CN105789019A - Delayed ion extraction module applicable to time-of-flight mass spectrometer - Google Patents
Delayed ion extraction module applicable to time-of-flight mass spectrometer Download PDFInfo
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- CN105789019A CN105789019A CN201610339197.0A CN201610339197A CN105789019A CN 105789019 A CN105789019 A CN 105789019A CN 201610339197 A CN201610339197 A CN 201610339197A CN 105789019 A CN105789019 A CN 105789019A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/022—Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
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Abstract
The invention discloses a delayed ion extraction module applicable to a time-of-flight mass spectrometer. The delayed ion extraction module comprises a signal capturing circuit for receiving a synchronous signal of a laser device; an output end of the signal capturing circuit is connected with a signal input end of a signal widening circuit; the output end of the signal widening circuit is connected with the signal input end of a signal delaying circuit; and the output end of the signal delaying circuit is composed of a first triggering signal output end and a second triggering signal output end. The delayed ion extraction module has the advantages that the circuit design is ingenious; when the synchronous signal of the laser device is accurately captured in real time, the synchronous signal with the pulse width of 5ns is widened into standard square wave pulse of 7us; and the intrinsic delay of a circuit is only 38ns, and can be adjusted in a delaying time range of 50-1200ns, so that the requirements on triggering signals of a high-speed acquisition card and a high-voltage pulse module are met. The ion transmission capability is improved to the greatest extent, and the sensitivity and the resolution ratio of a mass spectrum system are effectively improved; and the manufacturing cost can be reduced very well.
Description
Technical field
The present invention relates to time of-flight mass spectrometer, especially relate to be suitable to the delayed ion extraction module of time of-flight mass spectrometer.
Background technology
MALDI-TOFMS(Matrix Assisted Laser Desorption ionization time-of-flight mass spectrometer) mass spectrometer system is a kind of novel soft ionization biological mass spectrometry, instrument is mainly made up of two parts: Matrix Assisted Laser Desorption ionization ion source (MALDI) and time of flight mass analyzer (TOF).The principle of MALDI is to irradiate sample and substrate formed cocrystallization thin film with laser, and substrate absorbs energy from laser and passes to biomolecule；Biomolecule forms fragment after obtaining energy and flies out, and it is a kind of Soft ionization techniques, it is adaptable to mixture and the mensuration of biomacromolecule.The principle of TOF is that ion accelerates to fly over tof tube under electric field action, is detected according to the flight time difference arriving detector, and the mass-to-charge ratio (M/Z) i.e. measuring ion was directly proportional to the flight time of ion.
MALDI-TOF-MS instrument is that the ion allowing laser desorption ionize flies out, although laser ion source is a class surface ionization source, but actually desorption ionization is to produce during fast laser pulse a bit, some is then to be produced by collision in flight course after parsing, this space that also result in ion and the further dispersion of energy.Additionally, the neutral particle of laser desorption ionization or ion are angle stragging in a vacuum, this is also a source of spatial dispersion.If being added without ion to postpone lead-out process, different time is formed, the ion of different initial velocity, distance away from extraction electrode is different, suffered field intensity is the most different, so ion could not realize same off time, same off energy, thus the ion causing mass-to-charge ratio identical is flown to detector with different time and is affected resolution.Introducing ion in a mass spectrometer and postpone lead-out process, the ion allowing laser desorption ionize results between two pole plates added with identical high pressure, through time delay after a while, then applies rapidly electric field by Ion Extraction.The ion that different time is formed will be placed on the same off time, it will makes to fly to extraction pole at faster speed apart from remote ion, thus reaches the effect that different initial velocity ion is drawn simultaneously, improves mass spectrograph resolution.
Existing design time delay scheme, is the seizure being carried out Laser synchronisation signal by microprocessor, exports to high-voltage pulse module and capture card after microprocessor count time delay.Owing to microprocessor works based on crystal oscillator frequency, and the time that laser pulse arrives is random, so the time error capturing pulse is a crystal oscillator cycle.Therefore to reach the error within degree of stability ± 200ps, crystal oscillator frequency more than 2.5GHz to be reached in theory, it is contemplated that the error of crystal oscillator self, crystal oscillator frequency requires higher, and general processor is difficult to reach this frequency.The actual demand of degree of stability ± 200ps can not be met, had a strong impact on ion transmission and mass spectrograph sensitivity.
Summary of the invention
Present invention aim at providing a kind of delayed ion extraction module being suitable to time of-flight mass spectrometer.
For achieving the above object, the present invention takes following technical proposals:
The delayed ion extraction module being suitable to time of-flight mass spectrometer of the present invention, including the signal capture circuit for receiving Laser synchronisation signal, the outfan of described signal capture circuit is connected with the signal input part of signal broadening circuit, the described outfan of signal broadening circuit is connected with the signal input part of signal delay circuit, and the outfan of described signal delay circuit is triggered signal output part by first and the second triggering signal output part forms；
Described signal capture circuit is made up of audion Q1 and schmitt inverter U1；Described audion Q1 base stage is connected with Laser synchronisation signal output part through resistance R1, audion Q1 grounded emitter, and audion Q1 colelctor electrode one tunnel connects positive source through resistance R2, and another road is connected with the signal input part of described schmitt inverter U1；
Described signal broadening circuit is made up of two monostable flipflops U2A, U2B and d type flip flop U3；The input end of clock CLK of described d type flip flop U3 is connected with the signal output part of described schmitt inverter U1；The inverse output terminal of d type flip flop U3, data input pin D are connected with each other；The just triggering input B of d type flip flop U3 forward outfan Q and described monostable flipflop U2A is connected；Two monostable flipflops U2A, U2B constitute double monostable flipflop；Two monostable flipflops U2A, U2B are with two monostable flipflops within a piece of couple of monostable flipflop DM74HC221N；
The removing termination high level VCC of monostable flipflop U2A, the negative input A that triggers connects low level GND, external capacitor end Cext meets high level VCC by electric capacity C1, resistance R3, outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R3, and the negative triggering input A of positive pulse outfan Q and monostable flipflop U2B is connected；
The just triggering input B of monostable flipflop U2B and removing end all meet high level VCC, and negative pulse outfan is connected with the reset terminal CLR of d type flip flop U3；The external capacitor end Cext of monostable flipflop U2B meets high level VCC by electric capacity C2, resistance R4, and outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R4；
Described signal delay circuit is made up of with door U5A, U5B programmable time chip and two；The serial programming of described programmable time chip selects termination high level, selects serial mode, and output mode selects end MS to connect low level, it may be assumed that output signal is identical with input signal polarity；The signal input part IN of programmable time chip is connected with the just triggering input B of monostable flipflop U2A in described signal broadening circuit；The signal output part OUT of programmable time chip is connected with first input end with door U5A, U5B described in two respectively, and two all meet high level VCC with second input of door U5A, U5B.
The invention has the advantages that circuit design is ingenious, while the most accurately catching Laser synchronisation signal, by the standard block pulse that synchronizing signal broadening is 7us of 5ns pulsewidth, circuit inherent delay only has 38ns, in the range of the delay time of 50-1200ns adjustable, and degree of stability controls, within ± 200ps, to meet the triggering semaphore request of high-speed collection card and high-voltage pulse module.Improve ion transport capability to greatest extent, be effectively improved sensitivity and the resolution of mass spectrometer system, and can preferably reduce cost of manufacture.
Accompanying drawing explanation
Fig. 1 is the circuit structure block diagram of the present invention.
Fig. 2 is the circuit theory diagrams of the present invention.
Fig. 3 is the principle schematic that the present invention is applied to time of-flight mass spectrometer.
Detailed description of the invention
As Figure 1-3, the delayed ion extraction module being suitable to time of-flight mass spectrometer of the present invention, including the signal capture circuit for receiving Laser synchronisation signal, the outfan of described signal capture circuit is connected with the signal input part of signal broadening circuit, the described outfan of signal broadening circuit is connected with the signal input part of signal delay circuit, and the outfan of described signal delay circuit is triggered signal output part by first and the second triggering signal output part forms；
Described signal capture circuit is made up of audion Q1 and schmitt inverter U1；Described audion Q1 (model: S9013) base stage is connected with Laser synchronisation signal output part through resistance R1, audion Q1 grounded emitter, audion Q1 colelctor electrode one tunnel connects positive source through resistance R2, and another road is connected with the signal input part of described schmitt inverter U1.
Laser synchronisation signal waveform is the irregular waveform of 5ns pulsewidth, and afterbody is with vibration, therefore signal capture circuit requirement can the most accurately catch waveform, and is not disturbed by follow-up oscillator signal.As in figure 2 it is shown, when synchronizing signal inputs from adapter J1, carry out level upset through audion Q1, the level after upset is again through schmitt inverter U1(model: SN74LS14) again overturn.Synchronizing signal is through the junction voltage thresholding of audion Q1, schmitt inverter U1(model: SN74LS14) hysteresis upset, noise in synchronizing signal and oscillator signal will filter, accurately capture rising edge.Resistance R1 plays current-limiting function, and resistance R2 has pull-up and two functions of current limliting.Laser synchronisation signal overturns through twice level, and the level direction of output signal Signal_IN still keeps consistent with input signal.Owing to schmitt inverter U1 supply voltage is+5V, so the level magnitude of output signal Signal_IN is+5V.
Described signal broadening circuit is made up of two monostable flipflops U2A, U2B and d type flip flop U3；The input end of clock CLK of described d type flip flop U3 is connected with the signal output part of described schmitt inverter U1；The inverse output terminal of d type flip flop U3, data input pin D are connected with each other；The just triggering input B of d type flip flop U3 forward outfan Q and described monostable flipflop U2A is connected；Two monostable flipflops U2A, U2B are with two monostable flipflops within a piece of couple of monostable flipflop DM74HC221N；
The removing termination high level VCC of monostable flipflop U2A, the negative input A that triggers connects low level GND, external capacitor end Cext meets high level VCC by electric capacity C1, resistance R3, outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R3, and the negative triggering input A of positive pulse outfan Q and monostable flipflop U2B is connected；
The just triggering input B of monostable flipflop U2B and removing end all meet high level VCC, and negative pulse outfan is connected with the reset terminal CLR of d type flip flop U3；The external capacitor end Cext of monostable flipflop U2B meets high level VCC by electric capacity C2, resistance R4, and outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R4；
Signal capture circuit output signal Signal_IN rising edge arrives by d type flip flop U3(model: MM74HC74AJ) after the level reverse circuit built, the signal Signal_MID of d type flip flop U3 forward outfan Q output is risen to high level by low level, i.e. rising edge.Signal capture circuit output signal Signal_IN accesses the input end of clock CLK (3 foot) of d type flip flop U3；The inverse output terminal (6 foot) of d type flip flop U3 is connected with data input pin D (2 foot)；D type flip flop U3 forward outfan Q (5 foot) by signal Signal_MID send into monostable flipflop U2A(model: DM74HC221N) just triggering input B (2 foot).
When the rising edge of the signal Signal_MID of d type flip flop U3 forward outfan Q output arrives, i.e. when signal capture circuit output signal Signal_IN rising edge arrives, the positive pulse outfan Q(13 foot of monostable flipflop U2A) export a standard block pulse Pulses1, this standard block pulse Pulses1 width is 7us, 7us is calculated by electric capacity C1 and resistance R3 parameter, 7us=7000ns=0.7 × C1 × R3=0.7 × 1000pF × 10K Ω.
When the trailing edge of standard block pulse Pulses1 signal arrives, i.e. when after signal capture circuit output signal Signal_IN rising edge arrival 7us, the negative pulse outfan (12 foot) of monostable flipflop U2B exports drop-down pulse Pulses2, pulse width is 7us, and computational methods are identical with monostable flipflop U2A.
When the trailing edge of drop-down pulse Pulses2 signal arrives, i.e. when, after signal Signal_IN and signal Signal_MID rising edge arrival 7us, output signal Signal_MID of d type flip flop U3 is pulled into low level from high level.Owing to the supply voltage of two monostable flipflops U2A, U2B and d type flip flop U3 is+5V, so all above signal level amplitude is+5V.Therefore, functional analysis according to logic circuit above, when Laser synchronisation signal arrives, signal broadening circuit can produce the square-wave pulse signal Signal_MID of pulsewidth 7us, amplitude+5V, and Laser synchronisation signal is 38ns with the inherent delay of square-wave pulse signal Signal_MID.
Described signal delay circuit is made up of with door U5A, U5B programmable time chip and two；The serial programming of described programmable time chip selects termination high level, selects serial mode, and output mode selects end MS to connect low level, it may be assumed that output signal is identical with input signal polarity；The signal input part IN of programmable time chip is connected with the just triggering input B of monostable flipflop U2A in described signal broadening circuit；The signal output part OUT of programmable time chip is connected with first input end with door U5A, U5B described in two respectively, and two all meet high level VCC with second input of door U5A, U5B.
Being analyzed above and understand, after the present invention receives the arrival of Laser synchronisation signal, signal broadening circuit can produce the square-wave pulse signal Signal_MID of pulsewidth 7us, amplitude+5V.
In order to realize designing requirement, programmable time chip selects 8 programmable time chips (DS1023S-500+) that Maxim Integrated company produces, its maximum delay time is that 1275ns is controlled, control step-length 5ns, highest frequency 10MHz, fully meets the 50-1200ns required by this delayed ion extraction module, degree of stability to control in ± 200ps, the parameter request of the highest 200Hz of frequency.End (14 foot) is selected to connect high level the serial programming of programmable time chip (DS1023S-500+), select serial mode, output mode selects end MS (11 foot) to connect low level, that is: output signal is identical with input signal polarity, end LE (2 foot) can be made by input latch, serial clock input CLK/P1 (4 foot), serial data input D/P2 (5 foot) carries out delay time configuration, after having configured delay time, square-wave pulse signal Signal_MID signal enters the signal input part IN of programmable time chip, through signal output part OUT(15 foot after time delay) output same waveform Signal3.In order to meet follow-up high-speed collection card and the demand of high-voltage pulse module drive ability, two and door U5A, U5B(model: SN74HC08D connected below at signal Signa3), then trigger signal 2 through adapter J2, J3 output the first triggering signal and second.
Claims (1)
1. the delayed ion extraction module being suitable to time of-flight mass spectrometer, including the signal capture circuit for receiving Laser synchronisation signal, the outfan of described signal capture circuit is connected with the signal input part of signal broadening circuit, the described outfan of signal broadening circuit is connected with the signal input part of signal delay circuit, and the outfan of described signal delay circuit is triggered signal output part by first and the second triggering signal output part forms；It is characterized in that:
Described signal capture circuit is made up of audion Q1 and schmitt inverter；Described audion Q1 base stage is connected with Laser synchronisation signal output part through resistance R1, audion Q1 grounded emitter, and audion Q1 colelctor electrode one tunnel connects positive source through resistance R2, and another road is connected with the signal input part of described schmitt inverter；
Described signal broadening circuit is made up of two monostable flipflops U2A, U2B and d type flip flop U3；The input end of clock CLK of described d type flip flop U3 is connected with the signal output part of described schmitt inverter；The inverse output terminal of d type flip flop U3, data input pin D are connected with each other；The just triggering input B of d type flip flop U3 forward outfan Q and described monostable flipflop U2A is connected；
The removing termination high level VCC of monostable flipflop U2A, the negative input A that triggers connects low level GND, external capacitor end Cext meets high level VCC by electric capacity C1, resistance R3, outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R3, and the negative triggering input A of positive pulse outfan Q and monostable flipflop U2B is connected；
The just triggering input B of monostable flipflop U2B and removing end all meet high level VCC, and negative pulse outfan is connected with the reset terminal CLR of d type flip flop U3；The external capacitor end Cext of monostable flipflop U2B meets high level VCC by electric capacity C2, resistance R4, and outer meeting resistance/capacitance terminal Rext/Cext is connected with the cold end of described resistance R4；
Described signal delay circuit is made up of with door U5A, U5B programmable time chip and two；The serial programming of described programmable time chip selects termination high level, selects serial mode, and output mode selects end MS to connect low level, it may be assumed that output signal is identical with input signal polarity；The signal input part IN of programmable time chip is connected with the just triggering input B of monostable flipflop U2A in described signal broadening circuit；The signal output part OUT of programmable time chip is connected with first input end with door U5A, U5B described in two respectively, and two all meet high level VCC with second input of door U5A, U5B.
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Cited By (4)
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| CN107464738A (en) * | 2017-09-19 | 2017-12-12 | 珠海美华医疗科技有限公司 | A kind of high pressure coupled pulse generator and time of-flight mass spectrometer |
| CN109765779A (en) * | 2019-01-14 | 2019-05-17 | 上海联影医疗科技有限公司 | Time delay correction method, device, computer equipment and storage medium |
| CN113013016A (en) * | 2021-03-22 | 2021-06-22 | 浙江迪谱诊断技术有限公司 | PIE controller circuit of time-of-flight nucleic acid mass spectrometer and control method thereof |
| CN115799037A (en) * | 2023-02-08 | 2023-03-14 | 中国科学院苏州生物医学工程技术研究所 | Time delay circuit for time-of-flight mass spectrum |
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