CN105609401B - A kind of method and system for improving time-of-flight mass spectrometer dynamic detection range - Google Patents

A kind of method and system for improving time-of-flight mass spectrometer dynamic detection range Download PDF

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CN105609401B
CN105609401B CN201610089824.XA CN201610089824A CN105609401B CN 105609401 B CN105609401 B CN 105609401B CN 201610089824 A CN201610089824 A CN 201610089824A CN 105609401 B CN105609401 B CN 105609401B
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signal
range
ion
input channel
signal input
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CN105609401A (en
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谭国斌
麦泽彬
陈彦锐
侯志辉
蔡伟光
洪义
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Guangzhou Hexin Instrument Co Ltd
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GUANGZHOU HEXIN ANALYTICAL INSTRUMENT CO Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/26Mass spectrometers or separator tubes
    • H01J49/34Dynamic spectrometers
    • H01J49/40Time-of-flight spectrometers

Abstract

The invention discloses a kind of method and system for improving time-of-flight mass spectrometer dynamic detection range, method includes:Material molecule is ionized into by ion by the ion gun of ionisation chamber;Ion is transferred into accelerating region by ion transmission range;Ion is entered into MCP ion detectors by accelerating region;MCP ion detectors input power dispenser in electrical signal form, the power divider will be exported to high-speed data acquisition card after the signal segmentation of input and will be acquired.System includes:Ionization module, ion transmission unit, ion accelerator module and signal gathering unit.The present invention to signal by carrying out dividing processing, the dynamic detection that instrument can be effectively improved is divided into, instrument is met while detecting some contents across the demand of the components more than 5 orders of magnitude, and influence to Collection when effectively inhibiting the instrument to gather big signal, improves the sampling precision of instrument.It the composite can be widely applied in time-of-flight mass spectrometer.

Description

A kind of method and system for improving time-of-flight mass spectrometer dynamic detection range
Technical field
The present invention relates to detection technique field, more particularly to a kind of time-of-flight mass spectrometer dynamic detection range that improves Method and system.
Background technology
Time of-flight mass spectrometer measurement concentration dynamic detection range be time of-flight mass spectrometer major parameter index it One.In actual applications, because the component in sample is sufficiently complex, it usually needs while detecting some contents across 5 quantity Component more than level, the concentration range of the object often detected is 1ppb-100ppm.But current time of-flight mass spectrometer one As in the case of using single channel ADC capture cards carry out data acquisition, if capture card range is set to a, 8 single channel capture card energy The signal magnitude scope adopted is a/28To a, then dynamic detection range is 256:1.When detecting the sample of larger concentration, signal is just Saturation occurs, therefore can not meet while measuring demand of the content difference more than the sample of 5 orders of magnitude.
In order to be able to quickly and easily make a distinction collection to signal, the measurement that time-of-flight mass spectrometer detects sample is improved Ion dynamic linear response range.Single-particle aerosol is disclosed in Chinese invention patent specification CN102543647 Signal pickup assembly and method, the device include electron multiplier MCP, limiter, attenuator and signal synthesizer, limiter, Attenuator is connected between electron multiplier MCP and signal synthesizer, and ADC capture cards are provided with signal synthesizer;It is described Electron multiplier MCP is according to voltage magnitude by detector signal input chopper or attenuator:Small-signal less than preset value is defeated Enter limiter, and by, by CPU processing, the big signal more than preset value enters attenuator, can make big signal after the collection of ADC capture cards It is effectively retained by different multiples decay, and, by CPU processing, ADC capture cards will not be burnt out after the collection of ADC capture cards.
A kind of mass spectrograph with wide dynamic range, the matter are disclosed in Chinese invention patent specification CN102648510 Signal transacting and switching stage of the analog signal through downstream that the detector of spectrometer is produced are divided into two signal A1=mA and A2=nA, Wherein m>N, analog-digital converter is used to the analog signal A1 and A2 being converted to two values D1 and D2;Controller is by numerical value D1 Received with D2 as input, if D1 is less than the maximum scale value of the converter, controller then provides the single value equal to D1 As output, or if D1 is equal to the maximum scale value of the converter, controller, which is then provided, to be equal to(m/n)D2 value conduct Output.
The principle of both technologies has similar place, has used attenuator to handle signal, and it has the disadvantage to work as When signal magnitude is different, attenuator can not ensure to stablize constant attenuation ratio, it will the signal of influence final output it is accurate Property.In addition except attenuator, two kinds of technologies have also used limiter and the operational amplifier for amplified signal to be believed respectively Number processing, it has the disadvantage that the out of order probability of device will be increased using a part more than whole device.
The content of the invention
In order to solve the above-mentioned technical problem, sampling precision can be improved it is an object of the invention to provide one kind, reduces failure general A kind of method and system of raising time-of-flight mass spectrometer dynamic detection range of rate.
The technical solution used in the present invention is:
A kind of method for improving time-of-flight mass spectrometer dynamic detection range, comprises the following steps:
A, material molecule is ionized into by ion by the ion gun of ionisation chamber;
B, ion by ion transmission range is transferred into accelerating region;
C, by ion by accelerating region accelerate draw, after being reflected again by echo area into field-free region free flight with inertia, Separated by different mass-to-charge ratioes, and enter eventually into MCP ion detectors;
D, described MCP ion detectors receive and electron stream are produced after ion, and pass through signal wire in electrical signal form Input power dispenser, the power divider is exported to high-speed data acquisition card after the signal of input is split and is acquired.
It is described as a kind of further improvements in methods of described raising time-of-flight mass spectrometer dynamic detection range Power divider has 1 signal input channel and n signal output channels, defeated after n parts for input signal to be divided into Go out, wherein, n is positive integer.
It is described as a kind of further improvements in methods of described raising time-of-flight mass spectrometer dynamic detection range High-speed data acquisition card is 8 multichannel ADC capture cards, for gathering ion detection signal, with n signal input channel, This n passage can be separately provided passage range, wherein, n is positive integer.
It is described as a kind of further improvements in methods of described raising time-of-flight mass spectrometer dynamic detection range Step D includes:
D1, the range to the one of signal input channel of high-speed data acquisition card are set to range arranges value lower limit a, separately One signal input channel range is set to range arranges value upper limit b, and by the range of remaining signal input channel be set to a~ Arbitrary value between b;
Electron stream is produced after the ion that D2, the MCP ion detectors are received, and passes through signal wire in electrical signal form Input signal is divided into after n parts and exported respectively to high-speed data acquisition card by input power dispenser, the power divider N signal input channel;
D3, read in high-speed data acquisition card the signal of each signal input channel and calculate the output of MCP ion detectors Electric signal size.
It is described as a kind of further improvements in methods of described raising time-of-flight mass spectrometer dynamic detection range The electric signal size of calculating MCP ion detectors output in step D3, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the signal input channel Signal magnitude exceed the signal input channel range, then the signal of next signal input channel is judged, until this The signal magnitude of signal input channel is in the range ability of the signal input channel, then big to the signal of the signal input channel It is small to be multiplied by the electric signal size that n represents the output of MCP ion detectors;If the signal magnitude of the signal input channel exceedes each letter The range of number input channel, then maximum range is multiplied by the electric signal that n represents the output of MCP ion detectors in each signal input channel Size.
Another technical scheme of the present invention is:
A kind of system for improving time-of-flight mass spectrometer dynamic detection range, including:
Ionization module, ion is ionized into for the ion gun by ionisation chamber by material molecule;
Ion transmission unit, for ion to be transferred into accelerating region by ion transmission range;
Ion accelerator module, for accelerating ion by accelerating region to draw, enters field-free region free flight again with inertia After being reflected by echo area, separated by different mass-to-charge ratioes, and enter eventually into MCP ion detectors;
Signal gathering unit, receives for described MCP ion detectors and electron stream is produced after ion, and with electric signal Form is exported to high-speed data after the signal of input is split and adopted by signal wire input power dispenser, the power divider Truck is acquired.
It is described as a kind of further improvement of the system of described raising time-of-flight mass spectrometer dynamic detection range Power divider has 1 signal input channel and n signal output channels, defeated after n parts for input signal to be divided into Go out, wherein, n is positive integer.
It is described as a kind of further improvement of the system of described raising time-of-flight mass spectrometer dynamic detection range High-speed data acquisition card is 8 multichannel ADC capture cards, for gathering ion detection signal, with n signal input channel, This n passage can be separately provided passage range, wherein, n is positive integer.
It is described as a kind of further improvement of the system of described raising time-of-flight mass spectrometer dynamic detection range Signal gathering unit includes:
Range setting unit, range is set to for the range to the one of signal input channel of high-speed data acquisition card Arranges value lower limit a, another signal input channel range is set to range arranges value upper limit b, and by remaining signal input channel Range be set to arbitrary value between a~b;
Electron stream is produced after signal cutting unit, the ion received for the MCP ion detectors, and with electric signal Form by signal wire input power dispenser, the power divider input signal is divided into after n parts export respectively to N signal input channel of high-speed data acquisition card;
Signal of change reading unit, for reading the signal of each signal input channel and calculating in high-speed data acquisition card The electric signal size of MCP ion detectors output.
It is described as a kind of further improvement of the system of described raising time-of-flight mass spectrometer dynamic detection range The electric signal size of calculating MCP ion detectors output in signal of change reading unit, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the signal input channel Signal magnitude exceed the signal input channel range, then the signal of next signal input channel is judged, until this The signal magnitude of signal input channel is in the range ability of the signal input channel, then big to the signal of the signal input channel It is small to be multiplied by the electric signal size that n represents the output of MCP ion detectors;If the signal magnitude of the signal input channel exceedes each letter The range of number input channel, then maximum range is multiplied by the electric signal that n represents the output of MCP ion detectors in each signal input channel Size.
The beneficial effects of the invention are as follows:
A kind of method and system for improving time-of-flight mass spectrometer dynamic detection range of the present invention to signal by carrying out Dividing processing, the dynamic detection that can effectively improve instrument is divided into, meet instrument and meanwhile detect some contents across 5 orders of magnitude with On component demand, and influence to Collection when effectively inhibiting the instrument to gather big signal improves instrument Sampling precision.And the present invention has only used one part of power divider, compared to the prior art reduces device and is out of order Probability.
Brief description of the drawings
The embodiment to the present invention is described further below in conjunction with the accompanying drawings:
Fig. 1 is a kind of step flow chart for the method for improving time-of-flight mass spectrometer dynamic detection range of the present invention;
Fig. 2 is a kind of step flow for the method and step D for improving time-of-flight mass spectrometer dynamic detection range of the present invention Figure;
Fig. 3 is a kind of block diagram for the system for improving time-of-flight mass spectrometer dynamic detection range of the present invention;
Fig. 4 is the principle schematic of the specific embodiment of the invention;
Fig. 5 is the range of linearity curve map of the double channels acquisition card of the specific embodiment of the invention;
Fig. 6 is the range of linearity curve map of the single channel capture card of the specific embodiment of the invention.
Embodiment
With reference to Fig. 1, a kind of method for improving time-of-flight mass spectrometer dynamic detection range of the present invention, including following step Suddenly:
A, material molecule is ionized into by ion by the ion gun of ionisation chamber;
B, ion by ion transmission range is transferred into accelerating region;
C, by ion by accelerating region accelerate draw, after being reflected again by echo area into field-free region free flight with inertia, Separated by different mass-to-charge ratioes, and enter eventually into MCP ion detectors;
D, described MCP ion detectors receive and electron stream are produced after ion, and pass through signal wire in electrical signal form Input power dispenser, the power divider is exported to high-speed data acquisition card after the signal of input is split and is acquired.
It is further used as preferred embodiment, the power divider has 1 signal input channel and n signal defeated Go out passage, exported for input signal to be divided into after n parts, wherein, n is positive integer.
It is further used as preferred embodiment, the high-speed data acquisition card is 8 multichannel ADC capture cards, is used for Ion detection signal is gathered, with n signal input channel, this n passage can be separately provided passage range, wherein, n is just Integer.
With reference to Fig. 2, it is further used as preferred embodiment, the step D includes:
D1, the range to the one of signal input channel of high-speed data acquisition card are set to range arranges value lower limit a, separately One signal input channel range is set to range arranges value upper limit b, and by the range of remaining signal input channel be set to a~ Arbitrary value between b;
Electron stream is produced after the ion that D2, the MCP ion detectors are received, and passes through signal wire in electrical signal form Input signal is divided into after n parts and exported respectively to high-speed data acquisition card by input power dispenser, the power divider N signal input channel;
D3, read in high-speed data acquisition card the signal of each signal input channel and calculate the output of MCP ion detectors Electric signal size.
It is further used as preferred embodiment, the electric signal of the calculating MCP ion detectors output in the step D3 Size, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the signal input channel Signal magnitude exceed the signal input channel range, then the signal of next signal input channel is judged, until this The signal magnitude of signal input channel is in the range ability of the signal input channel, then big to the signal of the signal input channel It is small to be multiplied by the electric signal size that n represents the output of MCP ion detectors;If the signal magnitude of the signal input channel exceedes each letter The range of number input channel, then maximum range is multiplied by the electric signal that n represents the output of MCP ion detectors in each signal input channel Size.
With reference to Fig. 3, a kind of system for improving time-of-flight mass spectrometer dynamic detection range of the present invention, including:
Ionization module, ion is ionized into for the ion gun by ionisation chamber by material molecule;
Ion transmission unit, for ion to be transferred into accelerating region by ion transmission range;
Ion accelerator module, for accelerating ion by accelerating region to draw, enters field-free region free flight again with inertia After being reflected by echo area, separated by different mass-to-charge ratioes, and enter eventually into MCP ion detectors;
Signal gathering unit, receives for described MCP ion detectors and electron stream is produced after ion, and with electric signal Form is exported to high-speed data after the signal of input is split and adopted by signal wire input power dispenser, the power divider Truck is acquired.
It is further used as preferred embodiment, the power divider has 1 signal input channel and n signal defeated Go out passage, exported for input signal to be divided into after n parts, wherein, n is positive integer.
It is further used as preferred embodiment, the high-speed data acquisition card is 8 multichannel ADC capture cards, is used for Ion detection signal is gathered, with n signal input channel, this n passage can be separately provided passage range, wherein, n is just Integer.
It is further used as preferred embodiment, the signal gathering unit includes:
Range setting unit, range is set to for the range to the one of signal input channel of high-speed data acquisition card Arranges value lower limit a, another signal input channel range is set to range arranges value upper limit b, and by remaining signal input channel Range be set to arbitrary value between a~b;
Electron stream is produced after signal cutting unit, the ion received for the MCP ion detectors, and with electric signal Form by signal wire input power dispenser, the power divider input signal is divided into after n parts export respectively to N signal input channel of high-speed data acquisition card;
Signal of change reading unit, for reading the signal of each signal input channel and calculating in high-speed data acquisition card The electric signal size of MCP ion detectors output.
It is further used as preferred embodiment, the calculating MCP ion detectors in the signal of change reading unit are defeated The electric signal size gone out, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the signal input channel Signal magnitude exceed the signal input channel range, then the signal of next signal input channel is judged, until this The signal magnitude of signal input channel is in the range ability of the signal input channel, then big to the signal of the signal input channel It is small to be multiplied by the electric signal size that n represents the output of MCP ion detectors;If the signal magnitude of the signal input channel exceedes each letter The range of number input channel, then maximum range is multiplied by the electric signal that n represents the output of MCP ion detectors in each signal input channel Size.
In the specific embodiment of the invention, using the high-speed data acquisition card of 8 n signal input channels, range is the logical of a The minimum signal size that road can be read is a/28, peak signal size is a.The feelings so inputted simultaneously in the signal of n passage Under condition, if the minimum range of capture card is a, maximum range is b, and acquisition software adopts the minimum electricity of MCP ion detectors output Signal magnitude is na/28, maximum electric signal size is nb, then the dynamic detection range of instrument is 256b/a:1, b/a value is got over Greatly, the dynamic detection range of instrument is bigger.
With reference to Fig. 4, within some time, it is several orders of magnitude that MCP ion detectors export two size difference simultaneously Signal, is divided into two parts, two passages of high-speed collection card set two ranges of size respectively, in a small amount through power divider by signal Journey gathers small-signal, and wide range gathers big signal, and the data of most latter two passage merge through software processing, finally aobvious at interface Show.One specific application example is as follows:
Several signals in output 5mV-5V magnitude ranges are set respectively with signal generator, will be believed through power divider Number two-way is divided into, is respectively connected to CH1 the and CH2 passages of double channels acquisition card, CH1 range is sized to 0.25V, offset 0.125V, CH2 range are sized to 5V, offset 2.5V.The big of each signal is read by oscillograph and acquisition software respectively Small, then using the reading of oscillograph as transverse axis, the reading of acquisition software makes the range of linearity curve of capture card for the longitudinal axis.Fig. 5 For the range of linearity curve of double channels acquisition card.As a result show that double channels acquisition card can gather the signal of 5mV to 5V sizes, dynamic Scope is 1000:1.Because the signal of signal generator sets lower limit to be 5mV, the upper limit is 5V, and the double channels acquisition card is theoretical 2 × 5=10V of maximum detection signal, most I survey 2 × 0.25/256=0.0019V signal, and its theoretical dynamic range is 10/ 0.0019=5263:1, more than 1000:1.
Several signals input single channel capture card in output 5mV-5V magnitude ranges is set respectively with signal generator, Capture card range is sized to 5V, offsets 2.5V.The size of each signal is read by oscillograph and acquisition software respectively, then Using the reading of oscillograph as transverse axis, the reading of acquisition software makes the range of linearity curve of capture card for the longitudinal axis.Fig. 6 is single channel The range of linearity curve of capture card.It can be seen that single channel capture card can gather the signal of 20mV to 5V sizes, input signal is more than 5V There is saturation in the signal adopted afterwards, and its dynamic range is 5/0.02=250:1, it can be seen that method of the invention can improve instrument Dynamic detection range.
From the foregoing it can be that a kind of method and system for improving time-of-flight mass spectrometer dynamic detection range of the present invention By carrying out dividing processing to signal, the dynamic detection that can effectively improve instrument is divided into, and meets instrument while detecting some contents The demand of component more than across 5 orders of magnitude, and to the shadow of Collection when effectively inhibiting the instrument to gather big signal Ring, improve the sampling precision of instrument.And the present invention has only used one part of power divider, compared to the prior art drops The low out of order probability of device.
Above is the preferable implementation to the present invention is illustrated, but the invention is not limited to the implementation Example, those skilled in the art can also make a variety of equivalent variations or replace on the premise of without prejudice to spirit of the invention Change, these equivalent deformations or replacement are all contained in the application claim limited range.

Claims (8)

1. a kind of method for improving time-of-flight mass spectrometer dynamic detection range, it is characterised in that:
Comprise the following steps:
A, material molecule is ionized into by ion by the ion gun of ionisation chamber;
B, ion by ion transmission range is transferred into accelerating region;
C, by ion by accelerating region accelerate draw, after being reflected again by echo area into field-free region free flight with inertia, by not The score of homogeneity lotus is from and entering eventually into MCP ion detectors;
D, described MCP ion detectors receive and electron stream are produced after ion, and inputted in electrical signal form by signal wire Power divider, the power divider is exported to high-speed data acquisition card after the signal of input is split and is acquired, to height Unlike signal input channel in fast data collecting card sets different size of range and by relatively more each signal input channel Input signal and the size of corresponding range determine the electric signal size of MCP ion detectors output;
The power divider has 1 signal input channel and n signal output channels, for input signal to be divided into Exported after n parts, wherein, n is positive integer.
2. a kind of method for improving time-of-flight mass spectrometer dynamic detection range according to claim 1, its feature exists In:The high-speed data acquisition card is 8 multichannel ADC capture cards, defeated with n signal for gathering ion detection signal Enter passage, this n passage can be separately provided passage range, wherein, n is positive integer.
3. a kind of method for improving time-of-flight mass spectrometer dynamic detection range according to claim 2, its feature exists In:The step D includes:
D1, the range to the one of signal input channel of high-speed data acquisition card are set to range arranges value lower limit a, another Signal input channel range is set to range arranges value upper limit b, and by the range of remaining signal input channel be set to a~b it Between arbitrary value;
Electron stream is produced after the ion that D2, the MCP ion detectors are received, and is inputted in electrical signal form by signal wire Power divider, input signal is divided into by the power divider to be exported to n of high-speed data acquisition card respectively after n parts Signal input channel;
D3, read the signal of each signal input channel in high-speed data acquisition card and calculate the electricity of MCP ion detectors output Signal magnitude.
4. a kind of method for improving time-of-flight mass spectrometer dynamic detection range according to claim 3, its feature exists In:The electric signal size of calculating MCP ion detectors output in the step D3, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the letter of the signal input channel Number size exceedes the range of the signal input channel, then the signal of next signal input channel is judged, up to the signal The signal magnitude of input channel is in the range ability of the signal input channel, then the signal magnitude to the signal input channel multiplies The electric signal size of MCP ion detectors output is represented with n;If it is defeated that the signal magnitude of the signal input channel exceedes each signal Enter the range of passage, then in each signal input channel maximum range be multiplied by n represent MCP ion detectors output electric signal it is big It is small.
5. a kind of system for improving time-of-flight mass spectrometer dynamic detection range, it is characterised in that
Including:
Ionization module, ion is ionized into for the ion gun by ionisation chamber by material molecule;
Ion transmission unit, for ion to be transferred into accelerating region by ion transmission range;
Ion accelerator module, for accelerating ion by accelerating region to draw, enters field-free region free flight anti-again with inertia Penetrate after area's reflection, separated by different mass-to-charge ratioes, and enter eventually into MCP ion detectors;
Signal gathering unit, receives for described MCP ion detectors and electron stream is produced after ion, and in electrical signal form By signal wire input power dispenser, the power divider is exported to high-speed data acquisition card after the signal of input is split It is acquired, different size of range is set to the unlike signal input channel in high-speed data acquisition card and by relatively more each letter Number input signal of input channel determines the electric signal size of MCP ion detectors output with the size of corresponding range;
The power divider has 1 signal input channel and n signal output channels, for input signal to be divided into Exported after n parts, wherein, n is positive integer.
6. a kind of system for improving time-of-flight mass spectrometer dynamic detection range according to claim 5, its feature exists In:The high-speed data acquisition card is 8 multichannel ADC capture cards, defeated with n signal for gathering ion detection signal Enter passage, this n passage can be separately provided passage range, wherein, n is positive integer.
7. a kind of system for improving time-of-flight mass spectrometer dynamic detection range according to claim 6, its feature exists In:The signal gathering unit includes:
Range setting unit, is set to range for the range to the one of signal input channel of high-speed data acquisition card and sets It is worth lower limit a, another signal input channel range is set to range arranges value upper limit b, and by the amount of remaining signal input channel Journey is set to the arbitrary value between a~b;
Electron stream is produced after signal cutting unit, the ion received for the MCP ion detectors, and in electrical signal form By signal wire input power dispenser, input signal is divided into after n parts by the power divider to be exported at a high speed respectively N signal input channel of data collecting card;
Signal of change reading unit, for reading in high-speed data acquisition card the signal of each signal input channel and calculating MCP The electric signal size of ion detector output.
8. a kind of system for improving time-of-flight mass spectrometer dynamic detection range according to claim 7, its feature exists In:The electric signal size of calculating MCP ion detectors output in the signal of change reading unit, it is specially:
The signal of each signal input channel is judged according to the order of range from small to large, if the letter of the signal input channel Number size exceedes the range of the signal input channel, then the signal of next signal input channel is judged, up to the signal The signal magnitude of input channel is in the range ability of the signal input channel, then the signal magnitude to the signal input channel multiplies The electric signal size of MCP ion detectors output is represented with n;If it is defeated that the signal magnitude of the signal input channel exceedes each signal Enter the range of passage, then in each signal input channel maximum range be multiplied by n represent MCP ion detectors output electric signal it is big It is small.
CN201610089824.XA 2016-02-17 2016-02-17 A kind of method and system for improving time-of-flight mass spectrometer dynamic detection range Active CN105609401B (en)

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US8633841B2 (en) * 2009-09-14 2014-01-21 Hitachi High-Technologies Corporation Signal processing device, mass spectrometer, and photometer
IT1395787B1 (en) * 2009-09-16 2012-10-19 Dani Instr Spa MASS SPECTROMETER WITH WIDE RANGE OF DYNAMICS.
US8378296B1 (en) * 2010-04-05 2013-02-19 Stc.Unm Enhancement of concentration range of chromatographically detectable components with array detector mass spectrometry
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