WO2022249291A1 - Dispositif de spectrométrie de masse à ionisation par électronébulisation de sonde - Google Patents

Dispositif de spectrométrie de masse à ionisation par électronébulisation de sonde Download PDF

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WO2022249291A1
WO2022249291A1 PCT/JP2021/019834 JP2021019834W WO2022249291A1 WO 2022249291 A1 WO2022249291 A1 WO 2022249291A1 JP 2021019834 W JP2021019834 W JP 2021019834W WO 2022249291 A1 WO2022249291 A1 WO 2022249291A1
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mass
analysis
ions
ion source
ionization
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PCT/JP2021/019834
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English (en)
Japanese (ja)
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匡 村田
英志 井本
和樹 小松
留偉 千葉
芙美 川内谷
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株式会社島津製作所
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Priority to PCT/JP2021/019834 priority Critical patent/WO2022249291A1/fr
Priority to JP2023523768A priority patent/JPWO2022249291A1/ja
Publication of WO2022249291A1 publication Critical patent/WO2022249291A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission

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  • the present invention relates to a mass spectrometer equipped with an ion source based on the probe electrospray ionization (PESI) method.
  • PESI probe electrospray ionization
  • Patent Document 1 and Non-Patent Document 1 disclose a triple quadrupole mass spectrometer equipped with an ion source based on the PESI method.
  • an ion source based on the PESI method will be referred to as a PESI ion source
  • a mass spectrometer equipped with the PESI ion source will be referred to as a PESI mass spectrometer.
  • PESI mass spectrometers can simplify the complicated and time-consuming sample pretreatment work, so simple and rapid analysis is possible. Moreover, by using a PESI mass spectrometer, it is possible to observe temporal changes in the amount of a specific component in living tissues of living experimental animals or the like in real time.
  • PESI mass spectrometers unlike liquid chromatograph mass spectrometers (LC-MS), do not separate components by chromatography, so samples may contain a wide variety of components. Therefore, in many cases, a mass spectrum obtained by a PESI mass spectrometer contains ion peaks derived from a large number of components contained in the sample.
  • Non-Patent Document 1 the features of the triple quadrupole mass spectrometer are utilized to perform MS/MS analysis targeting a specific component. Specifically, by performing multiple reaction monitoring (MRM) measurement and product ion scan measurement, it is possible to accurately perform qualitative (identification) and quantitative determination of a specific component. This is very effective for drugs and toxic substances screening for listed prohibited substances.
  • MRM multiple reaction monitoring
  • the present invention has been made to solve these problems, and its object is to provide a simple and short measurement time for comprehensive analysis of various components contained in a sample. It is to provide a mass spectrometer.
  • an ion source by the probe electrospray ion method comprising a mass filter that selects specific ions among the ions generated by the ion source; a collision cell that dissociates ions selected by the mass filter; a mass analyzer including an orthogonal acceleration time-of-flight mass separator and an ion detector for mass analyzing product ions generated in the collision cell; an ion source control unit for controlling the ion source so as to repeat an operation of collecting the same sample and an operation of ionizing the collected sample by the ion source; When sampling and ionization of the sample are repeatedly performed in the ion source, ions having a mass-to-charge ratio included in a window of a predetermined mass-to-charge ratio width are allowed to pass through the mass filter, and the ions are filtered to the The operation of dissociating in the collision cell and acquiring the mass spectrum of the product ions generated by the
  • MS / MS analysis is performed by the DIA (Data Independent Acquisition) method, but the mass-to-charge ratio (m /z) width is considerably narrower than MS/MS analysis by the general DIA method. Therefore, even when a sample contains a large number of components, product ions derived from a plurality of components are less likely to be mixed in one MS/MS spectrum. Therefore, according to the PESI mass spectrometer according to the present invention, high-purity MS/MS spectra respectively corresponding to a plurality of components contained in a sample, including target components and contaminant components, can be easily measured in a short time. can be exhaustively obtained, and each component can be identified with high accuracy.
  • DIA Data Independent Acquisition
  • FIG. 1 is a schematic configuration diagram of an embodiment of a PESI mass spectrometer according to the present invention
  • FIG. FIG. 2 is a conceptual diagram showing an example of the relationship between the m/z range to be measured and one precursor ion to be analyzed by MS/MS in the PESI mass spectrometer of the present embodiment.
  • FIG. 2 is a conceptual diagram showing an example of the relationship between the operation cycle of the ion source and the timing of the mass spectrometry operation in the PESI mass spectrometer of the present embodiment.
  • FIG. 3 is a diagram showing part of measurement conditions in a measurement example using the PESI mass spectrometer of the present embodiment;
  • FIG. 1 is a schematic configuration diagram of the PESI mass spectrometer of this embodiment.
  • This PESI mass spectrometer is a mass spectrometer that combines a PESI ion source and a quadrupole-time-of-flight (Q-TOF) mass spectrometer.
  • Q-TOF quadrupole-time-of-flight
  • an ionization device 10 having an ionization chamber 100 provided therein is connected to the front of the vacuum chamber 1 .
  • the interior of the vacuum chamber 1 is roughly divided into five chambers: a first intermediate vacuum chamber 11 , a second intermediate vacuum chamber 12 , a third intermediate vacuum chamber 13 , a first analysis chamber 14 and a second analysis chamber 15 .
  • the ionization chamber 100 has a substantially atmospheric pressure, and from the ionization chamber 100, the first intermediate vacuum chamber 11, the second intermediate vacuum chamber 12, the third intermediate vacuum chamber 13, the first analysis chamber 14, and the second analysis chamber 15 are arranged in order. , a multi-stage differential pumping system in which the degree of vacuum increases step by step.
  • a sample plate 101 having a recess 102 is arranged in the ionization chamber 100, and the recess 102 accommodates a small amount of liquid sample.
  • a metal probe 103 held by a probe holder 104 is arranged above the sample plate 101 so as to extend in the vertical direction (Z-axis direction).
  • a probe driving unit 107 including a motor, a deceleration mechanism, and the like can move (lift) the probe holder 104 in the positive and negative directions of the Z-axis.
  • the high voltage generator 106 can apply a DC high voltage (the polarity depends on the ions to be measured) of about several kV at the maximum to the probe 103 .
  • the tip of the probe 103 enters the recess 102 and the liquid sample adheres to the tip surface of the probe 103 .
  • the high voltage generator 106 applies a DC high voltage to the probe 103 . Then, an electric field with strong intensity is formed near the tip of the probe 103, and components in the liquid sample adhering to the tip of the probe 103 are ionized by the electrospray phenomenon.
  • the ionization chamber 100 and the first intermediate vacuum chamber 11 are communicated through a thin desolvation pipe 105 .
  • the ions derived from the sample components generated in the ionization chamber 100 are drawn into the desolvation tube 105 mainly by the difference between the pressure in the ionization chamber 100 (approximately atmospheric pressure) and the pressure in the first intermediate vacuum chamber 11. , to the first intermediate vacuum chamber 11 .
  • a multipole ion guide 110 is arranged in the first intermediate vacuum chamber 11.
  • the ions are focused near the ion optical axis C1 by the ion guide 110 and passed through the top opening of the skimmer 111 to the second intermediate vacuum chamber. It enters the vacuum chamber 12 .
  • Multipole ion guides 120 and 130 are arranged in the second intermediate vacuum chamber 12 and the next third intermediate vacuum chamber 13, respectively. From the chamber 12 it is sent to the third intermediate vacuum chamber 13 and from the third intermediate vacuum chamber 13 to the first analysis chamber 14 .
  • the first analysis chamber 14 is equipped with a quadrupole mass filter 140 and a multipole ion guide 142 for separating ions according to their mass-to-charge ratio (hereinafter sometimes referred to as "m/z").
  • a collision cell 141 and a front stage portion of a transfer electrode 143 for transporting ions emitted from the collision cell 141 are arranged. Ions incident on the first analysis chamber 14 are introduced into the quadrupole mass filter 140, and only ions having a specific m/z value according to the voltage applied to each electrode constituting the quadrupole mass filter 140 are detected. passes through the quadrupole mass filter 140 .
  • a collision gas such as argon or nitrogen is continuously or intermittently supplied to the interior of the collision cell 141 . Ions that have a predetermined energy and enter the collision cell 141 come into contact with the collision gas and are dissociated by collision-induced dissociation to generate various product ions.
  • Various product ions emitted from the collision cell 141 are converged by the transfer electrode 143 and sent to the second analysis chamber 15 .
  • a post-stage section of the transfer electrode 143, an orthogonal acceleration section 150, a guide electrode section 151, a flight tube 152, a reflectron 153, a back plate 154, an ion detector 155, and the like are arranged in the second analysis chamber 15 .
  • the ions introduced into the second analysis chamber 15 as a thin, highly parallel beam by the transfer electrode 143 are ejected in the orthogonal acceleration section 150 in a direction substantially orthogonal to the incident direction of the beam (negative direction of the Z axis).
  • the ejected ions are introduced into the flight space within the flight tube 152 via the guide electrode portion 151 .
  • the flight tube 152, the reflectron 153, and the back plate 154 form an electric field in the flight space that causes the ions to return and fly along the path indicated by C2 in FIG. As a result, the ions fly back through the flight tube 152 again and reach the ion detector 155 .
  • the ions ejected from the orthogonal acceleration section 150 fly at a speed corresponding to the m/z of the ions. Therefore, various ions accelerated at the same time are separated according to m/z during flight and reach the ion detector 155 with a time lag.
  • the ion detector 155 generates a detection signal according to the amount of ions that have arrived. That is, the output signal from the ion detector 155 is a time-of-flight spectrum that indicates changes in ion intensity according to time-of-flight.
  • the time-of-flight spectrum of the product ions can be obtained, and the ion selection is not performed in the quadrupole mass filter 140 and the ions are separated in the collision cell 141. Without the dissociation operation, time-of-flight spectra for ordinary ions are obtained.
  • a data processing unit 30 that receives the output signal of the ion detector 155 includes a data storage unit 31, a component identification unit 32, and an identification library 33 as functional blocks.
  • the data storage unit 31 includes an analog-to-digital conversion unit that digitizes the input signal, converts the collected time-of-flight spectrum data into mass spectrum data, and stores the mass spectrum data.
  • the component identification unit 32 identifies a plurality of components contained in the liquid sample based on the mass spectrum and MS/MS spectrum obtained by measuring the liquid sample.
  • the identification library 33 is a database that is referred to when identifying components, and contains in advance precise molecular weights and standard MS/MS spectra for a large number of compounds.
  • the control unit 20 controls the high voltage generation unit 106, the probe driving unit 107, the voltage generation unit (not shown), and the like to measure the liquid sample. It includes functional blocks such as a source controller 22 and a DIA analysis controller 23 . An input section 40 and a display section 50 as a user interface are connected to the control section 20 .
  • control unit 20 and the data processing unit 30 can be configured by hardware, the entity thereof is usually a general-purpose computer such as a personal computer. By executing dedicated control and processing software installed in the computer, the function of each functional block in the control unit 20 and the data processing unit 30 described above can be achieved.
  • FIG. 2 is a conceptual diagram showing an example of the relationship between the m/z range to be measured in this PESI mass spectrometer and precursor ions to be subjected to MS/MS analysis.
  • FIG. 3 is a conceptual diagram showing an example of the relationship between the operation cycle of the ion source and the timing of the mass spectrometry operation in this PESI mass spectrometer.
  • the analysis described below is a comprehensive analysis aimed at identifying as many components contained in the liquid sample as thoroughly as possible.
  • the DIA method described in Patent Document 2, Non-Patent Document 2, etc. is well known.
  • a method based on the SWATH (Sequential Window Acquisition of all THEoretical fragment ion spectra mass spectrometry) (registered trademark) method which is a typical method in the DIA method described in those documents, is used. use.
  • a window with a predetermined m/z width is set within the m/z range to be measured, and the window is moved along the m/z axis. Ions having m/z values are collectively used as precursor ions for product ion scan measurement. As a result, an MS/MS spectrum (product ion spectrum) is obtained for each window different from each other. In this method, the window is moved so as to cover the entire m/z range of the measurement target, that is, without m/z gaps. Product ion information can be obtained for all components.
  • the standard m/z width of the window is about 25 Da.
  • the m/z width of the window is variable, but even in that case the m/z width of the window is within the range of about 5 to 50 Da.
  • the DIA method is usually used in LC-MS, but in LC-MS, the component separation is performed to a considerable extent by liquid chromatography, so the number of components contained simultaneously in the liquid sample introduced into the mass spectrometer is not so large. not many. Therefore, even if the m/z width of the window is 25 Da, it is not very likely that ions derived from different components will fall within the window.
  • the number of components contained in the sample introduced into the mass spectrometer is incomparably greater than in LC-MS, and the window m/z A width of 25 Da allows ions from many different components to fall within the window.
  • the MS/MS spectrum becomes complicated, and the load of data analysis for separating it into MS/MS spectra for each component increases.
  • the accuracy of the MS/MS spectrum separated into individual components may also be lowered accordingly.
  • the m/z width of the window is set to 1 Da, which is considerably narrower than the standard m/z width of the SWATH method.
  • the m/z width of this window is not limited to 1 Da, but should be set within the range of about 0.5 to 1.5 Da.
  • Narrowing the m/z width of the window for selection of precursor ions in this way increases the number of MS/MS analyzes to be performed for the same m/z range to be measured, thus increasing the number of measurements for one sample. it takes longer.
  • the PESI mass spectrometer measures a liquid sample in a retained state, unlike LC-MS, the types of components contained in the sample to be measured by the mass spectrometer do not change over time.
  • the amount of liquid sample prepared on the sample plate 101 is usually small, and the liquid sample tends to volatilize, so the time required to measure one liquid sample is limited.
  • the shorter measurement time also has the advantage of higher analysis throughput. Therefore, as an example, the maximum required time for measurement for one sample is set to 4 seconds, and the measurement time is set to about 3 seconds with a margin.
  • Blonanserin in plasma is the target component, and components in plasma including the target component are comprehensively analyzed.
  • Blonanserin has a compositional formula of C23H30FN3 and a molecular weight of 367.5028.
  • the m/z range to be measured was m/z 140-770.
  • the same MS/MS analysis is repeated a predetermined number of times, and the data obtained from the multiple MS/MS analyzes are integrated. The quality of the MS spectrum is degraded.
  • the event time is set to 20 msec here. Also, since the ionization cycle in the PESI ion source is approximately 0.4 sec, the loop time for MS/MS analysis was set at 420 msec. Then, 21 events were defined as one group, and 630 events covering the entire m/z range to be measured were divided into 30 groups. If the measurement time of 3 minutes (180 seconds) is allocated to 30 groups, the measurement time per group is 6 seconds. Therefore, by repeating the loop of 420 msec 14 times, the measurement time per group was set to 5.88 seconds. Since the number of groups is 30, the execution time of MS/MS analysis is simply calculated to be 176.4 seconds. However, since normal mass spectrometry is also performed in addition to MS/MS analysis, the measurement time for one sample is about 3 minutes.
  • the vertical axis is the event number corresponding to one unit of mass spectrometry performed on one sample.
  • Event 0 is normal mass spectrometry
  • Event 1 to Event 630 are MS/MS analyzes in which the m/z width of the precursor ion window is 1 Da. Analysis is performed in order of event numbers, that is, from top to bottom in FIG.
  • the horizontal axis represents the mass-to-charge ratio m/z, which represents the m/z range to be measured in normal analysis and the m/z value selected as precursor ions in MS/MS analysis.
  • FIG. 3 shows the relationship between the PESI cycle and the timing of MS/MS analysis in a group containing 21 events with event numbers Event 1 to Event 21.
  • the event number is indicated by symbol #.
  • the position indicated by the upward arrow in FIG. 3 is the timing at which the high voltage generator 106 starts applying the high voltage to the probe 103, and the high voltage is continuously applied for 260 msec. Thereafter, samples are taken by lowering and raising the probe 103 during a period of 160 msec.
  • samples are taken by lowering and raising the probe 103 during a period of 160 msec.
  • ions are generated during the voltage application period of 260 msec (however, the amount of ions generated is not always constant). After that, even if the voltage application to the probe 103 is stopped, the ions generated before that time remain around the probe 103, so the ions cannot be sent to the subsequent stage immediately. Although it does not stop, the amount of ions sent to the subsequent stage decreases and becomes almost zero after a certain period of time.
  • each loop is not limited to that illustrated in FIG. 3, and can be changed as appropriate. For 21 events included in one group, it is sufficient that the number of times of each event performed during the voltage application period in the 14 loops is approximately the same. The same applies to events included in groups other than the groups shown in FIG.
  • the analysis conditions as described above are created in advance as an analysis sequence as shown in FIG. 4 and stored in the analysis sequence storage unit 21 .
  • “+/-” is the polarity of the ion to be measured
  • “type” is the selection between normal analysis and MS / MS analysis
  • "start” is the analysis start time
  • "end” is the analysis end time
  • "precursor "Ion m/z” is the center value of the precursor ion m/z range
  • “Tof start m/z” is the start m/z of the product ion scan
  • Tof end m/z is the end m/z of the product ion scan.
  • CE is the collision energy value
  • CE Spread is the spread of the collision energy
  • event time is the execution time of the MS/MS analysis (or normal analysis)
  • number of injections is the number of repeated analyzes in that event
  • Q1 resolution indicates the m/z width of precursor ions.
  • Such an analysis sequence may be created by the user himself/herself, or may be provided to the user by the manufacturer of the apparatus as a standard analysis sequence according to the purpose of analysis, sample to be analyzed, and the like.
  • control unit 20 when the user inputs predetermined analysis conditions such as the m/z range of the measurement target and the event time from the input unit 40, the control unit 20 is provided with a function of creating an analysis sequence that satisfies the analysis conditions.
  • the ion source controller 22 controls the probe driver 107 and the high voltage generator 106 so as to repeat a predetermined PESI cycle. As a result, as shown in FIG. 3, the sampling operation by lowering and raising the probe 103 and the ionization operation by applying a high voltage to the probe 103 are alternately repeated.
  • the DIA analysis control unit 23 controls the voltage generation unit (not shown) so as to repeat the MS/MS analysis in synchronization with the PESI cycle according to the analysis sequence stored in the analysis sequence storage unit 21 . Thereby, MS/MS analysis is performed by the DIA method according to the analysis sequence.
  • the data storage unit 31 sequentially stores MS/MS spectral data for each event, that is, for each different precursor ion.
  • the data storage unit 31 stores MS/MS spectrum data respectively corresponding to 630 events.
  • Mass spectral data obtained by normal mass spectrometry are also stored in the data storage unit 31 .
  • the component identification unit 32 identifies components contained in the sample based on the collected mass spectrum and MS/MS spectrum. Specifically, the component identification unit 32 first detects peaks in the mass spectrum and obtains the m/z value corresponding to each peak. Since the time-of-flight mass spectrometer can obtain m/z values with high accuracy and resolution, it is possible to estimate the compositional formula of a component from the m/z values. In addition, the component identification unit 32 stores the information of the compositional formula estimated from the m/z value of the peak detected in the mass spectrum and the MS/MS spectrum corresponding to the peak in the identification library 33. The information is matched to identify the component corresponding to that peak.
  • product ions derived from multiple different components may be mixed in the MS/MS spectrum corresponding to that window. have a nature.
  • component identification is performed using the separated MS/MS spectra. When the component identification is completed in this way, the identification result is displayed on the display section 50 .
  • MS/MS analysis was performed even during the sampling period. MS/MS analysis may be performed only during periods when ionization is reliably occurring, and the execution of MS/MS analysis may be paused during the sampling period.
  • the PESI cycle and the loop time of MS/MS analysis are synchronized, but synchronization is not necessarily required.
  • the MS/MS analysis is performed during the sampling period as well, if the MS/MS analysis targeting a certain precursor ion happens to be repeatedly performed during the sampling period, sufficient MS/MS spectra of good quality cannot be obtained, and components may be missed. To avoid this, it is better to synchronize the PESI cycle and the MS/MS analysis loop time so that the MS/MS analysis targeting specific precursor ions is not repeated during the sampling period.
  • One aspect of the PESI mass spectrometer according to the present invention is an ion source by the probe electrospray ion method; a mass filter that selects specific ions among the ions generated by the ion source; a collision cell that dissociates ions selected by the mass filter; a mass analyzer including an orthogonal acceleration time-of-flight mass separator and an ion detector for mass analyzing product ions generated in the collision cell; an ion source control unit for controlling the ion source so as to repeat an operation of collecting the same sample and an operation of ionizing the collected sample by the ion source; When sampling and ionization of the sample are repeatedly performed in the ion source, ions having a mass-to-charge ratio included in a window of a predetermined mass-to-charge ratio width are allowed to pass through the mass filter, and the ions are filtered to the The operation of dissociating in the collision cell and acquiring the mass spectrum of the product ions generated by the mass analysis unit is performed
  • the m/z width of ions (precursor ions) selected by the mass filter is considerably narrower than in MS/MS analysis by the general DIA method. Therefore, even when a sample contains a large number of components, ions derived from a plurality of components are less likely to be selected as precursor ions, and product ions derived from a plurality of components are less likely to coexist in one MS/MS spectrum. Therefore, according to the PESI mass spectrometer described in item 1 or item 2, comprehensively acquire high-purity MS / MS spectra corresponding to multiple components contained in the sample, including the target component and contaminant components and each of these components can be identified with high accuracy.
  • the analysis control unit treats one sampling and ionization period in the ion source as one ionization cycle, and over a plurality of ionization cycles, Each part can be controlled to repeatedly perform MS/MS analysis operations for multiple windows of the same mass-to-charge ratio range.
  • the analysis control unit changes the mass-to-charge ratio range of the window performed at a predetermined timing in each ionization cycle included in the plurality of ionization cycles. Each part can be controlled so as to do so.
  • the ion source alternately repeats the sampling operation and the ionization operation, but naturally no ions are generated during the sampling period. Therefore, if MS/MS analysis is performed without distinguishing between the sampling period and the ionization operation period in one ionization cycle, a good MS/MS spectrum cannot be obtained in the MS/MS analysis during the sampling period.
  • the analysis control unit may perform MS/MS analysis only during the period when the ionization operation is being performed in the ion source. can.
  • the period during which the ionization operation is performed is typically the period during which a high voltage for ionization is applied to the probe.
  • the ions generated during the application of the high voltage exist in the ionization chamber, and the ions are transferred to the subsequent stage. can be transported to Therefore, not only the period during which the high voltage is applied to the probe, but also the period during which the ions can be substantially emitted even after the application of the high voltage is stopped is the "period during which the ionization operation is performed.” ” can be included in
  • MS / MS analysis is not performed during the period when ions derived from the components in the sample are not sent from the ion source to the subsequent mass filter, and the MS / MS spectrum is also acquired. not. Therefore, it is possible to avoid lowering the detection sensitivity of the MS/MS spectrum corresponding to a specific window.

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Abstract

Un mode de réalisation de la présente invention concerne un dispositif de spectrométrie de masse PESI comprenant : une source d'ions PESI (103, 104, 106, 107) ; un filtre de masse (140) qui sélectionne des ions spécifiques à partir des ions produits par la source d'ions ; une cellule de collision (141) qui dissocie les ions sélectionnés par le filtre de masse ; une unité de spectrométrie de masse (150-155) qui effectue une spectrométrie de masse sur les ions de produit produits par la cellule de collision ; une unité de commande de source d'ions (22) qui commande la source d'ions de sorte que, pour le même échantillon, la collecte de l'échantillon et l'ionisation de l'échantillon collecté sont effectuées de façon répétée dans la source d'ions ; et une unité de commande d'analyse (23) qui commande les unités de façon à effectuer une opération qui, lorsque la collecte et l'ionisation de l'échantillon sont effectuées de façon répétée sur l'échantillon dans la source d'ions, permet aux ions ayant un m/z compris dans une fenêtre ayant une largeur m/z prédéterminée de passer à travers le filtre de masse, dissocie les ions dans la cellule de collision, et obtient un spectre de masse des ions de produit produits par l'unité de spectrométrie de masse, tout en décalant la fenêtre sur la plage m/z à mesurer. La largeur m/z de la fenêtre est comprise dans la plage de 0,5 à 1,5 Da.　
PCT/JP2021/019834 2021-05-25 2021-05-25 Dispositif de spectrométrie de masse à ionisation par électronébulisation de sonde WO2022249291A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015107690A1 (fr) * 2014-01-20 2015-07-23 株式会社島津製作所 Dispositif de traitement de données de spectrométrie de masse en tandem
WO2019146078A1 (fr) * 2018-01-26 2019-08-01 株式会社島津製作所 Dispositif de spectrométrie de masse à ionisation par électronébulisation de sonde

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015107690A1 (fr) * 2014-01-20 2015-07-23 株式会社島津製作所 Dispositif de traitement de données de spectrométrie de masse en tandem
WO2019146078A1 (fr) * 2018-01-26 2019-08-01 株式会社島津製作所 Dispositif de spectrométrie de masse à ionisation par électronébulisation de sonde

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