individual non-sensitive district of j of i kind gas k one-component sample spectrum; Inv () representing matrix inversion operation.One-component sample is at above-mentioned 5 wave number section spectroscopic datas separately for employing formula (3) and methane, ethane, propane, and continuous 5 spectral lines of each band selection are averaged, and the sensitivity coefficient that can calculate them is:
S 600=[00.0000420.000076];S 1100=[0.0000290.0000960.000549]
S 2000=[0.0000220.0001510.000331];S 2500=[0.0000240.0001710.000352]
S 3400=[0.0000060.0001300.000281];(6)
Between all adjacent two non-sensitive districts, spectrum segment is carried out to translation and rotation, carry out baseline correction
For above-mentioned 5 non-sensitive districts, whole spectrogram can be divided into 4 intervals, translation and rotation are carried out in each interval, i.e. the regular distortion of rectifiable spectrum.Because each spectrogram is made up of two row, first row is wave number value, and secondary series is the spectral line value corresponding with first row, and near 3400,2500,2000,1100 and 600 wave numbers, corresponding spectral line sequence number is followed successively by 273,753,1023,1503,1758.So get 5 spectral line values and is averaging deviation in every section of non-sensitive district, the concentration vector of supposing 3 kinds of gases to be analyzed is C=[C 1, C 2, C 3], can adopt following source code to realize first spectral shift and rotation:
Baseline3400=1-mean (data (271:275,2))-S 3400c'; % asks the deviation at wave number 3400 places
Baseline2500=1-mean (data (751:755,2))-S 2500c'; % asks the deviation at wave number 2500 places
Baserate2500=(Baseline2500-Baseline3400)/(753-273); % asks the slope between wave number 2500 to 3400
Data (1:753,2)=data (1:753,2)+Baseline3400+ ([1:753] '-271) * Baserate2500; % corrects the spectrum between wave number 2500 to 3400
Baseline2000=1-mean (data (1021:1025,2))-S 2000c'; % asks the deviation at wave number 2000 places
Baserate2000=(Baserate2000-Baserate2500)/(1023-753); % asks the slope between wave number 2000 to 2500
Data (754:1023,2)=data (754:1023,2)+Baseline2500+ ([754:1023] '-753) * Baserate2000; % corrects the spectrum between wave number 2500 to 3400
Baseline1100=1-mean (data (1501:1505,2)) – S 1100c'; % asks the deviation at wave number 1100 places
Baserate1100=(Baseline1100-Baseline2000)/(1503-1023); % asks the slope between wave number 1100 to 2000
Data (1024:1503,2)=data (1024:1503,2)+Baseline2000+ ([1024:1503] '-1023) * Baserate1100; % corrects the spectrum between wave number 1100 to 2000
Baseline600=1-mean (data (1756:1760,2)) – S 600c'; % asks the deviation at wave number 1100 places
Baserate600=(Baseline600-Baseline1100)/(1758-1503); % asks the slope between wave number 600 to 1100
Data (1504:1866,2)=data (1504:1866,2)+Baseline1100+ ([1504:1866] '-1503) * Baserate600; % corrects the spectrum between wave number 600 to 1100
In continuous on-line optical spectroscopy analysis process, the gas concentration vector C in above-mentioned source code is set as last analysis result.If analyze for the first time, be set to 0.For the accompanying drawing 5 (a) in this embodiment, there are three spectrogram: data1, data2 and data3.Comparative drawings figs 5 (a) and accompanying drawing 4 (a) are known, since wave number does not have strong absorption peak near 2900 places, illustrate in the gas that these three spectrograms characterize, the concentration of various alkane is very little, therefore, in wave number 800 to wave number 1100, and in 2500 wave numbers in 3400 wave-number ranges, be almost a straight line that amplitude is 1.But in accompanying drawing 5 (a), wave number 800 is obviously greater than 1 to the spectral value of the spectrum segment of wave number 1100, and slightly tilt, be significantly less than 1 in 2500 wave numbers to the spectrum segment in 3400 wave-number ranges, its inclined degree is slightly larger to the spectrum segment of wave number 1100 than wave number 800, therefore there is baseline regular distortion, need to proofread and correct.It is 0 that gas concentration vector C is set, and the spectrogram obtaining after adopting the source code of this step to proofread and correct is as shown in accompanying drawing 5 (b);
By the analytical model of demarcating, the spectrum after proofreading and correct is analyzed, obtained gas composition and concentration thereof
In data1, data2 as shown in accompanying drawing 5 (b) and data3 spectrum substitution formula (3), calculate characteristic variable value v separately respectively m, v eand v p, and calculate concentration separately according to formula (4).
C 1=[0.01960.00320.0017];
C 2=[0.00710.00120.0003];(7)
C 3=[0.04730.00210.0023];
If portion gas concentration is larger, use in the gas concentration value substitution aforementioned spectral aligning step of latest computed, again spectrum is proofreaied and correct, until the difference of adjacent twice deviate in any one non-sensitive district is less than certain threshold value in this step.The Threshold in each non-sensitive district is the noise amplitude of this wave number section spectrum.Because each component gas concentration in this embodiment is very little, therefore proofreaied and correct once by this step, and the result of formula (4) can be regarded final analysis result.
The gas composition being obtained by analysis and concentration reconstruct spectrum thereof
For reconstruct spectrum, first need to estimate the conversion absorptance of each spectral line, i.e. absorptance and spectrometer light path product.J one-component sample of i kind gas in the conversion absorptance of k article of spectral line is:
δ ik,j=-log(v ikj)/c i, j(8)
V in formula ikjrepresent that j one-component sample of i kind gas is at the spectral value of k article of spectral line; Log () represents natural logarithm computing; c i,jrepresent j one-component concentration of specimens of i kind gas.If the concentration calculated value of i kind gas is ci, x, and c i,j<c i,x≤ c i, j+1, j=1,2 ..., N-1, k article of spectral line place, the conversion absorptance of this kind of gas is:
rate=(c i,x-c i,j)/(c i,j+1-c i,j)(9a)
δ ikx=(1-rate)×δ ik,j+rate×δ ik,j+1(9b)
For shortening computing time, can a reconstruct spectrum in target aspiration peak and near spectrum segment thereof.In the present embodiment, only need reconstruct wave number section 700~1300 and 2800~3200.The reconstruct of the spectral line of locating with the 579th article of spectral line (corresponding to wave number 2881.5) in the present embodiment for the sake of simplicity, illustrates the reconstructing method of spectral line.Due in small concentration situation, the conversion absorptance of each component gas changes with gas concentration hardly, conversion absorptance when therefore the conversion absorptance of the each component gas in the present embodiment directly adopts 0.1% concentration.For example, the spectral line value that 0.1% concentration n-pentane one-component sample is located at the 579th article of spectral line (corresponding to wave number 2881.5) is 0.9462, therefore its conversion absorptance is calculated by formula (10):
δ 7,579,4=-log(0.9462)/0.1=0.5530(10)
By that analogy, can try to achieve 3 component gas in the conversion absorptance of 579 spectral lines and form vectorial Δ and obtain:
Δ=[0.02000.14100.5393](11)
Can try to achieve respectively according to Lambert-Beer theorem the reconstruct spectral value that data1, data2 and tri-spectrograms of data3 go out at the 579th article of spectral line by formula (7) and (11) is respectively:
v 1,579=exp(-C 1Δ')=0.9982
v 2,579=exp(-C 2Δ')=0.9995
v 3,579=exp(-C 3Δ')=0.9974
By that analogy, can try to achieve the reconstruct spectral line value of every spectral line.So, for data1, data2 and data3 in accompanying drawing 5 (a), proofread and correct forward and backwardly, and the spectrum of reconstruct is respectively as shown in accompanying drawing 5 (c), 5 (d) and 5 (e).
Spectrum distortion identification and processing
For the regular distortion of spectrum, abovementioned steps is proofreaied and correct spectrum in fact, and this step is used for identifying the irregular local distortion of spectrum, and makes reasonable processing according to recognition result.
Observing spectrum in accompanying drawing 5 (c) can find, near wave number 1060, revised data1 spectral value obviously exceeds 1.0020, in fact, the noise amplitude at this place only has 0.0015 left and right, and therefore data1 spectrum may exist local distortion, this time analysis result deviation may be larger, if possible, need to rescan background, to obtain good analysis result; Observing accompanying drawing 5 (d) can find, near wave number 1045, the spectral value of revised data2 spectrum closely reaches 1.0020, and therefore data2 spectrum may also exist local distortion; Observing accompanying drawing 5 (e) can find, the spectral value maximum of revised data3 spectrum 1.0010 left and right only, and therefore data3 is the good spectrum that local distortion does not occur, and with peg model, this spectrum is analyzed, its confidence level is very high.In fact, can be found out by accompanying drawing 5 (b), in wave number 1000 to 1200 scopes, the spectrum of data1 and data2 is frequency ribbed not etc., and this itself is exactly the one performance of spectrum local distortion.
Certainly, in computer based Intelligent Recognition, can not identify by manual observation, need to identify by software.For this step, reconstruct spectrum and the difference of revising spectrum in wave number segment limit that only need to be more interested, be greater than noise level if correction spectral value is greater than the numerical value of corresponding reconstruct spectrum, may have local distortion.Difference is larger, and distortion degree is larger.If difference is excessive, abandon when time analysis result, and prompting makes mistakes; If difference in certain permissible range, is not enough to produce large impact, work on; If there is continuously the irregular distortion of spectrum local, rescan background.
4) decision-making
If can judge from spectral analysis result may there are one or more drugs in some monitored physical spaces, by note or internet, notice public security organ, content of announcement comprises may obtain drugs title, place, place, hotel/KTV title, room number.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by submitted to claims.

Claims (6)

1. drugs are sucked a situation infrared spectrum on-line monitoring system, it is characterized in that, comprise some solenoid directional control valves, Fourier transform infrared spectrometer, aspiration pump and industrial computer; Wherein, the air intake opening of some solenoid directional control valves is arranged in corresponding some monitored physical spaces, the gas outlet of some solenoid directional control valves is connected with the air chamber entrance of Fourier transform infrared spectrometer respectively, industrial computer is selected one of them solenoid directional control valve work within one time, aspiration pump is for the gas of monitored physical space being evacuated to the air chamber of Fourier transform infrared spectrometer, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer.
2. drugs are sucked a situation infrared spectrum on-line monitoring method, it is characterized in that, the method is sucked situation infrared spectrum on-line monitoring system based on a kind of drugs claimed in claim 1, comprises the following steps:
1) at one time, industrial computer is selected one of them solenoid directional control valve work, aspiration pump is evacuated to Fourier transform infrared spectrometer air chamber by this solenoid directional control valve by the air of a monitored physical space corresponding with this solenoid directional control valve and carries out on-line analysis, obtains absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another solenoid directional control valve work.
3. drugs are sucked a situation infrared spectrum on-line monitoring system, it is characterized in that, comprise some aspiration pumps, Fourier transform infrared spectrometer and industrial computer; Wherein, the air intake opening of some aspiration pumps is arranged in corresponding some monitored physical spaces, the gas outlet of some aspiration pumps is connected with the air chamber entrance of Fourier transform infrared spectrometer respectively, industrial computer is for selecting one of them aspiration pump work at one time, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer.
4. drugs are sucked a situation infrared spectrum on-line monitoring method, it is characterized in that, the method is sucked situation infrared spectrum on-line monitoring system based on a kind of drugs claimed in claim 3, comprises the following steps:
1) at one time, industrial computer is selected one of them aspiration pump work, the air that this aspiration pump is monitored physical space is evacuated to Fourier transform infrared spectrometer air chamber and carries out on-line analysis, obtains absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another aspiration pump work.
5. drugs are sucked a situation infrared spectrum on-line monitoring system, it is characterized in that, comprise some groups of fiber optic splitters and coupling mechanism, Fourier transform infrared spectrometer and industrial computer; Wherein, some groups of fiber optic splitters and coupling mechanism are arranged in corresponding some monitored physical spaces, and each group fiber optic splitter and coupling mechanism are coupled to Fourier transform infrared spectrometer light source by it at the absorbed interference light of corresponding monitored physical space, industrial computer is for selecting wherein one group of fiber optic splitter and coupling mechanism work at one time, Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space and Optical transmission spectrum data transmission to industrial computer.
6. drugs are sucked a situation infrared spectrum on-line monitoring method, it is characterized in that, the method is sucked situation infrared spectrum on-line monitoring system based on a kind of drugs claimed in claim 5, comprises the following steps:
1) at one time, industrial computer is selected one group of fiber optic splitter and coupling mechanism work, this group fiber optic splitter and coupling mechanism are monitored the absorbed interference light of physical space and are coupled to Fourier transform infrared spectrometer light source and carry out on-line analysis, obtain absorbance spectrum data and the Optical transmission spectrum data of monitored physical space gas;
2) Fourier transform infrared spectrometer by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data transmission to industrial computer, industrial computer is the absorption spectra data comparison with default several drugs gas by the absorbance spectrum data of monitored physical space gas and Optical transmission spectrum data, if the absorbance spectrum data of monitored physical space gas are all more than or equal to the absorption spectrum preset value of one or more default drugs gases, if or the Optical transmission spectrum data of monitored physical space gas are less than or equal to the absorption spectrum preset value of one or more default drugs gases, industrial computer sends alarm signal, if the absorbance spectrum data of monitored physical space gas or Optical transmission spectrum data do not reach the absorption spectrum preset value of any default drugs gas, industrial computer is selected another group fiber optic splitter and coupling mechanism work.
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