CN101789355B - Time-of-flight mass spectrometer with wide dynamic range, implementation method and application thereof - Google Patents
Time-of-flight mass spectrometer with wide dynamic range, implementation method and application thereof Download PDFInfo
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- CN101789355B CN101789355B CN2010101264009A CN201010126400A CN101789355B CN 101789355 B CN101789355 B CN 101789355B CN 2010101264009 A CN2010101264009 A CN 2010101264009A CN 201010126400 A CN201010126400 A CN 201010126400A CN 101789355 B CN101789355 B CN 101789355B
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Abstract
The invention provides a time-of-flight mass spectrometer with a wide dynamic range, which comprises an ion source, an ion extraction pulse electrode, an ion extraction lens, an orthogonal-injection time-of-flight mass spectrometer, an ion-selective repulsion electrode, an MCP ion detector, a high-speed data acquisition card and corresponding software. A method for increasing the dynamic range of detectable concentration, which is implemented by utilizing the instruments, includes the following steps that: a pulse voltage, i.e. ion extraction pulse, the pulse amplitude, duty ratio and frequency of which can be regulated, is applied on the ion extraction pulse electrode; a pulse voltage, i.e. ion-selective repulsion pulse, the delay, pulse width and amplitude of which can be regulated, is arranged on the ion-selective repulsion electrode of the orthogonal-injection time-of-flight mass spectrometer; and the ion extraction pulse and the ion-selective repulsion pulse are asynchronously applied. The instrument and the method increase the dynamic range of concentration detected by time-of-flight mass spectrometry to more than six orders of magnitude, and can be applied in cases needing to simultaneously detect greatly different concentrations of components in sample to be tested.
Description
Technical field
The present invention relates to the analytical instrument detection technique, particularly a kind of time-of-flight mass spectrometer of wide dynamic range and its implementation and application.
Background technology
Time-of-flight mass spectrometer (time-of-flight mass spectrometer, TOFMS) according to different ions in a vacuum the size of flight time judge its mass-to-charge ratio, analysis speed is fast, and can carry out the detection of single electric charge.The dynamic range that time-of-flight mass spectrometer is measured concentration is one of major parameter index of time-of-flight mass spectrometer.In practical application,, need measure some content difference usually simultaneously and surpass the above component of 6 one magnitude because the component in the sample is very complicated; Yet because time-of-flight mass spectrometer adopts the method for ion counting, (time-to-digitalconverter TDC) carries out data acquisition for example to use time-digital quantizer; And TDC is because the existence in dead time can not measure two ions that mass-to-charge ratio is identical simultaneously in same sense cycle; Therefore for the big component of concentration; When a plurality of ions in the very short time (for example 2ns) when arriving detector simultaneously, detector possibly think to have only an ion, this just causes the error of very big measurement.How when detecting single ion, can obtain the information of a plurality of ions again, be time-of-flight mass spectrometer major issue anxious to be solved.The at present existing several kinds of methods that improve ion detection efficient dynamic ranges all can increase the cost of instrument, increase the complexity of instrument.
Summary of the invention
The shortcoming that the objective of the invention is to overcome prior art provides a kind of simple in structure, realization convenience, lower-cost time-of-flight mass spectrometer with wide dynamic range with not enough.
Another object of the present invention is to provide the implementation method of the time-of-flight mass spectrometer of above-mentioned wide dynamic range.
A purpose more of the present invention is to provide the application of the time-of-flight mass spectrometer of above-mentioned wide dynamic range.
The object of the invention is realized through following technical proposals: a kind of time-of-flight mass spectrometer of wide dynamic range; Comprise that ion source, ion are drawn pulsed electrode, ion extraction lens, vertically introduction-type flying time mass spectrum analysis device, ion are selected repulsion electrode, MCP (Microchannel Plate) ion detector, high-speed data acquisition card and corresponding software; Said ion source is arranged at the front end that ion is drawn pulsed electrode; Said ion is drawn the front end that pulsed electrode is arranged at the ion extraction lens; The rear end of ion extraction lens is oppositely arranged with vertical introduction-type flying time mass spectrum analysis device; In vertical introduction-type flying time mass spectrum analysis device, ion is set and selects repulsion electrode and MCP ion detector; High-speed data acquisition card is used to gather ion detection signal, is arranged at the relative position of outlet with vertical introduction-type flying time mass spectrum analysis device intermediate ion passage.
Said ion source can be any ion source, comprises the electrospray ionization source under the electron bombardment ionization source that can produce ion continuously, chemical ionization source, glow discharge ion source, the atmospheric pressure, or the ion source of pulsed, like laser ionization source etc.
Said ion is drawn pulsed electrode, and the ion that ion source is produced obtains kinetic energy down at this to the electrode effect, and this has determined that to electrode institute making alive amplitude the kinetic energy of ion is big or small; Said ion is drawn pulsed electrode can be different to different ion source forms.
Said ion extraction lens is conventional electrostatic lens.
Said vertical introduction-type flying time mass spectrum analysis device can be conventional vertical introduction-type flying time mass spectrum analysis device; Ion selects repulsion electrode and MCP ion detector to be arranged at wherein.
Said MCP ion detector is the ion detector that conventional biplate MCP forms.
Described high-speed data acquisition card be TDC or high speed analogue-to-digital converters (Analog-Digital Converter, ADC).
Utilize the method for the raising detectable concentration dynamic range that the time-of-flight mass spectrometer of above-mentioned wide dynamic range realizes to comprise the steps:
(1) draw at ion and apply pulse amplitude, the duty pulse voltage of frequency adjustable when on the pulsed electrode, promptly ion is drawn pulse.The size of pulse voltage amplitude has determined ion concentration kinetic energy, has also just determined to be produced in the ion of MCP ion detector detection and the ion source at last the ratio of ion; Pulse duty factor determines two kinds of differences to draw the time scale that the kinetic energy pattern is applied, i.e. detection time of variable concentrations component ions, be used to regulate the dynamic range width of instrument; Pulse frequency is adjustable continuously from 0.1Hz~1KHz.
(2) ion in vertical introduction-type flying time mass spectrum analysis device selects to apply on the repulsion electrode pulse voltage of delay, pulsewidth and adjustable amplitude value, and promptly ion is selected the repulsion pulse.When this pulse applies and the analyzer modulating pulse have certain delay, the delay of this pulse what and pulsewidth and amplitude size depend on the mass-to-charge ratio and the flying speed of the ion of required repulsion removal.
(3) the described ion of step (1) is drawn the described ion of pulse and step (2) to select the repulsion pulse is asynchronous applying.
Said step (3) specifically can be:
When the ion concentration scope difference that (3-1) generates when while ionization was big, instrument was drawn the hocket detection of high and low density component ion of pulse duty factor according to ion.When being in detection low concentration group segregant pattern; Draw at ion and to apply low level in the pulse; Ion obtains lower kinetic energy, makes ion flight path in the flying time mass spectrum analysis device all drop on the MCP ion detector, at this moment just; Ion in the flying time mass spectrum analysis device is selected will apply pulse voltage on the repulsion electrode, and the repulsion of high concentration component ions selectivity is gone out the MCP ion detector.
(3-2) when being in detection high concentration component ions pattern; Draw at ion and to apply high level on the pulsed electrode; Ion obtains higher kinetic energy, and the ion in the flying time mass spectrum analysis device is selected not apply pulse voltage on the repulsion electrode, makes the flight path of ion in the flying time mass spectrum analysis device depart from the MCP ion detector; Have only a certain proportion of ion to arrive the MCP ion detector and be able to detect, prevent that MCP is saturated.This ion draws that pulse voltage amplitude is big more, and detected ion percentage is more little, and pulse duty factor is more little, and it is few more to detect high concentration component ions institute's time spent.
Time-of-flight mass spectrometer of this wide dynamic range and the method that improves the detectable concentration dynamic range thereof can be promoted to from 100% to 0.0001% with the time-of-flight mass spectrometer dynamic range more than 6 one magnitude; Can be applied to each bigger component of concentration difference in the testing sample needs the occasion that detects simultaneously, like the detection of organic micro-pollutant in the atmosphere etc.
Action principle of the present invention is: ion draws pulse and ion selection repulsion pulse is asynchronous applying.When detecting the low concentration group segregant; Ion is drawn and is applied low level in the pulse; Ion obtains lower kinetic energy, makes ion flight path in the flying time mass spectrum analysis device all drop on the MCP ion detector, at this moment just; Ion in the flying time mass spectrum analysis device is selected will apply pulse voltage on the repulsion electrode, and the repulsion of high concentration component ions selectivity is gone out the MCP ion detector.When detecting the high concentration component ions; Draw at ion and to apply high level on the pulsed electrode; Ion obtains higher kinetic energy, and the ion in the flying time mass spectrum analysis device is selected not apply pulse voltage on the repulsion electrode, makes the flight path of ion in the flying time mass spectrum analysis device depart from the MCP ion detector; Have only a certain proportion of ion to arrive the MCP ion detector and be able to detect, prevent that MCP is saturated.This ion draws that pulse voltage amplitude is big more, and detected ion percentage is more little, and pulse duty factor is more little, and it is few more to detect high concentration component ions institute's time spent.
The present invention has following advantage and effect with respect to prior art:
(1) to draw pulse amplitude according to ion adjustable continuously for ion concentration kinetic energy, as long as be the ratio that the scalable ion arrives the MCP ion detector through regulating ion concentration kinetic energy, adapts to the detection requirement of Different Dynamic scope.
(2) can draw pulse duty factor according to ion and realize continuous adjustable realization the detection time of different component ion.
(3) owing to regulate the parameter minimizing, MCP ion detector, anode and high-speed data acquisition card need not be made complicated multi-channel mode, have greatly reduced cost.
(4) reduced the quantity that big component ions finally arrives the MCP ion detector, avoided the generation of MCP ion detector saturation condition, prevented high-speed data acquisition card, as time-restriction in digital quantizer TDC dead time, improve the quantitative accuracy of instrument.
Description of drawings
Fig. 1 is apparatus structure of the present invention and schematic diagram.
Fig. 2 is pulse sequence figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but execution mode of the present invention is not limited thereto.
Embodiment
Fig. 1 shows principle of the present invention and structure.Visible by Fig. 1, this device comprises electron impact ion source, ion extraction lens, vertical introduction-type flying time mass spectrum analysis device three parts.
Described electron impact ion source comprises: bombardment electron beam 1, ion are drawn pulsed electrode 2, ion is drawn aperture plate 3 and formed.
Described ion extraction lens 5 is conventional electrostatic lens, and the ion 4 that electron impact ion source is produced is incorporated into vertical introduction-type flying time mass spectrum analysis device.
Described vertical introduction-type flying time mass spectrum analysis device is to add ion in the conventional vertical introduction-type flying time mass spectrum analysis device to select repulsion electrode 11.
Described vertical introduction-type flying time mass spectrum analysis device by: vertically introduce repulsion electrode 6, ion collector 7, accelerating region 8, field-free flight district 9, echo area 10, ion and select repulsion electrode 11 and MCP ion detector 13 to form.
Described ion is selected repulsion electrode 11 to be but not only can is two parallel poles.
The ion 4 that electron gun emitting electrons 1 bombarding gas molecule produces is drawn at ion under the effect of pulsed electrode 2 and is obtained certain kinetic energy, and is incorporated in the vertical introduction-type flying time mass spectrum analysis device by ion extraction lens 5 continuously.
In vertical introduction-type flying time mass spectrum analysis device; The vertical pulse voltage (frequency is generally greater than 10000 hertz) of introducing repulsion electrode 6 is introduced accelerating region 8 with ion and is picked up counting; Ion quickens the back and gets into field-free flight district 9, and 10 reflections are detected by MCP ion detector 13 at last through the echo area.
When detecting the low concentration group timesharing, ion as shown in Figure 2 is drawn pulses low district 17, and ion is drawn 2 making alives of pulsed electrode makes ion in the flight time, all arrive MCP ion detector 13 just, shown in Fig. 1 intermediate ion flight path 14.At this moment, make the MCP state that reaches capacity, need select to apply pulse voltage on the repulsion electrode 11, when high component ions arrives this electrode, pushed away track, absorbed by the instrument wall at ion in order to prevent the high concentration component ions.
When detecting the high concentration component; Ion as shown in Figure 2 is drawn pulse high level district 18; Ion is drawn pulsed electrode 2 and is attend institute's making alive and will make all ions have higher horizontal kinetic energy; Its ion flight track consequently have only the ion arrival MCP ion detector 13 of certain percentage to be able to detect, and other ions is absorbed shown in the curve among Fig. 1 15 by the instrument wall.In this process, select repulsion electrode 11 not apply pulse voltage.
Concrete application example:
, be 60mg/m for example to the limit value that has toluene in the pollutant sources Air Pollutant Emission source now according to national discharge standard of air pollutants (GB16297-1996) regulation
3Be equivalent in the gas that with the air is background, to detect the small component of 14.6ppm.The concentration of component ratio difference 78%:14.6ppm of nitrogen and toluene reaches and is about 50000 times.That is: in per 50000 nitrogen molecules 1 toluene molecule is arranged.
We know from the standard electronic bombardment source fingerprint of toluene, and its characteristic peak mass-to-charge ratio is 91 and 92.To this situation, when needs detect the toluene gas of low concentration, can in the ion flight process, utilize ion to select repulsion electrode 11, mass-to-charge ratio all ions in 17~44 scopes are pushed away track.
When detecting high concentration gases such as nitrogen, oxygen, argon gas, carbon dioxide simultaneously when needs; Draw pulsed electrode 2 at ion and apply high voltage; Duty ratio is about 1: 100, makes to have only part ion to arrive MCP ion detector 13, thereby has avoided the saturated of MCP ion detector 13.
The foregoing description is a preferred implementation of the present invention; But execution mode of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the time-of-flight mass spectrometer of a wide dynamic range; It is characterized in that: comprise that ion source, ion are drawn pulsed electrode, ion extraction lens, vertically introduction-type flying time mass spectrum analysis device, ion are selected repulsion electrode, MCP ion detector, high-speed data acquisition card and corresponding software; Said ion source is arranged at the front end that ion is drawn pulsed electrode; Said ion is drawn the front end that pulsed electrode is arranged at the ion extraction lens; The rear end of ion extraction lens is oppositely arranged with vertical introduction-type flying time mass spectrum analysis device; In vertical introduction-type flying time mass spectrum analysis device, ion is set and selects repulsion electrode and MCP ion detector, high-speed data acquisition card is used to gather ion detection signal, is arranged at the relative position of outlet with vertical introduction-type flying time mass spectrum analysis device intermediate ion passage.
2. the time-of-flight mass spectrometer of wide dynamic range according to claim 1; It is characterized in that: said ion source comprises the electrospray ionization source under the electron bombardment ionization source that can produce ion continuously, chemical ionization source, glow discharge ion source, the atmospheric pressure, or the ion source of pulsed.
3. the time-of-flight mass spectrometer of wide dynamic range according to claim 1; It is characterized in that: said ion is drawn pulsed electrode; The ion that ion source is produced obtains kinetic energy down at this to the electrode effect, this kinetic energy to electrode institute making alive amplitude decision ion is big or small; It is different to different ion source forms that said ion is drawn pulsed electrode.
4. the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: said ion extraction lens is conventional electrostatic lens; Said MCP ion detector is the ion detector that conventional biplate MCP forms.
5. the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: said vertical introduction-type flying time mass spectrum analysis device is conventional vertical introduction-type flying time mass spectrum analysis device; Ion selects repulsion electrode and MCP ion detector to be arranged at wherein.
6. the time-of-flight mass spectrometer of wide dynamic range according to claim 1, it is characterized in that: described high-speed data acquisition card is TDC or high speed analogue-to-digital converters.
7. the method for the raising detectable concentration dynamic range that realizes of a time-of-flight mass spectrometer that utilizes the described wide dynamic range of claim 1 is characterized in that comprising the steps:
(1) draw at ion and apply pulse amplitude, the duty pulse voltage of frequency adjustable when on the pulsed electrode, promptly ion is drawn pulse; The size of pulse voltage amplitude has determined ion concentration kinetic energy, has also just determined to be produced in the ion of MCP ion detector detection and the ion source at last the ratio of ion; Pulse duty factor determines two kinds of differences to draw the time scale that the kinetic energy pattern is applied, i.e. detection time of variable concentrations component ions, be used to regulate the dynamic range width of instrument;
(2) ion in vertical introduction-type flying time mass spectrum analysis device selects to apply on the repulsion electrode pulse voltage of delay, pulsewidth and adjustable amplitude value, and promptly ion is selected the repulsion pulse; When this pulse applies and the analyzer modulating pulse have certain delay, the delay of this pulse what and pulsewidth and amplitude size depend on the mass-to-charge ratio and the flying speed of the ion of required repulsion removal;
(3) the described ion of step (1) is drawn the described ion of pulse and step (2) to select the repulsion pulse is asynchronous applying;
Said step (3) is specially:
When the ion concentration scope difference that (3-1) generates when while ionization was big, instrument was drawn the hocket detection of high and low density component ion of pulse duty factor according to ion; When being in detection low concentration group segregant pattern; Draw at ion and to apply low level in the pulse; Ion obtains lower kinetic energy, makes ion flight path in the flying time mass spectrum analysis device all drop on the MCP ion detector, at this moment just; Ion in the flying time mass spectrum analysis device is selected will apply pulse voltage on the repulsion electrode, and the repulsion of high concentration component ions selectivity is gone out the MCP ion detector;
(3-2) when being in detection high concentration component ions pattern; Draw at ion and to apply high level on the pulsed electrode; Ion obtains higher kinetic energy, and the ion in the flying time mass spectrum analysis device is selected not apply pulse voltage on the repulsion electrode, makes the flight path of ion in the flying time mass spectrum analysis device depart from the MCP ion detector; Have only a certain proportion of ion to arrive the MCP ion detector and be able to detect, prevent that MCP is saturated; This ion draws that pulse voltage amplitude is big more, and detected ion percentage is more little, and pulse duty factor is more little, and it is few more to detect high concentration component ions institute's time spent.
8. method according to claim 7 is characterized in that: it is adjustable continuously from 0.1Hz~1KHz that the described ion of step (1) is drawn the frequency of pulse.
9. the application of the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: be applied to the occasion that the concentration difference is bigger in the testing sample each component needs detect simultaneously.
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CN112525980B (en) * | 2020-11-26 | 2022-09-06 | 厦门大学 | Mass spectrometry detection method for melamine in dairy products |
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Address after: 510000, A3 building, No. 11, Kaiyuan Avenue, Science City, Guangzhou hi tech Industrial Development Zone, Guangdong, Guangzhou, third Patentee after: Guangzhou Hexin Instruments Co., Ltd. Patentee after: Shanghai University Address before: The city on 510663 Guangzhou Road, No. 80 Guangdong province science and technology innovation base F/301 Patentee before: Guangzhou Hexin Analytical Instrument Co., Ltd. Patentee before: Shanghai University |