CN106290545B - A kind of method and device of detection trace compound - Google Patents
A kind of method and device of detection trace compound Download PDFInfo
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- CN106290545B CN106290545B CN201610609743.8A CN201610609743A CN106290545B CN 106290545 B CN106290545 B CN 106290545B CN 201610609743 A CN201610609743 A CN 201610609743A CN 106290545 B CN106290545 B CN 106290545B
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Abstract
The invention discloses a kind of method and devices of detection trace compound, including：Step 1 ionizes sample；Step 2 carries out the square wave frequency signal modulation that duty ratio is 50% to continuous ion stream；Step 3, by the step 2, treated that ion flows into that moving apparatus carries out Ion transfer separation；Step 4 rebuilds ion mobility spectrometry using Chirp Z transform.The utilization rate of ion can be increased to 50% by high sensitivity, method provided by the invention, improve 3~10 times compared with conventional method sensitivity, compared with conventional Fourier transform, sensitivity can be improved 12 times.High resolution.Method provided by the invention compared with conventional method can by common tailing peak, stick out one's tongue peak phenomena such as eliminate, to improve resolution ratio, and then improve mass spectrum database and quantitative effect.
Description
Technical field
The present invention relates to technical field of analytical instruments more particularly to a kind of method and devices of detection trace compound.
Background technology
Ion mobility spectrometry (Ion Mobility Spectrometry, IMS) technology is the one kind occurred the seventies in last century
Novel quick separating detection technique.Since separation can carry out under atmospheric pressure, vacuum is not needed, with traditional mass spectrometer phase
More simple in structure than having, high sensitivity, analyze speed is fast, as a result reliable feature.Meanwhile the separating rate of ion mobility spectrometry is non-
It is often fast, can complete once to analyze in usual a few tens of milliseconds, can be provided in several seconds to tens seconds analysis as a result, it is possible to
Trace level chemical substance is detected in atmospheric environment, instrument is particularly suitable for onsite application.Currently, ion mobility spectrometry airport,
The safety checks such as station occasion, the detection of precursor chemicals, the methods of detection of chemical warfare agent is widely applied, in tradition
Security fields have unique effect.Ion mobility spectrometry is usually by ion source, ion gate, transport area and detector group
At.Solid, liquid phase or gaseous sample ionize in an ion source generates ion, and ion is under the driving of electric field by periodically opening
Ion gate enter drift region, and during constantly being collided with the neutral drift gas molecule of adverse current, due to these ions
Respective migration rate is different in the electric field so that different ions obtains separation and successively arrival collector is detected.Therefore logical
It crosses and measures the presence that transit time just can determine analysis target substance, and peak area or peak height is applied to can determine the dense of respective substance
Degree.
Above process intermediate ion door opening time and ion enter the ratio between transit time behind migration area and are known as duty ratio
(Duty Cycle, DC), DC determine signal-to-noise ratio and the sensitivity of instrument, while also contributing to the resolution ratio of analysis.Compared to biography
Duty ratio can be increased to 50% by the periodical single door opening method of system, the Hadamard transform methods proposed in recent years, with
Conventional method is compared and decades of times can be improved.This mode is considered as a kind of encoding-decoding process to ion signal, entire to apply
Process can divide 3 stages.1st stage was design pseudo-random binary sequence.2nd stage be ion signal the generation stage into
Row Signal coding replaces traditional recurrent pulses to control ion door switch and generates ion signal by pseudo-random sequence.3rd stage
It is to carry out signal decoding in the processing stage of ion signal, using the Hadamard inverse matrixs of corresponding control sequence as deconvolution
Encoded signal is reduced into Ion transfer spectrum signal by core by deconvoluting.
A kind of similar also Fourier transform ion mobility spectrometry (Fourier Transform are converted with Hadamard
Ion Mobility Spectrometry), pseudo-random binary sequence is not used unlike Hadamard transformation, and make
Ion gate is modulated with the gate-control signal of different frequency.Traditional Fourier transformation ion mobility spectrometry is synchronized out using two
Frequency-region signal is converted to time-domain signal, work by the ion gate of pass again to receive interference signal in detector after acquiring signal
The duty ratio of work is 25%.Both signal modulating methods all substantially increase the duty ratio of Ion transfer spectrum analysis, to make
Sensitivity increases.Fourier transform is due to only sensitive to the fixed ion signal of mobility, thus resolution ratio is also carried
It is high.
In recent years, ion mobility spectrometry and mass spectrograph are combined the Disciplinary Frontiers competitively developed as each apparatus manufacture.
Although mass spectrometric resolution ratio is very high, the mass resolution of such as novel time of-flight mass spectrometer can reach 10,000 or more.But
It is, when analysis is with weight compound, even if mass resolution>1000000, still possibly these isomers can not be detached
Identification.For isomer, then advanced mass spectrograph is all helpless.But ion mobility spectrometry can just tied
Mass spectrum is supplemented well in terms of the identification of structure isomers.On the other hand, for the complexity containing multiple compounds type
For the analysis of mixture, separating capacity is particularly important.Depth analysis is carried out, individual chromatographic isolation is helpless,
Because it can not characterize several compounds of outflow altogether being eluted out from a liquid chromatogram peak.In addition, high-resolution
Mass spectrum may also be limited to MS sweep speeds, detached without effective front end, can not obtain allization in sample
Close the data of object.Effluent is total to for chromatography, if retention time is variant, mass spectrum can rebuild mass spectrum using deconvoluting
Figure.But if chromatography peak complete-superposing, chromatograph-mas spectrometer also can not be identified effectively, be missed so as to cause quantitative
Difference encounters difficulties to the identification of compound.The speed (millisecond) of ion mobility spectrometry separation is between HPLC (second) and mass spectrum (microsecond)
Time range in, system being capable of the trace compound that can not detach of separation chromatography.Studies have shown that using ion mobility spectrometry mass spectrum
Combined system can make total coverage rate of lipid improve 5 times or so, in proteomics research, be joined using ion mobility spectrometry mass spectrum
With identify come peptide and protein quantity than be used alone LC/MS analysis increase by 3 times.If by chromatography, Ion transfer
The separating capacity of spectrum and mass spectrometric mass resolution are combined together, and can obtain very high peak capacity, to complicated chemical combination
The separation of object is particularly useful.
But it is limited by the separation principle of ion mobility spectrometry at present, the resolution ratio of ion mobility spectrometry and the spirit of mass spectral analysis
Sensitivity is at a pair of parameter to condition each other.Resolution ratio is improved, must just shorten the time of ion implanting as possible, in this way meeting again
The quantity for reducing injection ion, to sacrifice sensitivity.To solve this problem, Hadamard transformation and Fourier transform are same
Also it has used in ion mobility spectrometry-mass spectrometer, but problem is still very prominent, while the problem for also bringing some new, such as
Hadamard transformation will produce some ghost peaks being originally not present, qualitative and mistake quantitatively occur.Due to the work of two ion gates
Waveform is all square wave, and Fourier transformation also will produce ghost peak, additional difficulty is brought to spectrum analysis.In addition, due to traditional
B-N ion gates have very strong discrimination effect to the ion of different mass-to-charge ratioes, so that the ion-sensitive degree of high mass-to-charge ratio reduces,
This phenomenon becomes more serious when using two ion gates, and the sensitivity raising of Fourier transformation is very limited, best
In the case of also only less than 3 times signal-to-noise ratio improve.Because the resulting ion transfer spectrogram of Fast Fourier Transform (FFT)
Temporal resolution is related with sweep velocity, and sweep velocity is limited by detector type (such as mass spectrograph) and the work of ion gate is former
Reason, thus the temporal resolution of the ion transfer spectrogram generated is very low, to bring difficulty to the qualitative analysis of compound.
On the instrument of some commercializations, to improve ion implanting efficiency to improve sensitivity, Ion transfer detaches quilt
It is placed under low pressure and carries out, while ion pulse is turned to capture ion and continuous ionic circulates by the way of trap collection.This
The structure of a little instruments becomes extremely complex, and volume is also very big, and instrument price is expensive.At the same time, due under low pressure ion in
Property gas molecule collision frequency be greatly reduced, to ion mobility spectrometry resolution ratio it is very limited, such as low pressure under uniform electric field
Ion transfer spectral resolution be usually less than 60, and the resolution ratio of traveling wave ion mobility spectrometry is usually less than 40.
Invention content
The purpose of the present invention is exactly to solve the above-mentioned problems, to provide a kind of method and device of detection trace compound,
Trace compound is detected under atmospheric pressure has the characteristics that highly sensitive, high-resolution.
To achieve the goals above, the present invention adopts the following technical scheme that：
A method of detection trace compound, including：
Step 1 ionizes sample；
Step 2 carries out continuous ion stream the square wave frequency signal modulation of setting duty ratio；
Step 3, by the step 2, treated that ion flows into that moving apparatus carries out Ion transfer separation；
Step 4 rebuilds ion mobility spectrometry using Chirp Z transform.
In the step 2, the square wave frequency signal modulation that duty ratio is 50% is carried out to continuous ion stream, modulation
The mode that mode is reduced using the raised mode of frequency or frequency, the method for frequency shift are linear frequency modulation, modulation range is 0~
10K Hz。
The neutral gas of setting pressure and flow velocity is passed through in the step 3, in moving apparatus, the neutral gas is nitrogen
Gas, helium or carbon dioxide.
Further include that treated includes the continuous ionic stream of ion mobility information directly through faraday by step 3
Disk detector detects, and is AD converted and obtains ion versus time curve or by interface importing to import computer
Mass spectrograph records the ionic strength versus time curve of different mass-to-charge ratioes.
Mathematical treatment is carried out to the change curve of record, the method specifically handled is：Using with square wave in the step 2
Frequency signal with mutually and reverse phase sinusoidal Chirp signals and square wave Chirp signals with from Faraday plate or it is mass spectrometric from
Sub- intensity variation curve is related respectively, carries out Chirp Z transform respectively to gained signal, and the result to converting twice compares
Compared with, filter out transformation generate ghost peak and noise.
In the step 1, before carrying out ionization processing to sample：Utilize capillary electric chromatogram, gas-chromatography, liquid
Phase chromatography or means of capillary electrophoresis carry out pre-separation to sample, or after dilution, enrichment, purifying, removal of impurities pretreatment directly
It connects and is imported into ion source with syringe pump.
The ionized mode of the step 1 includes electron spray, atmospheric pressure chemical ionization, atmospheric pressure photoionization, radioactive source
Ionization or Direct Analysis in Real Time ionization source.
Modulation is realized by following device in the step 2：B-N ion gates or TYNDALL ion gates.
It is a kind of using a kind of device of the method for detection trace compound, including ion source, the ion source face
The other end of the ion gate of migration tube one end, the migration tube is equipped with detector；The ion gate is equipped with ion door controller.
Further include the gas chromatograph being connect with the ion source, liquid chromatograph, capillary electrophoresis, ion chromatograph
Or supercritical fluid chromatograph.
Beneficial effects of the present invention：
1. high sensitivity.The utilization rate of ion can be increased to 50% by method provided by the invention, sensitive compared with conventional method
Degree improves 3~10 times, and compared with conventional Fourier transform, sensitivity can be improved 1-2 times.
2. high resolution.Method provided by the invention compared with conventional method can by common tailing peak, stick out one's tongue peak
Phenomena such as eliminate, to improve resolution ratio, and then improve mass spectrum database and quantitative effect.
3. simple.Method provided by the invention can may be used on existing ion directly or through seldom transformation and move
Move spectrometer, ion mobility spectrometry-mass spectrometer, gas-chromatography-ion mobility spectrometry combined instrument, liquid chromatogram-ion mobility spectrometry connection
With on instrument, and greatly improve its performance.
4. multidimensional detaches.Utilize method provided by the invention, it may be convenient to by ion mobility spectrometry-mass spectrometer and gas
Chromatography, liquid chromatograph, capillary electrophoresis, ion chromatograph, supercritical fluid chromatograph etc. are combined, and are not being damaged
The Ion transfer separation of extra dimension is provided in the case of the separating degree of eclipsed spectrum, mass spectrographic sensitivity, it is fixed to greatly improve
Property analysis and quantitative analysis efficiency and accuracy.
5. the temporal resolution of spectrogram is high.By adjusting relevant parameter, when Chirp Z transform can be made to concentrate on Ion transfer
Between position, to reach very high temporal resolution, and calculating speed is fast, can be reached using present mainstream computer
To real-time transform.
6. the ghost peak of Hadamard transformation and Fourier transformation generation is eliminated, to make chemical combination Physical Property Analysis and quantitative point
Analysis is more accurate.
Description of the drawings
Fig. 1 is one ion mobility spectrometry of embodiment-mass spectrometer schematic diagram；
Fig. 2 (a) is that conventional ion migrates spectrogram, and Fig. 2 (b) is Chirp Z transform ion transfer spectrogram；
Fig. 3 (a) is that conventional transformation method generates ghost peak at 3 times of transit times, and Fig. 3 (b), which is the method for the present invention, to be had
The ghost peak that effect removal transformation generates；
Fig. 4 is selection chromatography of ions figure of the present invention as gas chromatography detector；
Fig. 5 (a) is conventional Fourier transform ion mobility spectrometry, and Fig. 5 (b) is the Chirp Z transform ion mobility spectrometry of the present invention.
Wherein, 1. ion source, 2. high voltage power supplies, 3. ion door controllers, 4. ion gates, 5. migration gas entrances, 6. migrations
Pipe, 7. detectors.
Specific implementation mode
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
A method of detection trace compound is as follows：
(1) sample is ionized；The mode of the ionization includes electron spray, atmospheric pressure chemical ionization, atmospheric pressure
Photo-ionisation, radioactive source ionization or Direct Analysis in Real Time ionization source ionize continuous uninterrupted progress.According to the sample of analysis, electricity
From can be carried out in the positive-ion mode or under negative ion mode.
(2) frequency modulation(PFM), the method that raising frequency or frequency reducing may be used in frequency modulation(PFM), according to institute are carried out to continuous ion stream
When sampling rate, modulation period can select the noise needed between 200ms to 10s, and ion mobility spectrometry obtains frequency accordingly
Rate is 0.1~5Hz, can be adapted with the acquisition speed of HPLC or GC.The highest frequency of modulation is 10K Hz, lowest frequency
Rate is 0Hz.
(3) modulated ion stream is introduced under electric field action in moving apparatus and carries out ion isolation, the migration
Lead to the neutral gas of the antikinesis in fixation pressure, fixed flow rate in device, the neutral gas is nitrogen, helium or dioxy
Change carbon.
(4) by step (3) treated include ion mobility information continuous ionic flow through Faraday plate detection
Device detects, and digital signal is converted into after amplification, or import mass spectrograph by interface, records the ionic strength of variant mass-to-charge ratio
Versus time curve.
(5) frequency modulated signal, including square-wave signal and sinusoidal signal is related to the digital signal of (4) is come from, it is related
Phase it is identical as former square wave Chrip signals.Signal after correlation carries out multiplying window, and window function can be Welch functions, Hann
Window function, Gaussian function, Hamm window functions etc..
(6) signal after adding window is subjected to Chirp Z transform, and the signal after transformation is compared and is generated with filtering out transformation
Ghost peak, noise etc..
It (7) can be using the above Chirp Z transform ion mobility spectrometry as the detector of gas-chromatography or liquid chromatogram, to multiple
Miscellaneous system carries out two dimensional separation, and obtains the qualitative and quantitative informations such as retention time, the transit time of ion and intensity simultaneously.
(8) the above Chirp Z transform ion mobility spectrometry can be connected different types of mass detector, and connects gas-chromatography
Or liquid chromatogram, to carry out three-dimensional separation to complex system, and retention time, the transit time of ion, matter lotus are obtained simultaneously
When intensity etc. is qualitative and quantitative information.
Before carrying out ionization processing to sample：To complicated sample, capillary electric chromatogram, gas-chromatography, liquid are utilized
Phase chromatography or means of capillary electrophoresis carry out pre-separation to sample, or after dilution, enrichment, purifying, removal of impurities pretreatment directly
It connects and is imported into ion source with syringe pump.
Modulation is realized by following device in the step (2)：B-N ion gates, TYNDALL ion gates or other ion grid
Lattice.
As shown in Figure 1, using a kind of device of the method for detection trace compound：Include sequentially ion source 1, ion
Door 4, migration tube 6, detector 7, ion gate 4 are connect with ion door controller 3, and modulator approach makes the duty ratio of ion stream reach
50%, frequency raising can be used for warbled mode or frequency reduces or combination.Migration tube 6 is equipped with migration
Gas entrance 5, and migration tube 6 is connect with high voltage power supply 6.
Further include the gas chromatograph being connect with ion source 1, liquid chromatograph, capillary electrophoresis, ion chromatograph or
Supercritical fluid chromatograph, or pass through atmospheric pressure interface and mass spectrograph associated with ion mobility spectrometry phase.
Proteomics, metabolism group are being analyzed or detected to chromatography-ion mobility spectrometry and ion mobility spectrometry-mass spectrometer
Application and drugs, explosive, chemical warfare agent in, lipidomics, food security, natural products and environmental contaminants,
Application in the detections such as outburst surroundings accident.
Embodiment one
The structure of ionic migration spectrometer used in the present embodiment is as shown in Figure 1, ion mobility spectrometry is operated in atmospheric pressure
Under, ion source is63The temperature in Ni radiation ionizations source, ion mobility spectrometry is 150oC, and migration gas is nitrogen, and flow velocity is
900mL.min-1, the total length for moving pipe is referred to as 12.8 centimetres, is separated as two regions by a B-N type ion gate, front end be from
The areas Zi Hua, length are 2.8 centimetres, and rear end is migration area, and length is 10.2 centimetres.Migration area is followed by a Faraday plate detector.
The present invention can greatly improve the performance of spectrometric system, such as ion of traditional ionic migration spectrometer in 50ms
It migrates in spectrogram, to reach good separating effect, the opening time of ion gate is 0.25ms, then the utilization ratio of ion is：
0.25/50=0.5%
In the present embodiment：It is accounting for using B-N ion gates by warbled mode in the ion transfer spectrogram of 50ms
For sky than being 50%, the multiple of utilization ratio and raising from ion can see the present invention to ion mobility spectrometry-mass spectrometer
Role and its significant superiority.The present embodiment brings 2.4-lutidine into ion sources by carrier gas, and flow velocity is
300mL.min-1.
Extract the legacy migration spectrogram of 2,4-lutiddine and the Chirp Z transform of the present invention respectively according to the period of 50ms
Spectrogram, ion transfer spectrogram of the present invention proposes raising than conventional ion migration spectrogram signal-to-noise ratio it can be seen from Fig. 2 (a)-Fig. 2 (b)
5.27 times, while the phenomenon that eliminate baseline drift.
Fig. 3 (a) is the spectrogram without removing ghost peak, and Fig. 3 (b) is the spectrogram for eliminating ghost peak.The two can relatively understand
The display present invention superiority, you can to remove the interference ghost peak that is brought by transformation.
Fig. 4 is selection chromatography of ions figure of the present invention as gas chromatography detector.
Fig. 5 (b) is the Chirp Z transform spectrogram of the present invention, and Fig. 5 (a) is traditional Fourier transformation spectrogram, it can be seen that this hair
Bright spectrogram transit time is accurate, high resolution, and performance improves clearly compared with traditional spectrogram.
The present invention relates to from gas ion and neutral gas molecule are collided and according to the charge of gas ion, matter
Amount, collision cross-section are detached, and improve the control and measurement method of its resolution ratio and sensitivity.With usual ion mobility spectrometry
Measurement method unlike, this method to come from ion source continuous ion beam carry out frequency modulation(PFM), the duty ratio of modulation
It is 50%, then will be detached in electro-ionic osmosis to migration component.Ion after separation detects to obtain original by detector
Spectrogram, or enter mass spectrograph by interface and carry out quality analysis, and intensity and the measurement of each ion are obtained from mass spectrograph
Its ionic strength changes with time, and passes through mound after this spectrogram and square wave Chirp signals and sine wave Chirp signals are related respectively
General transform rebuilds ion mobility spectrometry, and filters out ghost peak and noise that transformation generates, obtains the transit time of each ion.The present invention
Easy to operate, the utilization ratio of ion is high, and the signal-to-noise ratio of quantitative analysis can be improved 3~10 times with common compared with quasi-instrument.
At the same time, the resolution ratio of ion mobility spectrometry also effectively improves, to help preferably to carry out qualitative point to compound
Analysis.The present invention can also be applied in existing ion mobility spectrometry-mass spectrometer, to improve the sensitivity and resolution of analysis
Rate.The invention is particularly suited to high performance liquid chromatography, ultra performance liquid chromatography, gas-chromatography, Capillary Electrophoresis, capillary electricity colors
Other separation means combinations such as spectrum make the effect of separation to increase a dimension in common analysis but not lose sensitivity
The accuracy of rate and qualitative analysis is greatly improved.
The purpose of the present invention is being to make full use of the ion beam from ion source, by electro-ionic osmosis more as possible to ion
It is detached in migration component.Meanwhile the ion after migration enters mass spectrograph by interface, and carried out according to the mass-to-charge ratio of ion
Analysis.It include ionic strength signal versus time curve in the signal that mass spectrograph obtains.Since ionic availability reaches
50%, the sensitivity of analysis greatly improves.At the same time, tailing peak is eliminated after Chirp Z transform and the peak that sticks out one's tongue etc. is existing
As so that the resolution ratio of ion mobility spectrometry is also improved, and is 500 or so for a mass-to-charge ratio in normal circumstances
The resolution ratio highest of ion, ion mobility spectrometry can reach 100 or more, to than existing method greatly improve separating capacity and
Sensitivity for analysis, analysis such as proteomics, metabolism group, lipidomics, food security, natural production for complex sample
The analysis of the samples such as object, environmental contaminants is most important.The invention is particularly suited to connect chromatography, ion mobility spectrometry and mass spectrum
Dimensional analytic system is constituted together.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (8)
1. a kind of method of detection trace compound, characterized in that including：
Step 1 ionizes sample；
Step 2 carries out continuous ion stream the square wave frequency signal modulation of setting duty ratio；
Step 3, by the step 2, treated that ion flows into that moving apparatus carries out Ion transfer separation；
Step 4 rebuilds ion mobility spectrometry using Chirp Z transform.
2. a kind of method of detection trace compound as described in claim 1, characterized in that in the step 2, to continuous
Ion stream carries out the square wave frequency signal modulation that duty ratio is 50%, and the mode of modulation is dropped using the raised mode of frequency or frequency
The method of low mode, frequency shift is linear frequency modulation, and modulation range is 0~10K Hz.
3. a kind of method of detection trace compound as described in claim 1, characterized in that in the step 3, moving apparatus
In be passed through setting pressure and flow velocity neutral gas, the neutral gas be nitrogen, helium or carbon dioxide.
4. a kind of method of detection trace compound as described in claim 1, characterized in that further include that treated by step 3
Include ion mobility information continuous ionic stream directly through Faraday plate detector detect, and be AD converted with import
Computer imports mass spectrograph by interface, records the ionic strength versus time curve of different mass-to-charge ratioes.
5. a kind of method of detection trace compound as claimed in claim 4, characterized in that the change curve of record into line number
Handle, and the method specifically handled is：Believe with the sinusoidal Chirp of phase and reverse phase using with square wave frequency signal in the step 2
Number and square wave Chirp signals to from Faraday plate or from matter instrument ionic strength change curve respectively it is related, to gained letter
Number Chirp Z transform is carried out respectively, and the result converted twice is compared, filter out ghost peak and noise that transformation generates.
6. a kind of method of detection trace compound as described in claim 1, characterized in that in the step 1, to sample
Before carrying out ionization processing：Using capillary electric chromatogram, gas-chromatography, liquid chromatogram or means of capillary electrophoresis to sample into
Row pre-separation, or directly imported into ion source with syringe pump after dilution, enrichment, purifying, removal of impurities pretreatment.
7. a kind of method of detection trace compound as described in claim 1, it is characterized in that：The ionized side of the step 1
Formula includes electron spray, atmospheric pressure chemical ionization, atmospheric pressure photoionization, radioactive source ionization or Direct Analysis in Real Time ionization source.
8. a kind of method of detection trace compound as described in claim 1, it is characterized in that：In the step 2 modulation by with
Lower device is realized：B-N ion gates or TYNDALL ion gates.
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| CN107219294B (en) * | 2017-05-05 | 2019-07-05 | 塔里木大学 | A method of improving ionic migration spectrometer resolution ratio and sensitivity |
| JP6781672B2 (en) * | 2017-06-21 | 2020-11-04 | 株式会社日立製作所 | Deposit inspection method |
| CN107478710A (en) * | 2017-09-14 | 2017-12-15 | 安徽理工大学 | One kind eliminates Hadamard ion mobility spectrometry baseline drift distortion methods |
| EP3710827A4 (en) * | 2017-11-15 | 2021-10-06 | Mécanique Analytique Inc. | Method and apparatus for analysing a gas chromatography elution peak |
| CN110108778B (en) * | 2019-04-19 | 2021-08-10 | 中国科学院合肥物质科学研究院 | UV-FAIMS quantitative detection method for volatile organic compounds |
| CN110146585B (en) * | 2019-06-22 | 2021-08-17 | 湘潭大学 | Method for predicting and eliminating Hadamard transform ion mobility spectrometry transform false peak |
| CN114388333B (en) * | 2022-01-13 | 2023-06-20 | 湘潭大学 | Method for improving signal-to-noise ratio of ion mobility spectrometer and ion mobility spectrometer |
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| Rapid profiling and identification of anthocyanins in fruits with Hadamard transform ion mobility mass spectrometry;Wenjie Liu et al.;《Food Chemistry》;20150110;第177卷;第225-232页 * |
| 多喷嘴电喷雾阵列离子源对离子迁移谱性能的影响;刘文杰 等;《分析化学》;20150531;第43卷(第5期);第789页2.1试剂与仪器，图1 * |
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