CN108008001A - Improve three peroxidating diamines of hexa-methylene（HMTD）The detection method of dosing accuracy - Google Patents
Improve three peroxidating diamines of hexa-methylene（HMTD）The detection method of dosing accuracy Download PDFInfo
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- CN108008001A CN108008001A CN201610969228.0A CN201610969228A CN108008001A CN 108008001 A CN108008001 A CN 108008001A CN 201610969228 A CN201610969228 A CN 201610969228A CN 108008001 A CN108008001 A CN 108008001A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The invention discloses a kind of detection method for improving three peroxidating diamines HMTD dosing accuracies in complex matrices chaff interferent of hexa-methylene.This method is based on time resolution Dynamic Thermal parsing sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectral technology, tracking three peroxidating diamines HMTD of hexa-methylene obtains the Thermal desorption curve of three peroxidating diamines HMTD of hexa-methylene and above-mentioned one or more of chaff interferents with the signal strength under one or more of chaff interferent difference Thermal desorption times in matrix interference thing, afterwards, the signal strength for selecting special time according to time resolution Dynamic Thermal analysis spectrogram quantifies HMTD, so as to improve HMTD accuracys quantitative in matrix interference thing.
Description
Technical field
The present invention is based on time resolution Dynamic Thermal parsing sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectrum
Technology, devises a kind of ionic migration spectrum detection method of time resolution Dynamic Thermal parsing sample introduction, it is quick-fried to realize new peroxidating
Time resolution Dynamic Thermal parsing sample detections of the fried thing HMTD in complex matrices perfume, using under the HMTD difference Thermal desorption times
Signal strength it is quantitative to it, eliminate the competition ionization of perfume matrix interference thing, improve HMTD in complex matrices perfume
Quantitative accuracy.
Background technology
Three peroxidating diamines of hexa-methylene (hexamethylene triperoxide diamine, HMTD) is a kind of new
Type organic peroxy explosive, since raw material is easy to get, preparation method is simple, is commonly used in the attack of terrorism and criminal activity, wraps
Israel guard station London embassy case of explosion in 1994, London Underground case of explosions in 2005 and trans-Atlantic flight in 2006 is included to fear
It is afraid of and attacks, great threat is caused to public safety.HMTD was made first by Legler in 1881, was consolidated for white powder
Body, molecular formula are (CH2)6N2(O2)3, it is all very sensitive to metal, shock, friction and heat.Different from traditional nitro explosive, such as
Trinitrotoluene (TNT), ammonium nitrate-fuel oil mixture (ANFO) and too grace (PETN), HMTD does not both contain nitryl group and aromatic group,
Metal ion is not contained, does not have obvious absorption band in ultraviolet region, also without fluorescent characteristic, the detection side for conventional explosives
Method is difficult to realize the detection of HMTD, and is often stashed carrying by offender, therefore for HMTD in complex matrices
Detection get more and more people's extensive concerning, be badly in need of development it is a kind of can be used for HMTD it is efficient, quick and reliable in complex matrices
Field assay quantitative detecting method.
At present, detecting the method for HMTD mainly has infrared spectrum (IR), Raman spectrum (Raman), mass spectrum (MS), electrochemistry
Detection method, chemiluminescence and high performance liquid chromatography (HPLC) etc..Infrared and Raman spectrum mainly realizes the qualitative analysis of HMTD,
Quantitative detection for HMTD, also there is limitation, it is difficult to the accurate quantitative analysis detection for HMTD in complex matrices；Mass spectrum skill
Although art detection sensitivity is higher, since instrument price is expensive, volume is bigger, cumbersome, it is difficult to explosive
Field quick detection；Electrochemical detection method and chemiluminescence, although apparatus is simple, need sample pre-treatments,
The catabolite H of HMTD can only be analyzed2O2；High performance liquid chromatography is long to the sample separated time, is difficult to realize complex matrices
The quick detection of middle HMTD, therefore, live quick and precisely quantitative measurement technologies of the development HMTD in complex matrices have important
Meaning.
Ion mobility spectrometry (Ion Mobility Spectrometry, IMS) is as a kind of mainstream skill for detecting explosive
Art, compared with the conventional arts such as mass spectrum, chromatography, it has the characteristics that simple in structure, high sensitivity, analyze speed are fast, wide
It is applied to on-line monitoring of explosive examination, drugs inspection and VOCs etc. generally.Ionic migration spectrometer is mainly by ion gun, ion
Door, migration area and detector composition.Ion gun ionizes reagent molecule, and the reagent ion of generation is easy to occur with sample molecule
Ion molecule reaction, obtains multi-products ion.Ion is entered under the driving of electric field by the ion gate periodically opened to be moved
Area is moved, is continually colliding with neutral drift qi leel of adverse current, since these ions have different migration rates in the electric field, makes
Obtain different ions to be separated, successively reach detector.In order to realize accurate quantitative analysis detections of the HMTD in complex matrices, this
Based on reagent molecule auxiliary photo-ionisation cation migration spectral technology, binding time differentiates Dynamic Thermal parsing sampling technique, real for invention
Show quantitative detections of the HMTD in complex matrices, using the signal strength of HMTD under the different Thermal desorption times, improve HMTD
The quantitative accuracy in complex matrices.
The content of the invention
In view of the above problems, the present invention provides one kind to improve hexa-methylene three peroxidating diamines (HMTD) dosing accuracy
Detection method, this method utilizes time resolution Dynamic Thermal parsing sampling technique and reagent molecule auxiliary photo-ionisation cation migration
Spectral technology, controls injector temperature so that sample molecule successively enters reaction zone, has be continued for being passed through in reaction zone
Machine reagent molecule reacts, it is achieved thereby that the time resolution Dynamic Thermal of HMTD samples and perfume matrix interference thing parses sample introduction, carries
High accuracy quantitative in complex matrices perfume HMTD, has widened the range of linearity of HMTD detections.
The technical solution adopted in the present invention is:
Sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectral technology are parsed based on time resolution Dynamic Thermal, with
In three peroxidating diamines HMTD of track hexa-methylene and matrix interference thing under the different Thermal desorption times of one or more of chaff interferents
Signal strength obtains the Thermal desorption curve of three peroxidating diamines HMTD of hexa-methylene and above-mentioned one or more of chaff interferents, afterwards,
The signal strength for selecting special time according to time resolution Dynamic Thermal analysis spectrogram quantifies HMTD, exists so as to improve HMTD
Quantitative accuracy in matrix interference thing.
Time resolution Dynamic Thermal parsing sampling technique refer to sample to be tested in Thermal desorption injector by transient heating,
Due to determinand and the volatile difference of matrix interference thing, successively parse in migration tube and be detected, so as to fulfill the time
Differentiate Dynamic Thermal parsing sample introduction；
The reagent molecule auxiliary photo-ionisation cation migration spectral technology refers under ion mobility spectrometry positive ion mode, leads to
Cross that addition ionization energy is low, the high reagent molecule of ionizing efficiency, photo-ionisation reagent molecule produces reagent ion and sample to be tested reaction
The product ion of determinand is generated so as to detected Ion mobility spectrometry；
The abscissa of time resolution Dynamic Thermal analysis spectrogram is the Thermal desorption time, and ordinate is target compound HMTD to be measured
With the signal strength of other chaff interferents that may be present.
The matrix interference thing is complex mixture, and one or more of chaff interferents in complex mixture produce Interference Peaks,
And the volatility of chaff interferent (tracked chaff interferent) is higher than the volatility of HMTD, volatilization temperature (is less than less than 100 DEG C
100 DEG C help preferably to distinguish the HMTD of tracking and chaff interferent).
The signal strength of the selection special time carries out HMTD quantitative method：Control the temperature of thermal desorption sampling device
Degree is more than 120 DEG C and is less than 180 DEG C, and the temperature of transference tube is more than 90 DEG C and is less than 130 DEG C, based on time resolution dynamic pyrolysis
In the time resolution Dynamic Thermal analysis spectrogram that analysis sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectral technology obtain
One or more of chaff interferents in matrix interference thing are selected to be parsed completely into line trace, the above-mentioned one or more of chaff interferents of selection,
The signal strength at a certain specific time point of the target compound to be measured also without parsing completely in this time range to HMTD into
The quantitative detection of row.
Each material is successively resolved out due to the difference of vapour pressure, is carried along into ion by sample carrier gas and moved in sample
Move the reagent ion produced in spectrum with reagent molecule ionization and ion molecule reaction, the effect of the product ion of generation in electric field occurs
The lower ion gate by periodically opening enters migration area, and due to the difference of mobility, each material successively reaches detection in sample
Device is detected.
Device used in this method includes thermal desorption sampling device and ion mobility spectrometry；
Ion mobility spectrometry includes the transference tube with Faraday plate receiving pole, and the transference tube close to Faraday plate moves
Move area one end and be equipped with sample carrier gas inlet equipped with drift gas entrance, transference tube reaction zone one end away from Faraday plate, in drift
Transference tube reaction zone end between gas entrance and carrier gas inlet, migration area front end are equipped with total gas outlet；
In away from Faraday plate transference tube reaction zone one end be equipped with carrier band organic agent molecule carrier gas stream into
Gas port, air inlet are located at the one end of reaction zone away from Faraday plate, and organic agent molecule enters reaction zone by air inlet.
Reagent molecule flow rate of carrier gas is 50-100ml/min, and sample flow rate of carrier gas is 200-300ml/min, and drift gas velocity is
500-600ml/min；
The vacuum UV lamp ionization source used is the low-voltage direct electric discharge krypton lamp of the magnesium fluoride optical window of the 10.0eV of business
(Cathodeon Ltd.,Cambridge,U.K.)；
The temperature of thermal desorption sampling device is 120-180 DEG C, and the temperature of transference tube is 90-130 DEG C, the electricity of migration area
Field intensity is 377V cm-1。
Sample carrier gas is consistent with reagent molecule carrier gas stream direction in reaction zone, opposite with migration area airflow direction；
All gas in transference tube leave transference tube by total gas outlet；
Reagent molecule air inlet and sample carrier gas inlet are into 0 ° of -180 ° of angle.
Organic agent molecule is acetone used by ion mobility spectrometry；
The concentration of organic agent molecule is 20-30ppm in gas of carrier gas containing organic agent molecule；
The sample carrier gas, reagent molecule carrier gas, the gas that floats gas are through activated carbon, silica gel, molecular sieve filtration
The air crossed.
Lower mask body lifts the example of an above method.
Matrix interference thing is used as using perfume：
1) samples of perfume is initially dissolved in acetone, obtains the perfume solution of 0.1vol%-1vol%, then will be suitable
HMTD solids are directly dissolved in the perfume solution of 0.1%vol%-1vol%, obtain the perfume solution of 5-100ng/ μ L HMTD；
2) perfume solution of 5-100ng/ μ L HMTD is added dropwise and is dried on sampling cloth；
3) the sampling cloth for containing HMTD samples is inserted into thermal desorption sampling device and heated, sample is pyrolyzed by sample carrier gas
The gaseous molecular carrier band separated out enters the reaction reagent ionic reaction in ionic reaction area, with transference tube reaction zone, raw
Into product ion, separated successively by migration area, reach Faraday plate and be detected.
Beneficial effects of the present invention are：
The present invention utilizes time resolution Dynamic Thermal parsing sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectrum
Technology, controls injector temperature so that sample molecule successively enters reaction zone, organic with being continued for being passed through in reaction zone
Reagent molecule reacts, it is achieved thereby that the time resolution Dynamic Thermal of HMTD samples and perfume matrix interference thing parses sample introduction, improves
Accuracy quantitative in complex matrices perfume HMTD, has widened the range of linearity of HMTD detections.
Brief description of the drawings
Fig. 1 is the structure diagram that reagent molecule fill-in light ionizes cation migration spectrum in the present invention, and reagent molecule is lasting
It is passed through reaction zone；
Wherein, 1 is sample carrier gas inlet, and 2 be Thermal desorption injector, and 3 be reagent molecule carrier gas inlet, and 4 be reagent molecule
Generating means, 5 be total gas outlet, and 6 be Bradbury-Nielsen, and 7 be conducting ring, and 8 be aperture plate, and 9 be drift gas entrance, and 10 are
Amplifier, 11 be 5000V high pressures, and 12 be current-limiting resistance, and 13 be the low-voltage direct Kr lamps of 10.0eV magnesium fluoride optical windows
(Cathodeon Ltd.,Cambridge,U.K.)。
Fig. 2 is time resolution dynamic pyrolysis analysis apparatus structure diagram；
Wherein, 14 be sample carrier gas inlet, and 15 be heating rod, and 16 come directly towards for sampling cloth, 17 for injector, and 18 be IMS samples
Product inlet port.
Fig. 3 is transit times of the embodiment 1-3 30ng/ μ L HMTD in three kinds of different brands perfume of complex matrices, solution
Analyse time 2-D spectrogram；
Fig. 4 is time resolution dynamics of the embodiment 1-3 30ng/ μ L HMTD in three kinds of different brands perfume of complex matrices
Thermal desorption spectrogram.
Embodiment
Following time resolution Dynamic Thermal parsing sample introductions with peroxidating explosive HMTD in complex matrices chaff interferent perfume
Exemplified by detection, the ionic migration spectrum detection method of raising HMTD dosing accuracies provided by the present invention is specifically described, by adopting
With reagent molecule auxiliary photo-ionisation cation migration spectral technology, binding time is differentiated Dynamic Thermal parsing sampling technique, is improved
Accuracy quantitative in complex matrices chaff interferent perfume HMTD.
Embodiment 1
1 solution of HMTD perfume that concentration is 30ng/ μ L is added dropwise on sampling cloth, after solvent slightly volatilizees and does, insertion temperature
Spend and be less than for 120 DEG C in the Thermal desorption injector in the range of 180 DEG C, perfume chaff interferent first parses, into ion mobility spectrometry
The reagent ion that produces of reaction zone and acetone reagent molecule ionization react, the temperature of transference tube is in 90 DEG C of -130 DEG C of scopes
It is interior, parsed after HMTD, the reagent ion produced into reaction zone and the ionization of acetone reagent molecule reacts, the product of generation from
The ion gate that son is opened under the action of electric field by periodicity enters migration area, and the electric field strength of migration area is 377V cm-1,
Due to the difference of mobility, successively reach detector and be detected, from figure 3, it can be seen that HMTD in perfume matrix 1 can by into
Detect work(, the transit time of HMTD be 9.48ms, the product ion peak of perfume matrix interference thing and the product of HMTD from
Sub- peak does not have cross jamming, due to HMTD and the volatile difference of perfume matrix interference thing, the volatility of perfume matrix interference thing
Height, first parses, and reaches maximum signal in Thermal desorption 1s, and the volatility of HMTD is relatively low, is solved after HMTD
Separate out, reach maximum signal in Thermal desorption 4s, so as to fulfill time resolution Dynamic Thermals of the HMTD in perfume matrix
Resolved detection.
Embodiment 2
2 solution of HMTD perfume that concentration is 30ng/ μ L is added dropwise on sampling cloth, after solvent slightly volatilizees and does, insertion temperature
Spend and be less than for 120 DEG C in the Thermal desorption injector in the range of 180 DEG C, perfume chaff interferent first parses, into ion mobility spectrometry
The reagent ion that produces of reaction zone and acetone reagent molecule ionization react, the temperature of transference tube is in 90 DEG C of -130 DEG C of scopes
It is interior, parsed after HMTD, the reagent ion produced into reaction zone and the ionization of acetone reagent molecule reacts, the product of generation from
The ion gate that son is opened under the action of electric field by periodicity enters migration area, and the electric field strength of migration area is 377V cm-1,
Due to the difference of mobility, successively reach detector and be detected, from figure 3, it can be seen that HMTD in perfume matrix 2 can by into
Detect work(, the transit time of HMTD be 9.48ms, the product ion peak of perfume matrix interference thing and the product of HMTD from
Sub- peak does not have cross jamming, due to HMTD and the volatile difference of perfume matrix interference thing, the volatility of perfume matrix interference thing
Height, first parses, and reaches maximum signal in Thermal desorption 1s, and the volatility of HMTD is relatively low, is solved after HMTD
Separate out, reach maximum signal in Thermal desorption 4s, so as to fulfill time resolution Dynamic Thermals of the HMTD in perfume matrix
Resolved detection.
Embodiment 3
3 solution of HMTD perfume that concentration is 30ng/ μ L is added dropwise on sampling cloth, after solvent slightly volatilizees and does, insertion temperature
Spend and be less than for 120 DEG C in the Thermal desorption injector in the range of 180 DEG C, perfume chaff interferent first parses, into ion mobility spectrometry
The reagent ion that produces of reaction zone and acetone reagent molecule ionization react, the temperature of transference tube is in 90 DEG C of -130 DEG C of scopes
It is interior, parsed after HMTD, the reagent ion produced into reaction zone and the ionization of acetone reagent molecule reacts, the product of generation from
The ion gate that son is opened under the action of electric field by periodicity enters migration area, and the electric field strength of migration area is 377V cm-1,
Due to the difference of mobility, successively reach detector and be detected, from figure 3, it can be seen that HMTD in perfume matrix 3 can by into
Detect work(, the transit time of HMTD be 9.48ms, the product ion peak of perfume matrix interference thing and the product of HMTD from
Sub- peak does not have cross jamming, due to HMTD and the volatile difference of perfume matrix interference thing, the volatility of perfume matrix interference thing
Height, first parses, and reaches maximum signal in Thermal desorption 1s, and the volatility of HMTD is relatively low, is solved after HMTD
Separate out, reach maximum signal in Thermal desorption 4s, so as to fulfill time resolution Dynamic Thermals of the HMTD in perfume matrix
Resolved detection.
Embodiment 4
The HMTD standard solutions that concentration is 5-100ng/ μ L are added dropwise on sampling cloth, after solvent slightly volatilizees and does, are inserted
Enter temperature for 120 DEG C to be less than in the Thermal desorption injector in the range of 180 DEG C, parsed after HMTD, into reaction zone and acetone
The reagent ion reaction that reagent molecule ionization produces, the product ion of generation under the action of electric field by periodicity open from
Cervical orifice of uterus enters migration area, and for the temperature of transference tube in the range of 90 DEG C -130 DEG C, the electric field strength of migration area is 377V cm-1,
Due to the difference of mobility, successively reach detector and be detected, the quantitative result of HMTD standard samples is as shown in table 1, utilizes
The HMTD ranges of linearity that HMTD maximum signals quantitatively obtain are 5-50ng/ μ L, are limited to by the S/N=3 detections calculated
0.2ng/ μ L, the HMTD ranges of linearity quantitatively obtained using the signal strength of HMTD 10s are 5-100ng/ μ L, and the range of linearity is opened up
One times wide, detection is limited to 0.3ng/ μ L.
The ion mobility spectrometry that a kind of present invention uses is provided below, which is included with Faraday plate receiving pole
Transference tube, drift gas entrance, the ion away from Faraday plate are equipped with close to transference tube migration area one end of Faraday plate
Migration tube reaction zone one end is equipped with sample carrier gas inlet, the transference tube reaction zone end between drift gas entrance and carrier gas inlet
End, migration area front end is equipped with total gas outlet；
The air inlet of the gas containing organic agent molecule is equipped with the side wall of transference tube, air inlet is located at reaction zone
Front end, enter reaction zone into 0 ° of -180 ° of angle, organic agent molecule with sample carrier gas inlet.Reagent molecule flow rate of carrier gas scope
For 50-100ml/min, sample flow rate of carrier gas scope is 200-300ml/min, and drift gas velocity scope is 500-600ml/min.
The vacuum UV lamp ionization source used is the low-voltage direct electric discharge krypton lamp of the magnesium fluoride optical window of the 10.0eV of business
(Cathodeon Ltd.,Cambridge,U.K.)。
The temperature range of thermal desorption sampling device is 120-180 DEG C, the temperature range of migration tube in the range of 90-130 DEG C,
The electric field strength of migration area is 377V cm-1。
Sample carrier gas is consistent with reagent molecule carrier gas stream direction in reaction zone, opposite with migration area airflow direction；
All gas in transference tube leave transference tube by total gas outlet.
Organic agent molecule is acetone used by ion mobility spectrometry.
The gas for carrying sample, reagent molecule and drift gas is the sky crossed through activated carbon, silica gel, molecular sieve filtration
Gas.
The concentration of organic agent molecule is 20-30ppm in carrier gas containing organic agent molecule.
The temperature range of thermal desorption sampling device is 120-180 DEG C, the temperature range of migration tube in the range of 90-130 DEG C,
The electric field strength of migration area is 377V cm-1。
Fig. 1 is a kind of structure diagram for transference tube that this method is related to, and Fig. 2 is time resolution Dynamic Thermal parsing dress
Put structure diagram.
As shown in figure 3, specially 30ng/ μ L HMTD and perfume matrix interference thing be after Dynamic Thermal parses sample introduction, perfume base
Matter chaff interferent first parses, transit time, the parsing time 2-D spectrogram parsed after HMTD；As shown in figure 4, it is specially
30ng/ μ L HMTD are in three kinds of different brands perfume after Dynamic Thermal parses sample introduction, and perfume chaff interferent first parses, HMTD
The time resolution Dynamic Thermal analysis spectrogram of the time resolution Dynamic Thermal parsing parsed afterwards.
Principle：Drop is had in the sampling cloth insertion Thermal desorption injector of sample, sample molecule is first due to the difference of vapour pressure
Afterwards be resolved out, by sample carrier gas be carried along into ion mobility spectrometry with reagent molecule ionization produce reagent ion occur from
Sub- molecule reaction, the ion gate that the product ion of generation is opened under the action of electric field by periodicity enter migration area, due to
The difference of mobility, successively reaches detector and is detected.
Fig. 3 and Fig. 4 can be seen that in the present invention, be understood in Fig. 3 in HMTD maximum signals, perfume matrix interference thing
Do not parse completely, and HMTD influences quantifying for HMTD there is competition ionization；The perfume matrix interference thing in 10s
Parse completely, it is smaller to the quantitative effect of HMTD, improve HMTD accuracys quantitative in perfume matrix.
Table 1
X is the mass concentration of HMTD, and unit is signal strength for ng/ μ L, y, unit mV.
The quantitative result of HMTD standard samples is as shown in table 1, the HMTD lines quantitatively obtained using HMTD maximum signals
Property scope be 5-50ng/ μ L, by S/N=3 calculate detection be limited to 0.2ng/ μ L, quantified using the signal strength of HMTD 10s
The obtained HMTD ranges of linearity are 5-100ng/ μ L, and the range of linearity has widened one times, and detection is limited to 0.3ng/ μ L.
Table 2
Table 2 is the rate of recovery of the 30ng/ μ L HMTD in three kinds of different brands perfume under two kinds of different basis weights methods, from table 2
In as can be seen that the standard sample of 30ng/ μ L HMTD is respectively using the recovery of standard addition that both quantitative approach obtain
102.2% and 98.0%, without obvious difference.Then, both quantitative approach are used for three kinds of different brands samples of perfume
The quantitative detection of middle HMTD, quantitative result is as shown in table 2, the rate of recovery of the 30ng/ μ L HMTD in three kinds of perfume, with HMTD's
Maximum signal is quantified, and recovery of standard addition is respectively 80.4%, 78.9% and 66.2%, and the rate of recovery is not high, because
In HMTD maximum signals, perfume matrix interference thing has not parsed completely, and HMTD is influenced there is competition ionization
HMTD's quantifies；Quantified using the signal strength of 10s HMTD, recovery of standard addition is respectively 96.1%, 91.0% He
96.4%, the rate of recovery is of a relatively high, because perfume matrix interference thing has parsed completely during 10s, to the quantitative shadow of HMTD
Sound is smaller, improves HMTD accuracys quantitative in perfume matrix.The detection times of 10s preferably in the present embodiment,
The parsing of perfume matrix interference thing is complete, and HMTD in the time range parsed also without can obtain preferable dosing accuracy.
Claims (10)
1. one kind improves the detection method of hexa-methylene three peroxidating diamines (HMTD) dosing accuracy, it is characterised in that：
This method is based on time resolution Dynamic Thermal parsing sampling technique and reagent molecule auxiliary photo-ionisation cation migration spectral technology,
Track in three peroxidating diamines HMTD of hexa-methylene and matrix interference thing under the different Thermal desorption times of one or more of chaff interferents
Signal strength obtain the Thermal desorption curve of three peroxidating diamines HMTD of hexa-methylene and above-mentioned one or more of chaff interferent, it
Afterwards, the signal strength for selecting special time according to time resolution Dynamic Thermal analysis spectrogram quantifies HMTD, so as to improve
Accuracy quantitative in matrix interference thing HMTD.
2. detection method according to claim 1, it is characterised in that：
Time resolution Dynamic Thermal parsing sampling technique refer to sample to be tested in Thermal desorption injector by transient heating, due to
Determinand and the volatile difference of matrix interference thing, successively parse in migration tube and are detected, so as to fulfill time resolution
Dynamic Thermal parses sample introduction；
The reagent molecule auxiliary photo-ionisation cation migration spectral technology refers under ion mobility spectrometry positive ion mode, by adding
Add ionization energy low, the high reagent molecule of ionizing efficiency, photo-ionisation reagent molecule produces reagent ion and sample to be tested reaction generation
The product ion of determinand is so as to detected Ion mobility spectrometry；
The abscissa of time resolution Dynamic Thermal analysis spectrogram is the Thermal desorption time, and ordinate is target compound HMTD to be measured and its
The signal strength of its chaff interferent that may be present.
3. detection method according to claim 1, it is characterised in that：
The matrix interference thing is complex mixture, and one or more of chaff interferents in complex mixture produce Interference Peaks, and
The volatility of chaff interferent is higher than the volatility of HMTD, and volatilization temperature is less than 100 DEG C.
4. detection method according to claim 1, it is characterised in that：
The signal strength of the selection special time carries out HMTD quantitative method：Control the temperature of thermal desorption sampling device big
Be less than 180 DEG C in 120 DEG C, the temperature of transference tube is more than 90 DEG C and is less than 130 DEG C, based on time resolution Dynamic Thermal parse into
Selected in the time resolution Dynamic Thermal analysis spectrogram that sample technology and reagent molecule auxiliary photo-ionisation cation migration spectral technology obtain
For one or more of chaff interferents in matrix interference thing into line trace, the above-mentioned one or more of chaff interferent parsings of selection are complete, to be measured
The signal strength at a certain specific time point of the target compound also without parsing completely in this time range determines HMTD
Amount detection.
5. detection method according to claim 4, it is characterised in that：
Each material is successively resolved out due to the difference of vapour pressure, ion mobility spectrometry is carried along into by sample carrier gas in sample
In the reagent ion that is produced with reagent molecule ionization ion molecule reaction occurs, the product ion of generation leads under the action of electric field
Cross the ion gate periodically opened and enter migration area, due to the difference of mobility, each material successively reaches detector quilt in sample
Detection.
6. detection method according to claim 1, it is characterised in that：
Device used in this method includes thermal desorption sampling device and ion mobility spectrometry；
Ion mobility spectrometry includes the transference tube with Faraday plate receiving pole, close to the transference tube migration area of Faraday plate
One end is equipped with drift gas entrance, transference tube reaction zone one end away from Faraday plate is equipped with sample carrier gas inlet, enters in drift gas
Transference tube reaction zone end between mouth and carrier gas inlet, migration area front end is equipped with total gas outlet；
The air inlet of carrier band organic agent molecule carrier gas stream is equipped with transference tube reaction zone one end away from Faraday plate,
Air inlet is located at the one end of reaction zone away from Faraday plate, and organic agent molecule enters reaction zone by air inlet.
7. detection method according to claim 6, it is characterised in that：
Reagent molecule flow rate of carrier gas is 50-100ml/min, and sample flow rate of carrier gas is 200-300ml/min, and drift gas velocity is 500-
600ml/min；
The vacuum UV lamp ionization source used is the low-voltage direct electric discharge krypton lamp of the magnesium fluoride optical window of the 10.0eV of business
(Cathodeon Ltd.,Cambridge,U.K.)；
The temperature of thermal desorption sampling device is 120-180 DEG C, and the temperature of transference tube is 90-130 DEG C, the electric-field strength of migration area
Spend for 377V cm-1。
8. detection method according to claim 6, it is characterised in that：
Sample carrier gas is consistent with reagent molecule carrier gas stream direction in reaction zone, opposite with migration area airflow direction；
All gas in transference tube leave transference tube by total gas outlet；
Reagent molecule air inlet and sample carrier gas inlet are into 0 ° of -180 ° of angle.
9. detection method according to claim 6, it is characterised in that：
Organic agent molecule is acetone used by ion mobility spectrometry；
The concentration of organic agent molecule is 20-30ppm in gas of carrier gas containing organic agent molecule；
The sample carrier gas, reagent molecule carrier gas, the gas that floats gas are to be crossed through activated carbon, silica gel, molecular sieve filtration
Air.
10. detection method according to claim 1, it is characterised in that：
Matrix interference thing is used as using perfume：
1) samples of perfume is initially dissolved in acetone, obtains the perfume solution of 0.1vol%-1vol%, then by suitable HMTD
Solid is directly dissolved in the perfume solution of 0.1%vol%-1vol%, obtains the perfume solution of 5-100ng/ μ L HMTD；
2) perfume solution of 5-100ng/ μ L HMTD is added dropwise and is dried on sampling cloth；
3) the sampling cloth for containing HMTD samples is inserted into thermal desorption sampling device and heated, sample is pyrolyzed and separates out by sample carrier gas
The gaseous molecular carrier band come enters the reaction reagent ionic reaction in ionic reaction area, with transference tube reaction zone, generation production
Thing ion, separates successively by migration area, reaches Faraday plate and is detected.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109283039A (en) * | 2018-10-22 | 2019-01-29 | 南京国科医工科技发展有限公司 | A kind of gas molecule concentrated method and device |
| CN112924529A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Trimethylamine oxide detection method based on ion mobility spectrometer and application thereof |
| CN113588767A (en) * | 2021-08-03 | 2021-11-02 | 大连工业大学 | Biogenic amine detection method based on time-resolved dynamic thermal desorption ion mobility spectrometry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675088A (en) * | 2012-09-13 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for rapidly separating and detecting mixed explosives |
| CN104374820A (en) * | 2013-08-15 | 2015-02-25 | 中国科学院大连化学物理研究所 | Method for measuring inorganic oxidants in inorganic explosive through thermal desorption ion mobility spectrometry |
| CN104713945A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for detecting explosive peroxide TATP |
| CN105548327A (en) * | 2014-10-28 | 2016-05-04 | 中国科学院大连化学物理研究所 | Rapid detection for improving sensitivity of ion mobility spectrometry |
-
2016
- 2016-10-28 CN CN201610969228.0A patent/CN108008001A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675088A (en) * | 2012-09-13 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for rapidly separating and detecting mixed explosives |
| CN104374820A (en) * | 2013-08-15 | 2015-02-25 | 中国科学院大连化学物理研究所 | Method for measuring inorganic oxidants in inorganic explosive through thermal desorption ion mobility spectrometry |
| CN104713945A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for detecting explosive peroxide TATP |
| CN105548327A (en) * | 2014-10-28 | 2016-05-04 | 中国科学院大连化学物理研究所 | Rapid detection for improving sensitivity of ion mobility spectrometry |
Non-Patent Citations (1)
| Title |
|---|
| DANDAN JIANG 等: ""Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex Matrices"", 《ANALYTICAL CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109283039A (en) * | 2018-10-22 | 2019-01-29 | 南京国科医工科技发展有限公司 | A kind of gas molecule concentrated method and device |
| CN109283039B (en) * | 2018-10-22 | 2023-06-13 | 南京国科精准医学科技有限公司 | Gas molecule concentration and enrichment method and device |
| CN112924529A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Trimethylamine oxide detection method based on ion mobility spectrometer and application thereof |
| CN113588767A (en) * | 2021-08-03 | 2021-11-02 | 大连工业大学 | Biogenic amine detection method based on time-resolved dynamic thermal desorption ion mobility spectrometry |
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