WO2010052752A1 - Spectromètre de masse du type temps de vol à circulation multiple - Google Patents

Spectromètre de masse du type temps de vol à circulation multiple Download PDF

Info

Publication number
WO2010052752A1
WO2010052752A1 PCT/JP2008/003200 JP2008003200W WO2010052752A1 WO 2010052752 A1 WO2010052752 A1 WO 2010052752A1 JP 2008003200 W JP2008003200 W JP 2008003200W WO 2010052752 A1 WO2010052752 A1 WO 2010052752A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
ions
analysis condition
flight
time
Prior art date
Application number
PCT/JP2008/003200
Other languages
English (en)
Japanese (ja)
Inventor
山口真一
Original Assignee
株式会社島津製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to PCT/JP2008/003200 priority Critical patent/WO2010052752A1/fr
Priority to JP2010536592A priority patent/JP5327228B2/ja
Publication of WO2010052752A1 publication Critical patent/WO2010052752A1/fr

Links

Images

Classifications

    • 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
    • H01J49/408—Time-of-flight spectrometers with multiple changes of direction, e.g. by using electric or magnetic sectors, closed-loop time-of-flight

Definitions

  • the present invention is a multi-round time-of-flight time type in which ions are separated and detected according to mass (strictly, mass-to-charge ratio m / z value) by repeatedly flying ions derived from a sample along a closed orbit.
  • the present invention relates to a mass spectrometer.
  • TOFMS Time of Flight Mass Spectrometer
  • ions accelerated by applying a certain amount of energy each have a flight speed corresponding to the mass.
  • Mass spectrometry is performed by measuring the time of flight required for such ions to fly a certain distance and converting the time of flight to mass. Therefore, in order to improve the mass resolution, the flight distance may be increased. However, in order to extend the linear flight distance, it is necessary to enlarge the apparatus.
  • Multi-Turn-TOF-MS hereinafter abbreviated as “MT-TOFMS”
  • MT-TOFMS orbiting time-of-flight mass spectrometer
  • a multi-reflection time-of-flight mass spectrometer has been developed that extends the flight distance by using a reciprocating orbit that reflects ions multiple times by a reflected electric field instead of the orbit as described above.
  • the ion optical system is different between the multi-round time-of-flight type and the multiple reflection time-of-flight type, the basic principle for improving the mass resolution is the same. Therefore, in this specification, the “multiple orbit flight time type” includes the “multiple reflection flight time type”.
  • an object of the present invention is to provide a multi-turn time-of-flight mass spectrometer capable of acquiring analysis data having performance according to demand by a simple operation of a user. Is to provide.
  • the present invention which has been made to solve the above-mentioned problems, detects an ion source that ionizes a sample, an ion optical system that forms a circular orbit that repeatedly flies ions derived from the sample, and ions that fly along the circular orbit.
  • a multi-turn time-of-flight mass spectrometer comprising: a) information input means for the user to set mass information relating to the target mass or mass range and performance information relating to measurement performance requirements; b) Analysis condition calculation means for calculating an analysis condition satisfying at least the measurement performance for ions having a target mass or included in a mass range based on the set mass information and performance information; c) control means for controlling each part so that ions are introduced into the detector after flying along a circular orbit according to the analysis conditions calculated by the analysis condition calculation means; It is characterized by having.
  • the “mass information” may be a mass (strictly speaking, mass-to-charge ratio m / z) or a numerical value in the mass range, or may be information capable of deriving a mass such as a substance name or molecular formula.
  • the “analysis condition” can be, for example, either the number of times of ion circulation on the orbit or the timing of detachment of ions from the orbit.
  • the timing of ion detachment from the orbit is, for example, the elapsed time from when the ion departs from the ion flight starting point of the ion source etc. until it leaves the orbit after flying along the orbit. is there.
  • the analysis condition calculation means calculates the measurement performance given the ions having the mass. It is sufficient to calculate the analysis conditions that satisfy the conditions, but when mass range is given as mass information or multiple masses are given, consider the timing so that ions that circulate delay or lap advance do not leave the orbit simultaneously. There is a need to. Therefore, the analysis condition calculation means first calculates an analysis condition that satisfies the given measurement performance, and then determines whether or not different kinds of ions are mixed under the analysis condition. It is advisable to gradually change the analysis conditions so as to find analysis conditions in which different kinds of ions are not mixed.
  • the analysis condition calculation means cannot find an appropriate analysis condition in one measurement under a predetermined constraint condition, for example, a constraint condition within a specified measurement time range, a plurality of masses or masses
  • the analysis conditions may be found under the condition that the measurement is performed a plurality of times by dividing the range into a plurality of ranges. That is, a series of measurements of ionization on the same sample ⁇ ion mass separation using a circular orbit ⁇ ion detection may be performed a plurality of times for different masses and mass ranges.
  • the user only needs to input the mass of the component to be analyzed, the desired resolution or accuracy according to the purpose, and the appropriate analysis conditions according to the input.
  • the setting and analysis itself are performed automatically. Therefore, the user can easily obtain data satisfying the desired performance without performing troublesome operations and operations.
  • the resolution and accuracy may be low, the number of ion circulations is inevitably reduced, so that the time required for measurement is shortened, contributing to the efficiency of analysis work and the improvement of throughput.
  • FIG. 1 is a schematic configuration diagram of a multi-turn time-of-flight mass spectrometer according to an embodiment of the present invention.
  • the flowchart which shows the analysis procedure in the multi-turn time-of-flight mass spectrometer of a present Example.
  • FIG. 1 is a schematic configuration diagram of MT-TOFMS according to the present embodiment.
  • an ion source 1 a gate electrode 2, a flight space 3 in which a plurality of fan-shaped electrodes 31 to 36 are disposed, an ion detector 4, and the like are disposed in a vacuum chamber (not shown).
  • the ion source 1 serves as a starting point of flight of ions to be analyzed.
  • the ion source 1 is an ionization unit that ionizes sample molecules to be analyzed, and the ionization method is not particularly limited.
  • the ion source 1 ionizes gas molecules by an electron impact ionization method or a chemical ionization method.
  • the mass spectrometer is used as a detector for liquid chromatography
  • the ion source 1 ionizes liquid molecules by atmospheric pressure chemical ionization or electrospray ionization.
  • the analysis target molecule is a polymer compound such as a protein
  • MALDI Microx Assisted Laser Desorption Ionization
  • the ion source 1 is not necessarily an ion generation source.
  • the ion source 1 may be an ion trap that temporarily holds ions generated in other portions and then emits them with energy.
  • a plurality of (six in this example) fan-shaped electrodes 31, 32, 33, 34, 35, 36 are arranged in the flight space 3 in order to fly ions along a substantially circular orbit P. .
  • Each of the six fan-shaped electrodes 31 to 36 having the same shape is formed by cutting a concentric double cylinder at a rotation angle of 60 °, and the fan-shaped electrodes 31 to 36 are rotated at an equal rotation angle about the axis O. They are spaced apart.
  • a predetermined voltage is applied to the sector electrodes 31 to 36, sector electric fields E1 to E6 are formed therein, respectively, and a substantially hexagonal cylindrical flight space is formed in the sector electric fields E1 to E6.
  • the central trajectory of ions passing through the space is indicated by P in FIG.
  • the gate electrode 2 provided between the adjacent sector electrodes 31 and 36 puts the ions generated by the ion source 1 on the orbit P, and the ions flying along the orbit P. It has a function for separating from P and sending it to the i
  • Voltages are applied to the sector electrodes 31 to 36 and the gate electrode 2 from the orbital flight voltage generator 5 and the gate voltage generator 6, respectively, and the voltage generators 5 and 6 are controlled by the controller 7.
  • Connected to the control unit 7 are an operation unit 9 operated by a user to perform various input settings and instructions related to analysis, and a display unit 10 for displaying analysis results and the like.
  • the detection signal from the ion detector 4 is input to the data processing unit 8, where the flight time from when the ion leaves the ion source 1 to the ion detector 4 is measured, and based on this flight time. The mass of the ion is calculated.
  • the control unit 7 and the data processing unit 8 can be embodied with a personal computer as a center.
  • the circular orbit P has a substantially circular shape, but the shape of the circular orbit is not limited to this, and may be an arbitrary shape such as an oval shape or an 8-shaped shape. Further, it may reciprocate along a linear or curved track.
  • control unit 7 includes an analysis condition calculation unit 71 that calculates an analysis condition when the analysis is actually performed according to the analysis parameter set from the operation unit 9, and an analysis condition storage unit that stores the calculated analysis condition 72 as a functional block.
  • the basic mass analysis operation in the MT-TOFMS of this example is as follows. That is, in the ion source 1, components in the sample to be measured are ionized, and the generated ions are given kinetic energy and start from the ion source 1 almost simultaneously. Ions entering the flight space 3 reach the gate electrode 2 and are put on the circular orbit P by the action of the deflection electric field generated by the voltage applied to the gate electrode 2 from the gate voltage generator 6. Since various ions have a time difference corresponding to the mass before the ions emitted from the ion source 1 reach the gate electrode 2, unnecessary ions whose mass is significantly different from the ions to be observed should not be put on the circular orbit P. Further, by controlling the voltage applied to the gate electrode 2, it is possible to eliminate some unnecessary ions.
  • the ions on the circular orbit P continue to fly by the action of the sector electric fields E1 to E6 generated by the voltage applied to the sector electrodes 31 to 36 from the orbital flight voltage generator 5. As the number of laps increases, the flight distance becomes longer. Therefore, ions with close mass gradually move away on the orbit P. Then, the voltage applied to the gate electrode 2 is switched so that the ions leave the orbit P and travel toward the ion detector 4 when a predetermined time elapses from the time when the ions start from the ion source 1. Then, thereafter, the ions circulating on the circular orbit P leave the circular orbit P in the order of arrival at the gate electrode 2 and reach the ion detector 4.
  • ions having very close masses for example, isotope ions
  • ions having very close masses for example, isotope ions
  • a time-of-flight spectrum with high mass resolution can be obtained. If the number of rounds of the peak corresponding to each ion appearing in this time-of-flight spectrum is known, the flight distance can be obtained, so that the time-of-flight can be converted into mass to obtain the mass spectrum.
  • the user inputs and sets one or more masses (m / z values) or mass ranges of interest (to be observed) as mass information from the operation unit 9 (step S1).
  • the mass information is not necessarily a numerical value itself, but may be information that can be used to derive a numerical value, and may be a molecular formula or a substance name of a component of interest. It should be noted that the numerical values input and set here do not need to be exact. Further, the user inputs and sets numerical values of measurement performance such as mass resolution and mass accuracy from the operation unit 9 as performance information in accordance with the purpose of analysis (step S2).
  • the mass resolution may be selected by the user from numerical values prepared in advance such as 0.2, 0.1, 0.05, 0.02, 0.01,..., And the mass accuracy is the same. If the default value is acceptable, the input setting in step S2 can be omitted.
  • the control unit 7 When the analysis command including the mass information and measurement information as described above is input and set, and the user instructs to execute the analysis (step S3), the control unit 7 first analyzes based on the set mass information and measurement information. Calculate the analysis conditions necessary for the performance. Specifically, the analysis condition calculation unit 71 obtains the number of ion laps required to satisfy the mass resolution and mass accuracy set as measurement information for each mass set as mass information, and the number of laps Is calculated (step S4). This orbital departure time Tg is applied to the gate electrode 2 at such a voltage that ions on the circular orbit P leave the circular orbit P and go to the ion detector 4 from the time when the ions leave the ion source 1. Is the elapsed time until.
  • the orbital separation time Tg with respect to the observation target mass can be obtained by the following calculation.
  • the flight path length L depends on the number of laps.
  • N the lap length (distance of one lap) of the lap orbit P
  • L N ⁇ C (6) It is.
  • the number of laps can be obtained, and the lap turnout time Tg and the lap turnaround time Tg ′ can be obtained using the lap number.
  • the turn-off time Tg and the turn-around introduction time Tg ′ obtained by calculation need to have a certain allowable range.
  • the switching timing of the voltage applied to the gate electrode 2 is controlled according to the orbital separation time Tg and the orbital introduction time Tg ′ obtained as described above. Ions can be put on the orbit P, and the ions that have been orbited a predetermined number of times can be selectively guided to the ion detector 4.
  • the observation target masses or the observation target mass is set as a mass range, it is necessary to consider the mixing of different types of ions. This is because, when ions having different masses fly along the orbit P, low-mass and high-velocity ions catch up with and overtake the high-mass and low-velocity ions.
  • the analysis condition calculation unit 71 determines, for each orbital departure time Tg obtained for each mass to be observed, whether or not other ions that are not in the desired number of circulations are separated at the separation timing (step). S5).
  • the number of laps calculated in step S4 is changed to be increased by 1, for example, and the lap detachment time Tg is recalculated (step S6). If the number of laps is increased, the mass resolution and mass accuracy do not decrease, so that these measurement performances can be satisfied. Thereafter, it is determined whether or not a constraint condition such as a preset maximum measurement time is satisfied (step S7), and if satisfied, the process returns to step S5 to re-determine whether or not the lap departure time Tg is appropriate. To do. By the determination in step S7, it can be avoided that the number of laps is much larger than the desired number of laps obtained by calculation first.
  • step S7 If it is determined in step S7 that the constraint condition is not satisfied, it is determined that an appropriate analysis condition cannot be set. This may be due to factors such as the number of set masses being too large or the mass range being too wide. Mass analysis that satisfies the set measurement performance can be performed with a single measurement. Means no. Therefore, the above-described analysis conditions are determined under the condition that a plurality of given masses are appropriately divided into a plurality of parts, a mass range is divided into a plurality of narrow mass ranges, and a plurality of measurements are performed (step S9). ).
  • step S5 if it is determined in step S5 that the orbital departure time Tg for each of the one or more observation target masses is appropriate, the orbital departure time Tg at that time is determined as an analysis condition and stored in the analysis condition storage unit 72. Store (step S8).
  • the control unit 7 emits ions derived from the sample to be measured from the ion source 1 as described above, and the analysis of the switching of the applied voltage from the gate voltage generating unit 6 to the gate electrode 2 is performed.
  • mass analysis of observation object ion is performed (step S10).
  • the data processing unit 8 acquires a time-of-flight spectrum, and converts the time-of-flight into mass, thereby creating a mass spectrum in which the peak of the observation target ion appears (steps S11 and S12).
  • the time-of-flight spectrum is acquired by sequentially executing the second and subsequent measurements after each measurement is completed. Create a spectrum. In this case, a separate mass spectrum may be created for each measurement, but this may be integrated into one mass spectrum.
  • the user only has to input and set information such as the mass to be observed and the mass resolution according to the purpose. No special experience or knowledge is required.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

Avant de lancer une analyse, l’utilisateur règle des paramètres comme la masse d’ions à observer ou la résolution de la masse en fonction d’un objectif à partir d’une unité opérationnelle (9). Une unité opérationnelle de condition analytique (71) d’une unité de commande (7) détermine un nombre de circulations tel que la résolution de masse des ions à observer corresponde à la résolution de masse établie, et calcule le moment où les ions sur une orbite de circulation (P) doivent être libérés à partir de ce nombre de circulations, établissant ainsi le moment pour une condition analytique. Si d’autres ions à observer émanent à ce moment, le nombre de circulations est modifié, et le moment de libération est recalculé. Si nécessaire, plusieurs mesures sont effectuées avec des masses divisées afin de déterminer les conditions analytiques pour les mesures individuelles. Si les conditions analytiques permettant d’obtenir la résolution de masse voulue sont déterminées pour les ions à observer individuels, l’unité de commande (7) va commander les unités individuelles en fonction des conditions analytiques stockées dans une unité de stockage de conditions analytiques (72), permettant ainsi de lancer l’analyse de masse des ions à observer. Par conséquent, il n’est pas nécessaire que l’utilisateur effectue des calculs compliqués du nombre de circulations, ce qui permet d’accroître le côté pratique et la fonctionnalité.
PCT/JP2008/003200 2008-11-05 2008-11-05 Spectromètre de masse du type temps de vol à circulation multiple WO2010052752A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2008/003200 WO2010052752A1 (fr) 2008-11-05 2008-11-05 Spectromètre de masse du type temps de vol à circulation multiple
JP2010536592A JP5327228B2 (ja) 2008-11-05 2008-11-05 多重周回飛行時間型質量分析装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/003200 WO2010052752A1 (fr) 2008-11-05 2008-11-05 Spectromètre de masse du type temps de vol à circulation multiple

Publications (1)

Publication Number Publication Date
WO2010052752A1 true WO2010052752A1 (fr) 2010-05-14

Family

ID=42152569

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/003200 WO2010052752A1 (fr) 2008-11-05 2008-11-05 Spectromètre de masse du type temps de vol à circulation multiple

Country Status (2)

Country Link
JP (1) JP5327228B2 (fr)
WO (1) WO2010052752A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005116343A (ja) * 2003-10-08 2005-04-28 Shimadzu Corp 質量分析方法及び質量分析装置
JP2006059739A (ja) * 2004-08-23 2006-03-02 Jeol Ltd 質量分析方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0622689D0 (en) * 2006-11-14 2006-12-27 Thermo Electron Bremen Gmbh Method of operating a multi-reflection ion trap

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005116343A (ja) * 2003-10-08 2005-04-28 Shimadzu Corp 質量分析方法及び質量分析装置
JP2006059739A (ja) * 2004-08-23 2006-03-02 Jeol Ltd 質量分析方法

Also Published As

Publication number Publication date
JP5327228B2 (ja) 2013-10-30
JPWO2010052752A1 (ja) 2012-03-29

Similar Documents

Publication Publication Date Title
Shvartsburg et al. Modeling the resolution and sensitivity of FAIMS analyses
JP5198260B2 (ja) 質量スペクトル測定における複数イオン注入
JP4033133B2 (ja) 質量分析装置
JP4182843B2 (ja) 飛行時間型質量分析装置
WO2018109920A1 (fr) Dispositif de spectrométrie de masse
JP4569349B2 (ja) 飛行時間型質量分析装置
JP6305543B2 (ja) 標的化した質量分析
JP2003123685A (ja) 質量分析装置およびこれを用いる計測システム
JP5024387B2 (ja) 質量分析方法及び質量分析システム
JP4182853B2 (ja) 質量分析方法及び質量分析装置
WO2010038260A1 (fr) Spectromètre de masse de temps de vol multitours
JP5136650B2 (ja) 質量分析装置
JP6627979B2 (ja) 質量分析装置
JP5126368B2 (ja) 質量分析方法
US8093555B2 (en) Mass spectrometer
JP6022383B2 (ja) 質量分析システム、及び方法
JP5327228B2 (ja) 多重周回飛行時間型質量分析装置
JP6160472B2 (ja) 飛行時間型質量分析装置
JP5972662B2 (ja) タンデム飛行時間型質量分析計
JP2005322429A (ja) 質量分析装置
JP4273917B2 (ja) 質量分析装置
JP2006012747A (ja) 飛行時間型質量分析装置
JP2005116246A (ja) 質量分析装置
Nagao et al. Development of a miniaturized multi-turn time-of-flight mass spectrometer with a pulsed fast atom bombardment ion source
JP7225743B2 (ja) スペクトル演算処理装置、スペクトル演算処理方法、スペクトル演算処理プログラム、イオントラップ質量分析システムおよびイオントラップ質量分析方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08877948

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010536592

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08877948

Country of ref document: EP

Kind code of ref document: A1