WO2007077245A1 - Procédé et appareil pour la spectrométrie de masse de temps de vol en tandem sans sélection de masse primaire - Google Patents

Procédé et appareil pour la spectrométrie de masse de temps de vol en tandem sans sélection de masse primaire Download PDF

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Publication number
WO2007077245A1
WO2007077245A1 PCT/EP2007/050059 EP2007050059W WO2007077245A1 WO 2007077245 A1 WO2007077245 A1 WO 2007077245A1 EP 2007050059 W EP2007050059 W EP 2007050059W WO 2007077245 A1 WO2007077245 A1 WO 2007077245A1
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Prior art keywords
fragment
flight
mass
fragments
charged
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PCT/EP2007/050059
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English (en)
Inventor
David Scigocki
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Physikron
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Priority claimed from FR0600036A external-priority patent/FR2895832A1/fr
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Publication of WO2007077245A1 publication Critical patent/WO2007077245A1/fr

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/025Detectors specially adapted to particle spectrometers
    • 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

Definitions

  • the present invention relates to a method for mass spectrometry and to an apparatus capable of implementing this method.
  • the present invention relates to a tandem, time-of-flight (TOF) mass spectrometry method without primary mass selection.
  • TOF time-of-flight
  • MS-MS tandem mass spectrometry
  • tandem, time-of-flight mass spectrometers without primary mass selection are also known.
  • Time-of-flight (TOF) mass spectrometry includes in particular the general steps consisting in accelerating a ion packet with an electrical field applied in vacuum, and in measuring the difference in their time of arrival on a ion detector after having traveled through a time-of-flight distance in a determined time-of-flight space.
  • the ions having the smaller M/Q rations reach the detector before the ions having greater M/Q ratios.
  • One advantage of the TOF spectrometry is its capacity to measure the masses of all ions at the same time.
  • the sensitivity and the acquisition speed of the TOF systems are thus improved relative to other systems based on the principle of the measurement of one mass at a time and a subsequent scanning on all the masses.
  • a first type of these tandem mass spectrometers (MS-TOF) with primary mass selection relies on two successive TOF times spectrometers (TOF-TOF and a time window for performing said mask selection after the dissociation between these two TOF mask spectrometers.
  • a second type of these spectrometers relies on the time frame at the second mass spectrometer only and a scanning system for the first mass spectrometers.
  • the ions penetrating inside the reflectron are then reflected and re-focussed on the ion detector.
  • the ions having the greater kinetic energy, and therefore the faster ones enter more deeply into the reflectron, and spend there more time there than the ions of same mass but having a lower kinetic energy (therefore slower).
  • tandem mass spectrometers with mass selection can generate only one secondary dissociation spectrum at a time.
  • a first known TOF mass spectrometry method without primary mass selection [1] is known, which consists in simultaneously measuring the time of flight and the kinetic energy of each charged fragment.
  • This method has been implemented in an apparatus made of :
  • This method operates both for single charge and multiple charge ions.
  • the dissociation mass spectra are obtained by selecting with the electrostatic sector all the possible kinetic energy to charge ratios E/q of the fragments.
  • a TOF mass spectrum is generated for each E/q ratio selected by the electrostatic sector.
  • a second TOF mass spectrometry method allowing to generate dissociation spectra without primary mass selection [2] is also known.
  • This method relies upon a reflectron and operates only with single charge primary ions.
  • this method consists in particular in measuring the times of flight of these fragments originating from each primary ion before dissociation.
  • this method provides that each dissociated primary ion generates a neutral fragment and a charged fragment having the same velocity and the same direction as their parent primary ion between the ion source and the reflectron.
  • Two mass spectra corresponding respectively to the time of flight measurements generated by the two detectors are obtained at the same time by accumulating the dissociation events of all the primary masses present in the analyzed sample.
  • Each dissociation spectrum corresponding to a primary mass value is then obtained from the two above-mentioned mass spectra, i.e. a mass spectrum for the neutral fragments and another one for the charged fragments.
  • the mass peak corresponding to the primary ion for which the dissociation spectrum is sought is selected.
  • a third TOF mass spectrometry method without primary mass selection is known, which uses two TOF mass spectrometers separated by a dissociation system in which a variable intensity electrical field is applied [3].
  • this method lacks accuracy for identifying the different dissociation spectra corresponding to different primary masses close to each other.
  • this method requires several acquisitions for identifying the mass peaks which overlap in the obtained mass spectrum.
  • a fourth TOF mass spectrometry method without primary selection is known, which uses a reflectron [4].
  • Each dissociation spectrum is identified by the relative movement of the various TOF mass peaks which is characteristic of each dissociation spectrum.
  • the identification of the various dissociation spectra corresponding to the various primary masses remains difficult in mass spectra having a high density of primary peaks.
  • This method can therefore be used only which samples comprising a small number of different molecules, and therefore a small number of different primary mass peaks.
  • a fifth TOF mass spectrometry method without primary mass selection is known, which is based on the transformation of the times of flight into measured positions [5].
  • This method relies upon a TOF mass spectrometer made of a pulsed ion source, a dissociation system, a second orthogonal pulsation system, and a ion detector capable of measuring the arrival position and the time of flight of the ions.
  • the primary ion originating from the first pulsation of the primary ion beam are accelerated along a direction.
  • the time of flight difference due to the difference between the velocities of different ions corresponds to a difference in position along the axis parallel to the primary ion beam.
  • a second pulsation is then applied on the fragments by the orthogonal pulsation system.
  • the primary range is limited by the length of the detector which is used.
  • An objective of this invention is to remedy the drawbacks of the state of the art such as explained herein above, in the case of single charge primary ions.
  • a purpose of the invention is to provide a mass spectrometry method without primary mass selection which is capable of generating at the same time, through a single acquisition, all the dissociation spectra for all the various primary mass present in a sample to be analyzed.
  • the present invention provides a method for tandem time-of- flight mass spectrometry without primary mass selection, comprising a step of ionization of molecules which, once ionized, form respective single charge primary ions, the method further comprising the following steps:
  • the identification step includes determining a trajectory of each fragment of the fragment pairs between the device input and the or each detector by determining its position on the or each detector.
  • the identification step includes determining a velocity of each fragment of the fragment pairs between the device input and the or each detector by determining its time of flight.
  • the method further comprises a step of generating a 3D spectrum of identified fragment pairs, this spectrum comprising on the one hand two axes representing the times of flight of the neutral fragments and of the charged fragments, respectively, and on the other hand a third axis representing a detection occurrence of fragment pairs on the or each detector.
  • the method further comprises using two detectors for detecting the neutral fragments and the charged fragments, respectively.
  • the present invention provides a tandem time- of-flight mass spectrometer without primary mass selection, comprising means for ionizing molecules, means for dissociating single charge primary ions formed by said molecules once ionized, said dissociation means being capable of transforming each primary ion into a neutral fragment and a charged fragment forming together a fragment pair, a device for applying an electrical and/or magnetic field to the fragments in order to change, depending on their mass, the times of flight of the charged fragments between an input of this device and at least one detector comprised in the spectrometer and on which said fragments arrive, wherein
  • the spectrometer further comprises means for differentiating each of the neutral and charged fragment pairs on the basis of a criterion involving the measured positions and the measured times of flight of the detected fragments, so as to make possible the generation of different dissociation spectra each defined as comprising the charged fragments which originate from the dissociation of primary ions of a same mass.
  • FIG. 1 is a block-diagram of a preferred embodiment of the method of this invention
  • - Figure 2 illustrates by way of a non-limiting example the main components of a spectrometer capable of implementing the method of the invention
  • - Figure 3 shows a TOF mass spectrometer according to a preferred embodiment of the invention, which comprises in particular a reflectron, and
  • tandem TOF mass spectrometry method without primary mass selection of the invention is based on an identification of all the dissociated fragment pairs.
  • the method according to the preferred embodiment of the invention comprises in particular the steps which will be explained hereinunder and illustrated in figure 1.
  • the molecules are first ionized in a pulsed single charge ion source 100.
  • the single charge primary ions thus produced are in addition accelerated by an electrical field up to a velocity which varies depending on their mass to charge ratio M/Q.
  • part of these primary ions is fragmented, or dissociated, in a dissociation system 200 without primary mass selection.
  • the fragmentation generates a pair of a neutral fragment and a charged fragment for each dissociated single charge primary ion.
  • Each of these pairs of neutral and charged fragments generated by the dissociation retains approximately the same velocity and the same trajectory as their parent primary ion at the time of dissociation, and this is true up to the input of a device 300.
  • a step 12 is performed, which consists in particular in applying an electrical or magnetic field.
  • each neutral fragment keeps approximately the same velocity and the same trajectory as its parent primary ion between device 300 and at least one detector 400 placed downstream in the direction of the ions and the fragments.
  • the time of flight TOF tot (m n ) of each neutral fragment between the pulsed ion source 100 and the ion detector 400 is therefore approximately the one which its parent primary ion would have if the electromagnetic field of device 300 did not exist.
  • the time of flight space between device 300 and ion detector 400 the time of flight of each charged fragment is changed by the electrical or magnetic field.
  • this time of flight is made dependent from the mass of each charged fragment, because the field changes their velocity and/or their trajectory depending on their mass to charge ratio.
  • the time of flight TOF tot (m c ) between the pulsed ion source 100 and the ion detector 400 for each charged fragment is changed as a function of its mass, compared to the time of flight that its parent primary ion would have.
  • a step 13 of the method two measurements with ion detector 400 are then simultaneously made.
  • the time of flight as well as the position of arrival of each neutral and charged fragment coming on detector 400 are measured.
  • each pair originating from one same dissociation event i.e. each pair originating from a same parent ion, is identified among the whole fragment set.
  • this event is included in the set of all dissociation events which have happened during a time of flight cycle.
  • the identification of the fragment pair is made possible by virtue of the above- mentioned measurement, at the ion detector 400, of the time of flight and arrival position of each neutral and charged fragment.
  • the measured positions and times of flight of the neutral and charged fragments are used in order to determine the trajectories and the velocities of these fragments. Then these trajectories and velocities allow in a very simple manner to identify each of the pairs, i.e. to retrieve among the set of all detected fragments which neutral fragment originates from the same parent primary ion as such or such charged fragment.
  • the skilled person will thus understand that, from the identified fragment pairs, it is possible to generate one or several dissociation spectra, in various manners.
  • each dissociation spectrum corresponding to a primary mass value can be obtained from the generation of a mass spectrum for the neutral fragments and a mass spectrum for the charged fragments.
  • the mass peak corresponding to the primary mass for which the dissociation spectrum is sought is then selected in the mass spectrum of the neutral fragments.
  • said dissociation spectrum is generated by selecting, in the charged fragment spectrum, the charged fragments corresponding to the selected neutral fragment.
  • the set of all dissociation spectra is generated at the same time in a step 15, in the form of a 3D correlation mass spectrum as shown by way of example in figure 4.
  • the 3D spectrum according to the invention includes a first axis representing the time of flight values of each neutral fragment TOF tot (m n ), a second axis (preferably perpendicular) representing the time of flight values of each charged fragment TOF to t(m c ), and a third axis (preferably perpendicular to the two others) representing the number of events, or else the detection occurrences of the identified fragment pairs.
  • the pair designated by reference Pl has the coordinates (TOFl, TOF2, Nl), TOFl and TOF2 being the time of flights measured for the neutral fragment and the charged fragment of this pair, and Nl corresponding to the number of times this pair has been detected at values TOFl and TOF2 in the mass peak.
  • the method of the invention is advantageous in that it can generate simultaneously all the dissociation spectra in the form of the 3D dissociation spectrum.
  • another 3D spectrum may correspond to a situation where TOF t ot(m n ) and TOF to t(m c ) are replaced with functions of this values (for instance
  • each dissociation spectrum corresponding to each primary mass value present in the analyzed sample is first identified in the 3D mass spectrum, through the position in a plane ⁇ TOF tot On)'TOF tot Oc) ⁇ of a straight line parallel to the axis of the times of flight of the charged fragments. More precisely, this straight line connects the maxima of the number of events for each dissociation mass peak belonging to the same dissociation spectrum.
  • line Dl connects the maxima of pairs Pl, P2 and P3.
  • this line Dl is characteristic of the primary mass Ml.
  • the position of each straight line D in the plane ⁇ TOF tot On)'TOF tot Oc) ⁇ is characteristic of the value of a specific primary mass value M.
  • the value of the masses of primary ions and of dissociated charged fragments of yet unknown molecules can for instance be determined as a step preliminary to the performance of the method of the invention by calibrating the positions of the mass peak maxima along the axes of the neutral and charged fragments in the 3D spectrum.
  • the calibration can be performed in relation with molecules having known primary masses and dissociation spectra.
  • a primary mass selection device such as for instance a time gate, can be incorporated in the system and used for calibration.
  • the above-mentioned mass selection device can also be used to select all the primary mass peaks for each laser pulse, so as to limit this continuous background noise (so-called multigating technique).
  • each dissociation mass spectrum is obtained at step 16 by projecting the mass peaks of the characteristic lines on the axis of the times of flight of the dissociated charged fragments.
  • the pulsed ion source 100 can be a single charge ion source such as : - a pulsed laser desorption-ionization source (MALDI for "Matrix-Assisted
  • EI source an electronic impact ionization source
  • API source an atmospheric pressure ionization source
  • CI source chemical ionization source
  • APCI source atmospheric pressure chemical ionization source
  • FI source field ionization source
  • FD source field desorption source
  • LDM source laser desorption ionization source
  • DIOS source desorption/ionization on silicon source
  • ICP source inductively-coupled plasma source
  • the ions generated by ion source 100 can be stored in a ion trap or in any other ion storage system before pulsating the ion beam toward the time of flight zone.
  • the acceleration of the ions generated in the ion source 100 can be produced by an electrical field.
  • the extraction of the ions from this source 100 can be made at constant energy, at constantMlpulse or by any method giving to the ions a velocity which depends from their mass to charge ratio.
  • the pulsation of the ion beam can be made at the ion source 100 or between the latter and device 300.
  • the pulsation of the ion beam can be made by laser pulse, by continuous ion beam scanning through a slot by means of a variable electrical field applied between two deflections plates, by means of a technique known as orthogonal injection by applying a variable electrical field between two electrodes in a direction perpendicular to the ion beam, or by any other ion beam pulsation device.
  • the dissociation system 200 can be a collision box containing a gas allowing collision-induced dissociation (OD) at a high kinetic energy level, a time of flight space allowing spontaneous dissociation (PSD for "Post Source Decay") after increasing the internal energy of the ionized primary molecule by absorption of photons in the ion source 100 or downstream of the latter (photodissociation), or any other primary ion fragmentation device.
  • OD collision-induced dissociation
  • PSD spontaneous dissociation
  • Device 300 can be a reflectron, or else two deflection plates between which an electrical field is applied, or a collision box in which a potential allowing to re- accelerate the dissociated charged fragments at the output of the box is applied, or a combination of the above devices, or else any device where an electrical or magnetic field is applied and allows to change the time of flight of the charged fragments between device 300 and ion detector 400, compared to the time of flight that their parent primary ion would have (for instance a device that can change the velocity and/or the trajectory of the charged fragments).
  • It includes a pulsed single charge ion source 100, a dissociation device 200, a reflectron 300, a first ion detector 400a intended to detect neutral fragments 600 and allowing to measure at the same time their time of flight and their arrival position on detector 400a, and a second ion detector 400b detecting charged fragments 700 and allowing to measure at the same time their time of flight and their arrival position on detector 400b.
  • the first detector 400a is aligned with reflectron 300, dissociation device 200 and source 100, along a main axis of the spectrometer which substantially corresponds to the direction of propagation of neutral fragments 600.
  • the second detector 400b is arranged, relative to the reflectron, on the sode opposite the first detector 400a.
  • the second detector 400b is located on the side of source 100 and dissociation device 200. Indeed, this detector 400b has to be located on the way of the charged fragments, the time of flight of which is changed in reflectron 300 by the change of their respective trajectories.
  • the pulsed ion source 100 can be a pulsed laser source comprising a MALDI target and a Nd: YAG type laser emitting at a wavelength of 355 nm, with pulse durations lower than 600 ps and operating at a pulsation frequency of 1 kHz, with an average energy per pulse of 15 ⁇ J.
  • the dilution rate of the molecules in the MALDI source must be greater (by several orders of magnitude) than those of current commercial apparatus in order to limit the number of primary ions per laser pulse.
  • the counting electronics allows to detect at most one ion per time channel and per laser pulse.
  • an individual detection of the fragments is necessary in order that the method of the invention can identify each pair of dissociated neutral and charged fragments.
  • the dissociation device 200 preferably is a collision box containing a gas promoting by high kinetic energy CID metastable spontaneous fragmentation (PSD for "Post Source Decay") of the primary ions in the time of flight space between the MALDI source 100 and the refiectron 300.
  • PSD kinetic energy CID metastable spontaneous fragmentation
  • the primary ions which dissociate have been previously excited in the MALDI source by laser pulses having power densities equal to or greater than 10 7 W/m 2 .
  • Detectors 400a and 400b each comprise two superimposed microchannel wafers and two superimposed anode planes each made of a delay line. These two planes allow to measure the 2D arrival position (X, Y) of each ion on the microchannel wafers.
  • the measurement is made in the following manner.
  • An ion having reached the entry of a channel at the upper part of the microchannel wafer generates an electron avalanche at the output of this wafer.
  • Part of the generated electrons are collected by the delay line.
  • the arrival position of each detected ion is then determined by measuring the arrival time difference at each end of the delay line, compared to a non-delayed signal generated by part of the electron avalanche.
  • the non-delayed signal is for instance detected by a grid placed upstream of the delay line planes. This signal also allows to measure the time of flight of the detected ion.
  • Each delay line plane allows to determine the one-dimension arrival position of each ion.
  • the two planes allow to measure the 2D arrival position (X, Y) of the ion on the detector.
  • each delay line is provided with two identical electronic acquisition circuitries which measure the signal at each end of each delay line.
  • An additional electronic acquisition channel is used for the non-delayed signal.
  • the detector is thus equipped with at least five electronic acquisition channels each comprising an amplifier, a constant fraction discriminator and a time digital converter (TDC).
  • TDC time digital converter
  • the positional resolution of the detector depends from the characteristics of the time digital converter TDC which is used. The positional resolutions obtained with this type of detector are lower than
  • the device 300 used in this example can be either a single-stage reflectron, or a curved field reflectron CFR.
  • the spectrometer of the invention as described above implements the method of the invention in the following manner.
  • the neutral and charged fragments which are formed retain substantially the same velocity and the same direction as their parent primary ion up to the entry into reflectron 300. In a similar way, the neutral fragments retain substantially the same velocity and the same direction as their parent primary ion between the input of reflectron 300 and the ion detector 400a where they are detected.
  • the length of penetration of a charged fragment into the volume of reflectron 300 depends on its mass and is lower than that of its parent primary ion because its kinetic energy is lower.
  • the time of flight and the position of arrival on ion detector 400a are measured for each neutral fragment.
  • time of flight and the position of arrival on ion detector 400b are measured for each charged fragment.
  • each neutral fragment easily allows to determine at the same time, at least approximately, both its velocity, the velocity of the parent primary ion and the velocity of the charged fragment which is supposed to have been associated when it entered the reflectron.
  • a set of possible trajectories in the reflectron 300 due to the angular dispersion at the entry into the reflectron, the position of emission of the parent primary ion and the position of arrival of the charged fragment on the ion detector, is determined.
  • These trajectories are estimated by combining the measurement of its position on detector 400b with said positions and said trajectories determined up to the entry into reflectron 300. Then, from the velocities of the charged fragment at the entry in reflectron 300; which have been determined (cf. supra), and from said possible trajectories, a set of possible times of flight for the selected charged fragment is estimated.
  • each possible time of flight correspond to one possible trajectory and one possible velocity.
  • the neutral fragment originating from the same dissociation event as a selected charged fragment is the neutral fragment whose velocity and trajectory at the entry into reflectron 300 lead to the measured time of flight of said selected charged fragment.
  • the identification of each pair thus made allows to obtain all the dissociation spectra of the analyzed molecules, whether by a conventional method or by a method of the invention as described in the foregoing, which comprises generating a 3D spectrum.
  • the background noise due to the non-dissociated primary ions can be eliminated by applying to the reflectron 300 a voltage which is slightly smaller to the voltage used for accelerating the primary ions, in order that these ions are not re-focussed on the ion detector 400va and travel through the reflectron 300.
  • a device such as a set of deflection plates is then provided, the plates beings positioned between the upper part of the reflectron 300 and the ion detector 400a, so as to eliminate these primary ions and avoid that they are detected by ion detector 400a used for detecting the dissociated neutral fragments.

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

Abstract

La présente invention concerne un procédé et appareil pour la spectrométrie de masse de temps de vol en tandem sans sélection de masse primaire, comprenant une étape d'ionisation de molécules qui, une fois ionisées, forment des ions primaires à charge simple respective, le procédé comprenant également les étapes suivantes: la dissociation d'au moins une partie des ions primaires à charge simple afin d'obtenir pour chacun d'eux, un fragment neutre et un fragment chargé formant ensemble une paire de fragments; l'application d'un champ électrique et/ou magnétique prédéterminé aux paires de fragments au moyen d'un dispositif afin de modifier, en fonction de leur masse, les temps de vol des fragments chargés entre une entrée de ce dispositif et au moins un détecteur; la détermination du temps de vol ainsi que de la position d'arrivée sur le ou chaque détecteur des fragments neutres et chargés; suivie de l'identification de chacune des paires de fragments selon un critère intégrant les positions mesurées et les temps de vol mesurés des paires de fragments neutres et chargés qui sont parvenus au ou à chaque détecteur, afin de permettre la génération de spectres de dissociation différents chacun défini comme comportant les fragments chargés dérivés de la dissociation d'ions primaires d'une même masse. La présente invention concerne également un spectromètre de masse apte à la mise en oeuvre du procédé, et un spectre de masse en trois dimensions généré selon le procédé.
PCT/EP2007/050059 2006-01-03 2007-01-03 Procédé et appareil pour la spectrométrie de masse de temps de vol en tandem sans sélection de masse primaire WO2007077245A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0600036A FR2895832A1 (fr) 2006-01-03 2006-01-03 Procede de spectrometrie de masse en tandem a temps de vol sans selection de masse primaire par identification de chaque paire de fragments dissocies
FR0600036 2006-01-03
FR0602920 2006-04-04
FR0602920A FR2895833B1 (fr) 2006-01-03 2006-04-04 Procede et systeme de spectrometrie de masse en tandem sans selection de masse primaire et a temps de vol

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Cited By (3)

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US8847152B2 (en) 2009-11-30 2014-09-30 Physikron Sa Multiplexed tandem mass spectrometry method
DE102012203150B4 (de) * 2011-03-30 2015-10-01 Agilent Technologies, Inc. (N.D.Ges.D. Staates Delaware) Massenspektrometer und masseanalysator, der einen impulsgeber aufweist
CN108376637A (zh) * 2018-04-19 2018-08-07 南京信息工程大学 实现对自由飞行区解离碎片分辨的离子速度成像仪

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WO2009080833A2 (fr) * 2007-12-26 2009-07-02 Physikron Procédé et système de spectrométrie de masse en tandem sans sélection primaire en masse des ions monochargés

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US4472631A (en) * 1982-06-04 1984-09-18 Research Corporation Combination of time resolution and mass dispersive techniques in mass spectrometry
US4894536A (en) * 1987-11-23 1990-01-16 Iowa State University Research Foundation, Inc. Single event mass spectrometry
EP0378281A2 (fr) * 1984-02-29 1990-07-18 Centre National De La Recherche Scientifique (Cnrs) Spectromètre de masse à temps de vol
US5898173A (en) * 1996-09-03 1999-04-27 Bruker Daltonik Gmbh High resolution ion detection for linear time-of-flight mass spectrometers
US6031227A (en) * 1995-11-03 2000-02-29 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Time-of-flight mass spectrometer with position-sensitive detection

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Publication number Priority date Publication date Assignee Title
US4472631A (en) * 1982-06-04 1984-09-18 Research Corporation Combination of time resolution and mass dispersive techniques in mass spectrometry
EP0378281A2 (fr) * 1984-02-29 1990-07-18 Centre National De La Recherche Scientifique (Cnrs) Spectromètre de masse à temps de vol
US4894536A (en) * 1987-11-23 1990-01-16 Iowa State University Research Foundation, Inc. Single event mass spectrometry
US6031227A (en) * 1995-11-03 2000-02-29 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Time-of-flight mass spectrometer with position-sensitive detection
US5898173A (en) * 1996-09-03 1999-04-27 Bruker Daltonik Gmbh High resolution ion detection for linear time-of-flight mass spectrometers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8847152B2 (en) 2009-11-30 2014-09-30 Physikron Sa Multiplexed tandem mass spectrometry method
DE102012203150B4 (de) * 2011-03-30 2015-10-01 Agilent Technologies, Inc. (N.D.Ges.D. Staates Delaware) Massenspektrometer und masseanalysator, der einen impulsgeber aufweist
CN108376637A (zh) * 2018-04-19 2018-08-07 南京信息工程大学 实现对自由飞行区解离碎片分辨的离子速度成像仪
CN108376637B (zh) * 2018-04-19 2023-05-26 南京信息工程大学 实现对自由飞行区解离碎片分辨的离子速度成像仪

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FR2895833A1 (fr) 2007-07-06

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