CN102324377A - Four polar form quality analysis apparatus - Google Patents
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Abstract
In the scanning survey of the mass scanning that repeats whole definite quality scope is carried out; Take place to dash down to wait during owing to the beginning voltage that returns to next time scanning in the end voltage that makes voltage from single pass and cause magnitude of voltage to become unstable, stand-by period that therefore need be suitable.In the past, waiting time and analysis condition had nothing to do and were made as fixing value.Therewith relatively, in four polar form quality analysis apparatus involved in the present invention, calculate end of scan quality and the Δ M of poor quality that scans the beginning quality, the adjusting time different according to this setting of poor quality according to specified mass range.The voltage stabilizing time lacks under the situation about getting final product in that Δ M of poor quality is less, sets the less relatively adjusting time.Thus, the repetition period of mass scanning shortens, and temporal resolution improves.
Description
The application be international filing date be on May 26th, 2008 (get into date in China national stage be on November 26th, 2010), national applications number be 200880129479.1, denomination of invention divides an application for the application for a patent for invention of " four polar form quality analysis apparatus ".
Technical field
The present invention relates to a kind of four polar form mass filters that used as the four polar form quality analysis apparatus that come the mass analyzer of isolating ions according to quality (being strictly speaking) according to m/z.
Background technology
As one of quality analysis apparatus, known a kind of four polar form quality analysis apparatus that in the mass analyzer that comes isolating ions according to quality, use four utmost point mass filters.Fig. 6 is the summary structure chart of common four polar form quality analysis apparatus.
With the sample molecule ionization, the ion that is produced is assembled (also being accelerated sometimes) by ion lens plasma feeding optical system 2 in ion source 1, and imports in the space of long axis direction of four utmost point mass filters 3.Four utmost point mass filters 3 are made up of 4 (only having described 2 among Fig. 6) bar electrodes around ion optical axis C configured in parallel.Each bar electrode is applied respectively direct voltage ± U and voltage ± (U+Vcos ω t) that high frequency voltage ± Vcos ω t addition obtains; Apply voltage according to this and only optionally make the ion with extra fine quality pass the space of long axis direction, ion is in addition dispersed halfway.Detector 4 outputs and the corresponding signal of telecommunication of amount that has passed the ion of four utmost point mass filters 3.
As stated,, therefore apply voltage, can scan the quality of the ion that will arrive detector 4 in the whole definite quality scope through scanning this because the quality of the ion through four utmost point mass filters 3 correspondingly changes with the voltage that applies that the bar electrode is applied.Scanning survey in Here it is the four polar form quality analysis apparatus.For example gas chromatography mass analytical equipment (GC/MS), liquid chromatogram quality analysis apparatus (LC/MS) etc. are such; Under the situation that sample constituents in importing to quality analysis apparatus changes along with the process of time; Through repeating above-mentioned scanning survey, can roughly detect the various compositions that occur successively continuously.Fig. 7 be outlined be illustrated in when repeating scanning survey the figure of the mass change of the ion that arrives detector 4.
In such scanning survey; Make and apply voltage from beginning to increase at leisure with the corresponding voltage of minimum mass M1 to what the bar electrode applied; When reaching, make voltage turn back to 1 corresponding voltage rapidly with minimum mass M with the corresponding voltage of biggest quality M2.When changing voltage so sharp, can't avoid the generation of overshoot (overshoot) (undershoot: dash down), therefore after changing voltage, till voltage is stable, need stand-by period (setting time: the adjusting time).
For example, it is inevitable in patent documentation 1, having put down in writing the adjusting time is set in selecting ionic monitoring (SIM) measurement, and this also is identical in scanning survey.Thus, as shown in Figure 7, by each time mass scanning is set the adjusting time.During this adjusting time, not to importing to the composition implementation quality analysis of ion source 1.Thereby the time interval of long more mass scanning of adjusting time is long more, that is to say, the cycle of mass scanning is elongated, thereby temporal resolution descends.
In addition; Usually; In quality analysis apparatus,, the user (when being M1～M2) in the example of Fig. 7, makes the mass spectrum of this scope when specifying the mass range want to observe; But, expanded the mass range implementation quality scanning behind the Rack up and down to comparing with specified mass range as the internal actions of device.That is, also be to be the starting point of mass scanning, to be that the terminal point of mass scanning comes implementation quality scanning, with M2+ Δ M2 with M1～Δ M1 even under the situation of the mass range of having specified M1～M2.This is because initial object ion is wanted spended time from inciding four utmost point mass filters till penetrating; Therefore cause before the object ion outgoing, remaining in four utmost point mass filters, the 3 inner ions of not expecting and arrive detector 4, thereby can't obtain correct signal strength signal intensity.Enumerating an example, is that m/z is under 100～1000 the situation in the mass range of wanting to observe, to this mass range guaranteed respectively up and down m/z be 10 scanning surplus, m/z is that 90～1010 mass range is carried out scanning.
Like this, be arranged on the outside that makes the needed mass range of mass spectrum the scanning surplus that is used for stably measuring during also with the above-mentioned adjusting time likewise, for the quality analysis of essence useless during.Thereby, in order to improve the temporal resolution of analysis, preferably also dwindle this scanning margin widths as much as possible.
Patent documentation 1: TOHKEMY 2000-195464 communique
Summary of the invention
The problem that invention will solve
The present invention accomplishes in view of the above problems; Its main purpose is to provide following a kind of four polar form quality analysis apparatus: under the situation of the mass scanning in repeating the definite quality scope or repeating to set successively under the situation of a plurality of quality of regulation; Through shortening the time useless for the quality analysis of essence as much as possible; Shorten the repetition period, thereby improve temporal resolution.
The scheme that is used to deal with problems
First invention of accomplishing in order to address the above problem is a kind of four polar form quality analysis apparatus; Possess four utmost point mass filter and detectors; Above-mentioned four utmost point mass filters optionally make the ion with extra fine quality pass through; Above-mentioned detector detects the ion that has passed through this four utmost points mass filter; This four polar forms quality analysis apparatus is carried out scanning survey or is carried out the measurement that cycle of setting a plurality of quality is successively repeated, and in this scanning survey, makes the cycle repetition of the quality of ion that will be through above-mentioned four utmost point mass filters in the gamut interscan of the mass range of regulation, and this four polar forms quality analysis apparatus is characterised in that; Possess: a) four utmost point driver elements, it applies the voltage of regulation to each electrode that constitutes above-mentioned four utmost point mass filters; And b) control unit; When carrying out scanning survey or make the measurement of the cycle repetition of setting a plurality of quality successively; This control unit applies under the voltage condition what each electrode that constitutes above-mentioned four utmost point mass filters applied correspondingly to scan with quality or to change at above-mentioned four utmost point driver elements of control, changes from the end of one-period according to of poor quality between the beginning quality in cycle and the end quality and plays the stand-by period till the beginning of following one-period.
At this,, for example enumerate and select ionic monitoring (SIM) is measured, selectivity the is higher MRM that utilizes MS/MS to analyze to measure etc. as the measurement that cycle of setting a plurality of quality is successively repeated.
In four polar form quality analysis apparatus in the past, the mass range during with scanning survey etc. are analyzed conditional independence ground, and the stand-by period of playing from the finish time of a mass scanning till zero hour of mass scanning is next time fixed.Therewith relatively, in four related polar form quality analysis apparatus of first invention, control unit is controlled and is made in scanning survey, and the difference of scanning beginning quality and end of scan quality is more little, and the stand-by period (adjusting time) is short more.
If the difference of scanning beginning quality and end of scan quality is less; Then to the electrode that constitutes four utmost point mass filters apply apply voltage and return to and scan beginning quality corresponding voltage the time overshoot (dashing down) less relatively, the time till voltage is stable is shorter.Thereby, even shorten the above-mentioned stand-by period, also can begin mass scanning next time from the sufficiently stable state of voltage.Thus, the useless stand-by period that the collection mass analysis data is not done to contribute shortens, and can shorten the repetition period of the mass scanning in the scanning survey.The scanning survey that this is not only applicable to scan widely the mass range of regulation is applicable to that too the considerably less SIM of quality quantity that in one-period, sets measures, MRM measures.
Second invention of accomplishing in order to address the above problem is four polar form quality analysis apparatus; Possess four utmost point mass filter and detectors; Above-mentioned four utmost point mass filters optionally make the ion with extra fine quality pass through; Above-mentioned detector detects the ion that has passed through this four utmost points mass filter; This four polar forms quality analysis apparatus is carried out scanning survey, in this scanning survey, makes the cycle repetition of the quality of ion that will be through above-mentioned four utmost point mass filters in the gamut interscan of the mass range of regulation, and this four polar forms quality analysis apparatus is characterised in that; Possess: a) four utmost point driver elements, it applies the voltage of regulation to each electrode that constitutes above-mentioned four utmost point mass filters; And b) control unit; When carrying out scanning survey; This control unit set to specified mass range be positioned on this scope with under at least one side's scanning surplus; Control above-mentioned four utmost point driver elements and the voltage that applies that each electrode that constitutes above-mentioned four utmost point mass filters applies to scan having increased with the corresponding mass range of measuring of this scanning surplus, and this control unit changes the quality width of above-mentioned scanning surplus according to sweep speed with scanning.
In four polar form quality analysis apparatus in the past, with the above-mentioned stand-by period (adjusting time) likewise, with conditional independence such as sweep speed ground, the quality width of scanning surplus (below be called the scanning margin widths) is also fixed.Therewith relatively, in the related four polar form quality analysis apparatus of second invention, control unit is set and is made specified sweep speed more little (slowly), and it is short more to scan margin widths.Sweep speed is more little, and is long more for the sweep time with the one scan margin widths.In other words, under the less situation of sweep speed,, also can guarantee the time enough and to spare of and situation same degree that scanning margin widths bigger big with sweep speed even reduce to scan margin widths.During this time enough and to spare, can get rid of and remain in the inner unwanted ion of four utmost point mass filters and make initial object ion through four utmost point mass filters.
Like this, with respect in the past under the less situation of sweep speed, also set excessive time enough and to spare, in four related polar form quality analysis apparatus of second invention,, can shorten the repetition period of mass scanning through cutting down this excessive time enough and to spare.
In addition, even sweep speed is identical, the mass scanning scope moves to the high-quality zone more, and needed scanning margin widths is big more.This is because the ion of big quality is slow more in the flying speed that four utmost point mass filters are inner, and initial object ion is long more from the time of inciding four utmost point mass filters and playing till the ejaculation.Thereby, in four related polar form quality analysis apparatus of second invention, comparatively it is desirable to, control unit also changes the quality width of scanning surplus according to scanning beginning quality.Specifically, it is more little to be made as the quality width of the more little scanning surplus of scanning beginning quality.
In addition, ion also depends on the kinetic energy that the moment had that this ion is directed to four utmost point mass filters through the needed time of four utmost point mass filters, and kinetic energy is big more, and the time of passing through is short more.Therefore, comparatively it is desirable to, above-mentioned control unit also changes the quality width of scanning surplus according to the accelerating voltage that is directed to the ion of four utmost point mass filters.Specifically, it is more little to be made as expose thoroughly the more quality width of surplus of accelerating voltage.
Possess the structure of the ion lens plasma feeding optical system that is used for carrying ion in the prime of four utmost point mass filters, above-mentioned accelerating voltage is equivalent to the DC potential difference between ion feeding optical system and four utmost point mass filters.Thereby; Under the situation that the dc offset voltage that ion feeding optical system is applied is fixed, as long as change the quality width that scans surplus according to the dc offset voltage that four utmost point mass filters are applied (selecting with the different direct voltage of voltage) with the quality of ion.
The effect of invention
According to four related polar form quality analysis apparatus of first invention; In scanning survey, SIM measurement, MRM measure; Between the adjacent cycle, change to four utmost point mass filters apply apply voltage the time, can shorten the useless stand-by period above required time.Thus,, also can shorten the repetition period of mass scanning,, can improve temporal resolution through shortening the so-called dead time that can't obtain mass analysis data even for example sweep speed is identical.
According to the related four polar form quality analysis apparatus of second invention, when carrying out scanning survey, can shorten being set in being used to mass range outside and making the quality width of the stable scanning surplus of measurement.Thus, for example in the less or mass range under the situation in the relatively low zone of quality, the repetition period of mass scanning can be shortened,, data resolution can be improved through shortening the so-called dead time that can't obtain mass analysis data in sweep speed.
Description of drawings
Fig. 1 is the structure chart as the major part of the four polar form quality analysis apparatus of one embodiment of the present of invention.
The figure of the state of the mass change when Fig. 2 is the expression scanning survey.
Fig. 3 is the figure that the scanning in the expression scanning survey begins the measured result of the of poor quality and required voltage stabilizing time relation between quality and the end of scan quality.
The figure of the state of the mass change when Fig. 4 is expression SIM measurement.
Fig. 5 is the figure of the measured result of the relation between expression sweep speed and scanning beginning quality and the scanning margin widths.
Fig. 6 be common four polar form quality analysis apparatus be the summary structure chart at center with the ion-optic system.
Fig. 7 is the figure of the state of the mass change in the outlined ground expression scanning survey.
Description of reference numerals
1: ion source; 2: ion feeding optical system; 3: four utmost point mass filters; 3a, 3b, 3c, 3d: bar electrode; 4: detector; 10: control part; 101: regulate the time determination section; 102: scanning margin widths determination section; 11: input part; 12: the voltage control data store; 13: ion is selected the electricity consumption living portion that cuts down output; 15: high frequency voltage generation portion; 16: direct voltage generation portion; 17: high frequency/direct current addition portion; 18: bias voltage generation portion; 19,20: bias voltage addition portion; 21: ion-optic system voltage generation portion.
Embodiment
With reference to accompanying drawing four polar form quality analysis apparatus as one embodiment of the present of invention are described.Fig. 1 is the structure chart of major part of four polar form quality analysis apparatus of present embodiment.Structural element to identical with the Fig. 6 that has explained has added identical Reference numeral.Four polar form quality analysis apparatus of present embodiment are that gasiform sample is imported to the device in the ion source 1, can connect gas chromatograph in the prime of quality analysis apparatus.Under the situation that is made as the structure that liquid sample is analyzed; As ion source 1; Use atmospheric pressure ionizationions such as electric spray ion source; In order this ion source 1 to be made as roughly atmospheric pressure environment and four utmost point mass filters 3, detector 4 to be configured in the high vacuum environment, as long as be made as the structure of multipole differential gas extraction system.In this case, can connect liquid chromatograph in the prime of quality analysis apparatus.
In four polar form quality analysis apparatus of present embodiment, as above-mentioned, dispose ion source 1, ion feeding optical system 2, four utmost point mass filters 3 and detector 4 in the inside of not shown vacuum chamber.Four utmost point mass filters 3 possess and are configured to and the cylinder four bar electrode 3a, 3b, 3c, the 3d of inscribe mutually that with ion optical axis C are the predetermined radius at center.Clipping ion optical axis C and relative two bar electrodes, be that bar electrode 3a is connected respectively with 3d with 3c, bar electrode 3b among these four bar electrode 3a, 3b, 3c, the 3d.As four utmost point driver elements that these four bar electrode 3a, 3b, 3c, 3d are applied the unit of voltage is that ion is selected electricity consumption cut down output living portion 13, bias voltage generation portion 18, bias voltage addition portion 19,20.Ion selects the electricity consumption living portion 13 that cuts down output to comprise direct current (DC) voltage generation portion 16, high frequency (RF) voltage generation portion 15, high frequency/direct current (RF/DC) addition portion 17.
The ion feeding optical system 2 of the prime of 21 pairs four utmost point mass filters 3 of ion-optic system voltage generation portion applies direct voltage Vdc1.10 pairs of ion-optic system voltage of control part generation portion 21, ion select the cut down output action of living portion 13, bias voltage generation portion 18 etc. of electricity consumption to control, and are connected with voltage control data store 12 in order to carry out this control.In addition, control part 10 also is connected with the input part of being operated by the operator 11.In addition, control part 10 is that its function is realized at the center with the computer that comprises CPU, memory etc.
In living portion 13 was cut down output in ion selection electricity consumption, direct voltage generation portion 16 is the mutually different direct voltage ± U of polarization under the control of control part 10.High frequency voltage generation portion 15 likewise produces the high frequency voltage ± Vcos ω t of 180 ° of phase phasic differences under the control of control part 10.High frequency/direct current addition portion 17 is direct voltage ± U and high frequency voltage ± Vcos ω t addition, produces the voltage of U+Vcos ω t and-two systems of (U+Vcos ω t).The ion of the quality (being m/z strictly speaking) of the ion that control that Here it is will be passed through selects to use voltage.
Bias voltage generation portion 18 is in order to form the DC electric field in space that ion is imported to efficiently the long axis direction of four utmost point mass filters 3 in the front side of four utmost point mass filters 3, and generate to apply each bar electrode 3a～3d, and direct voltage Vdc1 that ion feeding optical system 2 is applied between have the suitable voltage difference shared dc offset voltage Vdc2.Bias voltage addition portion 19 selects ion with voltage U+Vcos ω t and dc offset voltage Vdc2 addition; Formed voltage Vdc2+U+Vcos ω t is imposed on bar electrode 3a, 3c; Bias voltage addition portion 20 selects ion with voltage-(U+Vcos ω t) and dc offset voltage Vdc2 addition formed voltage Vdc2-(U+Vco s ω t) to be imposed on bar electrode 3b, 3d.In addition, can come dc offset voltage Vcd1, Vcd2 are set best value through the automatic adjustment of using standard specimen etc. to carry out.
Four polar form quality analysis apparatus of present embodiment are carried out following scanning survey: to the voltage (the amplitude V of direct voltage U and high frequency voltage specifically) that each bar electrode 3a～3d of four utmost point mass filters 3 applies, repeat the mass scanning by the whole mass range of user's setting through scanning.When carrying out this scanning survey, carry out unique voltage control.This control action below is described.
In scanning survey; That kind makes and applies voltage from beginning to increase at leisure with scanning beginning mass M 1 corresponding voltage shown in Fig. 2 (a); When reaching, make to apply voltage and turn back to and scan beginning mass M 1 corresponding voltage rapidly with end of scan mass M 2 corresponding voltages.Here it is mass scanning, be one-period.Dash under when voltage is sharply reduced, taking place, till magnitude of voltage steadily, need the time to a certain degree.Therefore, wait for till voltage is stable, begin then to be used for mass scanning next time voltage scanning, be next cycle.Voltage variety before taking place to dash down, be that end of scan voltage is big more with the voltage difference that scanning begins between the voltage, following momentum is big more.Thereby the Δ M of poor quality between end of scan mass M 2 and the scanning beginning mass M 1 is big more, and the time (voltage stabilizing time) till stablizing to voltage is long more.
Fig. 3 is the figure that comes the result that investigation quality difference Δ M and the relation between the voltage stabilizing time obtain through actual measurement.Can know according to this result, for example under the situation that Δ M of poor quality is 2000 [u], need the voltage stabilizing time of 5 [msec], relative therewith, be under the situation of 200 [u] at Δ M of poor quality, the voltage stabilizing time of 0.5 [msec] is just enough.In four polar form quality analysis apparatus in the past, with this Δ M of poor quality irrespectively, consider that the maximum voltage stabilizing time sets the fixing adjusting time.Therefore, for example if the adjusting time of 5 [msec], then under the situation that Δ M of poor quality is 200 [u], wasted the time of 4.5 [msec].The time that is equivalent in the past waste with the leg-of-mutton zone shown in the oblique line among Fig. 3.Said here " time of waste " is although be meant that voltage is stable but do not begin next time mass scanning and time of standby still.
In four polar form quality analysis apparatus of present embodiment, in order to reduce the time of above-mentioned waste as much as possible, and change the length of the stand-by period (that is adjusting time) till beginning mass scanning next time according to Δ M of poor quality.Therefore, the adjusting time determination section 101 that comprised of control part 10 stores the information that is used for deriving according to Δ M of poor quality the suitable adjusting time in advance.This information for example is to depict the calculating formula of the straight line of representing the relation between time of voltage stabilizing as shown in figure 3 and the Δ M of poor quality, table etc.
When implementing scanning survey, before implementing this scanning survey, the user sets the analysis condition that comprises mass range, sweep speed etc. from input part 11.Like this, in control part 10, regulate time determination section 101, use the above-mentioned adjusting time to derive and obtain and this Δ M corresponding adjusting time of poor quality with information according to specified mass range calculated mass difference Δ M.Thus, Δ M of poor quality is big more, and the adjusting time is set longly more.Control part 10 is when repeating the mass scanning that whole specified mass range is carried out, and the stand-by period that mass scanning is finished to play till mass scanning begins next time was set at by the adjusting time of regulating 101 decisions of time determination section.Consequently shown in Fig. 2 (b), under the less situation of Δ M of poor quality, regulate time t2 and shorten, the cycle of mass scanning shortens in fact.Can't obtain during this adjusting time during the mass analysis data, can improve temporal resolution during this period through shortening.
And, in four polar form quality analysis apparatus of present embodiment, according to analysis condition, except the change adjusting time, the scanning margin widths Δ Ms when also changing mass scanning.Shown in Fig. 2 (c), scanning margin widths Δ Ms is meant that specified scanning begins of poor quality between mass M s and the actual quality that begins mass scanning.Ideal situation this scanning margin widths Δ Ms down is zero, but in fact in order to eliminate the influence that remains in the unwanted ion in four utmost point mass filters 3 before beginning at mass scanning, needs to set scanning margin widths Δ Ms to a certain degree.In this case, begin to carry out mass scanning from Ms-Δ Ms, but the data of being obtained during till becoming Ms do not have reliability, therefore go out of use, actual reflection is the data more than the mass M s in mass spectrum.In addition, not only the scope below the scanning beginning mass M s is set the scanning surplus similarly in the scope more than end of scan mass M e.
Fig. 5 begins quality and the result's that the relation between the margin widths Δ Ms that scans obtains figure through actual measurement investigation sweep speed and scanning.This is the result who under following situation, obtains: set under the state of different sweep speeds, the variation investigation that changes scanning beginning quality and scanning margin widths and observation signal intensity respectively can access the scanning margin widths of the signal strength signal intensity with reliability.Hence one can see that, more for example is under the situation of 1000 [Da/sec] in sweep speed, can make scanning margin widths Δ Ms very little.Therewith relatively, comparatively fast for example be under the situation of 15000 [Da/sec] in sweep speed, need to scan margin widths Δ Ms and also establish greatlyyer.The identical scanning margin widths Δ Ms even this is, sweep speed is fast more, and the corresponding time is short more.In addition, when scanning beginning quality is big, needs to scan margin widths Δ Ms and establish greatlyyer.This is because the quality of ion is big more, and it is long more to pass the 3 needed times of four utmost point mass filters.As an example, sweep speed is that 15000 [Da/sec], scanning beginning quality are under the situation of 1048 [u], needs to scan margin widths Δ Ms and is made as 3 [u].That is to say,, in fact also need begin to carry out mass scanning from m/z 1045 even mass spectral lower end quality is 1048.
Fig. 5 is the result under the fixing condition of the voltage difference between the accelerating voltage of ion, the dc offset voltage Vdc2 that promptly four utmost point mass filters 3 is applied and the dc offset voltage Vdc1 that ion feeding optical system 2 is applied, also depends on ion accelerating voltage but from experiment, can confirm required scanning margin widths Δ Ms.That is, obtain scanning margin widths Δ Ms with following formula.
Δ Ms=k * [sweep speed] * [m/z value]
1/2
At this, k is that accelerating voltage is big more by the constant of the accelerating voltage decision of ion, and constant k is more little.In addition, constant k also depends on the length of the bar electrode 3a～3d of four utmost point mass filters 3, but because this length is not the analysis condition of being set by the user, therefore inessential.
In four polar form quality analysis apparatus in the past, scanning margin widths Δ Ms also with the above-mentioned adjusting time likewise, be set to and considered the fixed value of poor condition.Therefore, during or situation that scanning beginning quality less slow in sweep speed etc., the scanning margin widths is excessive, we can say that the part of the time of this mass range of scanning is above-mentioned " time of waste ".Therewith relatively, in four polar form quality analysis apparatus of present embodiment, change scanning margin widths Δ Ms according to sweep speed, scanning beginning quality and ion accelerating voltage.Therefore, the scanning margin widths determination section 102 that comprised of control part 10 stores in advance and is used for deriving the information of suitable scanning margin widths Δ Ms according to sweep speed, scanning beginning quality and ion accelerating voltage.This information for example is to depict the calculating formula, table etc. of straight line of expression sweep speed and the relation between scanning beginning quality and the scanning margin widths of that kind as shown in Figure 5.And, prepare different calculating formula, table by each bias direct current voltage of the accelerating voltage that determines ion.
When implementing scanning survey; When user's setting comprised the analysis condition of mass range, sweep speed etc., the scanning margin widths determination section 102 in the control part 10 used above-mentioned scanning margin widths to derive with information and obtains the corresponding scanning margin widths of the accelerating voltage Δ Ms that begins quality and determined by bias direct current voltage Vdc1, Vdc2 with specified sweep speed, scanning.Bias direct current voltage Vdc1, Vdc2 also do not rely on the analysis condition of being set by the user, are decided to be the result of the adjustment that makes the ionic strength maximum and automatically perform usually.
Thus, sweep speed is big more, and scanning beginning quality is big more, and the scanning margin widths is set longly more.Control part 10 is when repeating the mass scanning that the whole mass range of specified for example M3～M4 is carried out; Scanning margin widths Δ Ms according to by 102 decisions of scanning margin widths determination section confirms as M3-Δ Ms～M4+ Δ Ms with the mass scanning scope of reality.Begin under the less situation of quality in sweep speed less (slower) or scanning, the scanning margin widths diminishes relatively, so the repetition period of mass scanning shortens in fact.Can't obtain during this scanning margin widths during the effective mass analysis data, can improve temporal resolution through shortening this scanning margin widths.
In addition; In above-mentioned explanation, recorded and narrated the situation of carrying out scanning survey; But that kind as shown in Figure 4; Even under the situation that repeats the SIM measurement of preassigned a plurality of quality being carried out successively quality analysis or in the MS/MS analysis, repeat under the situation of MRM measurement, as above-mentioned, changing the length of adjusting time according to Δ M of poor quality also is effective certainly.
In addition, in the above-described embodiments,, be prerequisite with the situation that scans to the high-quality direction from low quality for mass scanning, this is common situation, but also can scan to the low quality direction from high-quality on the contrary.In this case, also can directly utilize above-mentioned technology.
In addition, the foregoing description is an example of the present invention, the distortion of in the scope of aim of the present invention, suitably carrying out, appends, revises in the claim scope that is also contained in the application certainly.
Claims (6)
1. polar form quality analysis apparatus; Possess four utmost point mass filter and detectors; Above-mentioned four utmost point mass filters optionally make the ion with extra fine quality pass through; Above-mentioned detector detects the ion that has passed through this four utmost points mass filter, and this four polar forms quality analysis apparatus is carried out scanning survey or carried out the measurement that cycle of setting a plurality of quality is successively repeated, and in this scanning survey, makes the cycle repetition of the quality of ion that will be through above-mentioned four utmost point mass filters in the gamut interscan of the mass range of regulation; This four polar forms quality analysis apparatus is characterised in that also possess:
A) four utmost point driver elements, it applies the voltage of regulation to each electrode that constitutes above-mentioned four utmost point mass filters; And
B) control unit; When carrying out scanning survey or make the measurement of the cycle repetition of setting a plurality of quality successively; This control unit applies under the voltage condition what each electrode that constitutes above-mentioned four utmost point mass filters applied correspondingly to scan with quality or to change at above-mentioned four utmost point driver elements of control, changes from the end of one-period according to of poor quality between the beginning quality in cycle and the end quality and plays the stand-by period till the beginning of following one-period.
2. four polar form quality analysis apparatus according to claim 1 is characterized in that,
The beginning quality in cycle and finish of poor quality more little between the quality, above-mentioned control unit makes the above-mentioned stand-by period short more.
3. four polar form quality analysis apparatus according to claim 1; It is characterized in that; When carrying out scanning survey; This control unit set to specified mass range be positioned on this scope with under at least one side's scanning surplus; Control above-mentioned four utmost point driver elements and come to scan, and this control unit changes the quality width of above-mentioned scanning surplus according to sweep speed having increased with the corresponding mass range of measuring of this scanning surplus to change the voltage that applies that each electrode that constitutes above-mentioned four utmost point mass filters is applied.
4. four polar form quality analysis apparatus according to claim 3 is characterized in that,
Sweep speed is more little, and above-mentioned control unit makes the quality width of above-mentioned scanning surplus more little.
5. according to claim 3 or 4 described four polar form quality analysis apparatus, it is characterized in that,
Above-mentioned control unit also changes the quality width of above-mentioned scanning surplus according to scanning beginning quality.
6. four polar form quality analysis apparatus according to claim 5 is characterized in that,
Above-mentioned control unit also changes the quality width of above-mentioned scanning surplus according to the accelerating voltage that is directed to the ion of above-mentioned four utmost point mass filters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110720133A (en) * | 2017-06-29 | 2020-01-21 | 株式会社岛津制作所 | Quadrupole rod mass spectrometry device |
| CN114531769A (en) * | 2022-03-03 | 2022-05-24 | 清华大学 | Multi-energy extraction method of synchrotron |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1484742A (en) * | 1974-05-16 | 1977-09-01 | Universal Monitor Corp | Mass spectrometric system for rapid automatic and specific identification and quantification of compounds |
| JPH04286848A (en) * | 1991-03-15 | 1992-10-12 | Hitachi Ltd | Mass spectrometer |
| US5397894A (en) * | 1993-05-28 | 1995-03-14 | Varian Associates, Inc. | Method of high mass resolution scanning of an ion trap mass spectrometer |
| JP2000195464A (en) * | 1998-12-25 | 2000-07-14 | Shimadzu Corp | Quadrupole mass spectrometer |
| JP3147914B2 (en) * | 1991-03-18 | 2001-03-19 | 株式会社日立製作所 | Mass spectrometry method and mass spectrometer |
-
2008
- 2008-05-26 CN CN201110250005.6A patent/CN102324377B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1484742A (en) * | 1974-05-16 | 1977-09-01 | Universal Monitor Corp | Mass spectrometric system for rapid automatic and specific identification and quantification of compounds |
| JPH04286848A (en) * | 1991-03-15 | 1992-10-12 | Hitachi Ltd | Mass spectrometer |
| JP3147914B2 (en) * | 1991-03-18 | 2001-03-19 | 株式会社日立製作所 | Mass spectrometry method and mass spectrometer |
| US5397894A (en) * | 1993-05-28 | 1995-03-14 | Varian Associates, Inc. | Method of high mass resolution scanning of an ion trap mass spectrometer |
| JP2000195464A (en) * | 1998-12-25 | 2000-07-14 | Shimadzu Corp | Quadrupole mass spectrometer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110720133A (en) * | 2017-06-29 | 2020-01-21 | 株式会社岛津制作所 | Quadrupole rod mass spectrometry device |
| CN110720133B (en) * | 2017-06-29 | 2022-05-06 | 株式会社岛津制作所 | Quadrupole rod mass spectrometry device |
| CN114531769A (en) * | 2022-03-03 | 2022-05-24 | 清华大学 | Multi-energy extraction method of synchrotron |
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| CN102324377B (en) | 2015-01-07 |
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