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WO2008148557A2 - Dispositif de support d'échantillon destiné à des chambres d'ionisation pour spectrométrie de masse - Google Patents

Dispositif de support d'échantillon destiné à des chambres d'ionisation pour spectrométrie de masse Download PDF

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Publication number
WO2008148557A2
WO2008148557A2 PCT/EP2008/004499 EP2008004499W WO2008148557A2 WO 2008148557 A2 WO2008148557 A2 WO 2008148557A2 EP 2008004499 W EP2008004499 W EP 2008004499W WO 2008148557 A2 WO2008148557 A2 WO 2008148557A2
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WO
WIPO (PCT)
Prior art keywords
sample holder
holder device
sample
ionization
ionization chamber
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2008/004499
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English (en)
Other versions
WO2008148557A3 (fr
Inventor
Gaetano Corso
Dott.Ssa Oceania D'apolito
Dott. Giuseppe Paglia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universita' Degli Studi di Foggia
Original Assignee
Universita' Degli Studi di Foggia
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 Universita' Degli Studi di Foggia filed Critical Universita' Degli Studi di Foggia
Publication of WO2008148557A2 publication Critical patent/WO2008148557A2/fr
Publication of WO2008148557A3 publication Critical patent/WO2008148557A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/14Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0409Sample holders or containers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample

Definitions

  • the present invention relates to the field of mass spectrometry.
  • the present invention relates to a sample holder device for mass spectrometry.
  • the present invention relates to a sample holder device for ionization chambers for desorption electrospray ionization mass spectrometry (DESI).
  • DESI desorption electrospray ionization mass spectrometry
  • Mass spectrometry is an analytical technique based on the measurement of the mass-to- charge ratio (m/z) of charged particles coming from the sample to be analyzed (analyte).
  • m/z mass-to- charge ratio
  • ESI electrospray ionization mass spectrometry
  • DESI desorption electrospray ionization mass spectrometry
  • the ESI technique was first proposed by Malcolm Dole in 1968 [1] and it was further developed, in particular with respect to the measurement of biological macromolecules, by John Fenn [2] who was awarded, for this reason, with the Chemistry Nobel Prize in 2002.
  • the charged particles are obtained from the sample to be analyzed (analyte) in the liquid phase.
  • the liquid comprising the analyte diluted in a solvent is pushed through a capillary tube (internal diameter in the order of 100 ⁇ m) ending with a narrow metallic tip usually held at high voltage.
  • the capillary tube and the narrow tip form the so called electrospray source.
  • the liquid coming out of the electrospray source forms an aerosol, i.e.
  • the droplets forming the aerosol undergo a series of breaking up processes leading to smaller and smaller droplets and ultimately to single charged molecules of the analyte.
  • an inert carrier gas such as nitrogen or argon is employed to improve the nebulization process.
  • the single charged molecules of the analyte are detected by the typical analyzers of the mass spectrometers such as quadrupole mass filters, quadrupole ion traps, ion cyclotron resonance instruments and magnetic sector instruments. More details about the ESI technique could be found for instance in [3].
  • the ESI technique is particularly advantageous with respect to other mass spectrometry techniques, and it is for this reason commonly used in analytical laboratories all over the world, it has a major drawback due to the limited success of the automation of the method.
  • the shortest achievable time per analysis in the ESI technique is 20 - 40 seconds.
  • Atmospheric Pressure Chemical Ionization (APCI) is similar to ESI but it takes place at atmospheric pressure and involves a gas phase ionization process instead of the liquid phase ionization process typical for ESI measurements.
  • APCI measurements are performed in modified ESI facilities. More details about the APCI technique could be found for instance in reference [4].
  • the DESI technique has been recently introduced, and it is described for instance in references [5] and [6] and in the International Patent Application PCT/US2005/011212.
  • an electrospray source similar to the one employed in the ESI technique is used to produce the so called DESI-active spray (i.e. an aerosol of charged droplets) which is directed towards a sample to be analyzed (analyte).
  • the impingement and the subsequent interaction of the charged droplets of the DESI-active spray with the surface of the analyte result in the desorption and ionization of molecules of the analyte.
  • These charged molecules of the analyte are then detected by the analyzer of the mass spectrometer.
  • the DESI spectrometers known in the art are provided with an ion transfer line adapted to collect the ions of the analyte desorbed from the sample and to drive them to the analyzer.
  • the DESI technique has been successfully applied on solid samples, both conductive and insulating, on liquid samples and even on living organisms. In particular, this technique allows to analyze intact samples that have not undergone any kind of preparation procedure or samples rapidly pre-treated.
  • the DESI technique is for these reasons particularly advantageous, and it is currently being developed in several fields of application such as medical and biological research, environmental sciences, pharmaceutical industry, toxicology and forensics. Contrary to the ESI technique, the DESI technique allows to obtain rates of up to 10 analysis per second [6].
  • several kinds of DESI-based imaging techniques have been developed in order to create, for example, a map of the distribution of constituents of a sample, as described, for instance, in the International Patent Application PCT/US2005/011212.
  • the DESI apparatuses known in the art are provided with classical ion trap analyzers or with linear ion trap analyzers coupled with electrospray sources customized in order to provide desorption and ionization of the analyte molecules. Moreover, it is necessary to provide the system with an ion transfer line to drive the analyte ions to the analyzer. For these reasons, it is extremely complex to adapt DESI sources to already operating mass spectrometers. Consequently, the DESI sources known in the art are not easy-fitting to every kind of mass spectrometry analyzers and, even if they are manual and not automatic, they are extremely costly.
  • a sample holder device for ionization chambers comprising a base comprising a curved portion adapted to match the internal surface of a ionization chamber so that said sample holder device can be translated in at least one translation direction inside said ionization chamber, and that said sample holder device can be rotated around an axis of rotation being parallel to said translation direction.
  • a sample holder device for ionization chambers wherein said curved portion is adapted to match the internal surface of a cylindrical ionization chamber so that said sample holder device can be translated in a direction parallel to the axis of the ionization chamber.
  • a sample holder device for ionization chambers comprising a base comprising a curved portion whose curvature radius corresponds to the curvature radius of the ionization chamber.
  • a sample holder device comprising a base and a sample holder, and wherein said base further comprises supporting means for supporting said sample holder.
  • the position of the sample holder on the supporting means is adjustable.
  • the sample holder comprises an inclined portion.
  • the slope angle of said inclined portion could be predefined and fixed or, alternatively, it could be adjustable so as to add a further degree of freedom in the choice of the position and orientation of the sample in the ionization chamber.
  • the sample holder comprises a protruding portion located at the bottom of the inclined portion.
  • said protruding portion is provided with a notch.
  • said notch has a semicircular shape.
  • said notch is located in the centre of said protruding portion.
  • the sample holder device according to the present invention may further comprise other devices suitable for several kinds of measurements.
  • the sample holder devices is provided with means for measuring the temperature of the sample.
  • means for measuring temperatures means such as sensors, thermocouples and the like could be integrated in the sample holder device of the present invention.
  • the sample holder device is provided with means for regulating the temperature of the sample.
  • Heating means such as heating filaments or cooling means such as liquid nitrogen means could be integrated in the sample holder device of the present invention.
  • the sample holder device is provided with a mask for selecting the area of the sample to be probed.
  • the sample holder device is provided with a grid located above the position of the sample.
  • a mass spectrometer is provided, as defined in claim 19.
  • an automated transfer system for mass spectrometers is provided, as defined in claim 20 and in the following specification.
  • Fig. 1 schematically represents a sample holder device for ionization chambers according to a preferred embodiment of the present invention.
  • Fig. 2 schematically displays a ionization chamber comprising a source, a collector and a sample holder device according to a preferred embodiment of the present invention.
  • Fig. 3 shows the mass spectrum of the amino acid Methionine (quasi-molecular ion, m/z: 150) obtained employing a sample holder device for ionization chambers according to a preferred embodiment of the present invention and the optimized parameters listed in Table 1 in the experimental section.
  • Fig. 4 shows the neutral loss mass spectra of an amino acids mixture obtained with the DESI technique employing a sample holder device according to a preferred embodiment of the present invention (upper spectrum), and with the ESI technique in the same ionization chamber (lower spectrum).
  • Fig. 5 shows the mass spectra of blood samples (normal and pathological-MSUD) obtained with the DESI technique employing a sample holder device according to a preferred embodiment of the present invention.
  • Fig. 1 schematically displays a sample holder device for ionization chambers according to a preferred embodiment of the present invention.
  • the sample holder device comprises a base (2) and a sample holder (1).
  • the sample holder (1) is shown in perspective in the upper part of the figure.
  • the bottom part of the figure shows a cross-sectional view of the sample holder device in its entirety (base (2) and sample holder (1)).
  • the base (2) comprises a curved portion (2 1 ).
  • the presence of the curved portion is particularly advantageous in order to adapt the sample holder device to be supported on the internal surface of a ionization chamber.
  • the sample holder device provided with a base (2) comprising a curved portion (2') can be easily translated inside the ionization chamber in a direction perpendicular to the cross-sectional direction of Fig. 1 , and it can be easily rotated around an axis of rotation parallel to the translation direction.
  • the base (2) of the sample holder device of Fig. 1 further comprises supporting means (2", 2'") for supporting the sample holder (1).
  • supporting mean 2" forms a surface connected at one end with the curved portion (2') and oriented along a radius of said curved portion (2').
  • Supporting mean 2'" connects the curved portion (2 1 ) with the second end of the supporting mean 2" so as to form in the cross-sectional view an angle ⁇ of 90°.
  • the angle ⁇ formed by the supporting means 2" and 2'" can be arbitrarily fixed to any value, for instance to any value comprised between 0° and 90°, but also to values higher than 90".
  • the sample holder (1) is placed on the surface formed by the supporting mean 2".
  • the sample holder (1) can be fixed to the surface formed by the supporting mean 2" by any kind of fixing means known to those skilled in the art.
  • the sample holder (1) can be simply placed on the base (2) without being fixed to it, so that it can be moved on the surface formed by the supporting mean 2" in order to easily and finely adjust the position of the sample holder (1) with respect to the base (2).
  • the sample holder (1) is not fixed to the base (2), it is possible to insert and extract the sample form the ionization chamber by inserting and extracting only the sample holder (1) while leaving the base (2) inside the ionization chamber.
  • the sample holder (1) is formed by an inclined plane (8) with a slope angle ⁇ .
  • the slope angle ⁇ could be fixed.
  • the slope angle ⁇ could be adjustable so as to add a further degree of freedom to the orientation of the sample.
  • the sample is placed on the inclined plane (8).
  • the sample could be directly placed on the inclined plane (8), for instance in the case of a solid sample.
  • the sample could be attached to the plane (8) by any mean known to those skilled in the art, for instance by adhesive means.
  • the sample could be positioned on a plate (3) placed on the inclined plane (8).
  • the inclined plane (8) could be provided with supporting means for supporting said plate (3).
  • the plate (3) could be made of glass, PTFE, stainless steel, paper or any other solid material.
  • the sample can be positioned on the plate (3) by any known method known to those skilled in the art.
  • a sample in the solid phase could be for instance fixed to the plate (3) by adhesive means; a sample in the liquid phase could be sprayed or deposited on the plate (3); a sample in the gas phase could be sprayed on the plate (3).
  • the sample holder (1) further comprises a protruding portion (4) located at the bottom of the inclined plane (8).
  • the protruding portion could serve to prevent the sample or the plate (3) to slip off the inclined plane (8).
  • the protruding portion (4) is further provided with a notch (5) located at the centre of said protruding portion (4) and having a semicircular shape.
  • the notch (5) could house the ending portion of the ion collector so as to allow to position the sample close to the ion collector and to improve the collection of analyte ions.
  • the sample holder device could be provided with several devices suitable for several kinds of measurements, such as DESI- based imaging measurements, reactions measurements, temperature-dependent measurements and so on.
  • the sample holder device could be provided with means for measuring the temperature of the sample.
  • means for measuring the temperature of the sample Several kinds of means such as sensors, thermocouples and the like could be integrated in the sample holder device according to the present invention. These means could be for instance integrated in the sample holder (1).
  • the sample holder device of the present invention could be provided with means for heating and/or cooling the sample.
  • heating means suitable to be integrated in the sample holder device of the present invention are heating filaments.
  • cooling means suitable to be integrated in the sample holder device of the present invention are liquid nitrogen based means. Heating or cooling the sample during the measurements could be important for several kinds of studies such as reaction mechanisms studies, activation energies studies and the like.
  • the sample holder device of the present invention could be provided with a mask for selecting the area of the sample to be probed. The mask delimits the area of the sample targeted by the DESI-active spray so that the analyte ions are collected from a predefined area of the sample. This could be employed, for instance, to create a map of the distribution of constituents of the sample.
  • the mask could be for instance fixed to the protruding portion (4) located at the bottom of the inclined plane (8), and it could be placed parallel to said inclined plane (8) so as to create a space between said mask and said inclined plane (8).
  • a plate (3) comprising a sample (10) could be placed on the inclined plane (8) in the space comprised between said inclined plane (8) and the mask.
  • the sample holder device could be provided with a grid located above the position of the sample.
  • a grid positioned between the sample and the source of the DESI-active spray allows to improve the resolution of DESI-based imaging techniques.
  • the grid could be for instance fixed to the protruding portion (4) located at the bottom of the inclined plane (8), and it could be placed parallel to said inclined plane (8) so as to create a space between said grid and said inclined plane (8).
  • a plate (3) comprising a sample (10) could be placed on the inclined plane (8) in the space comprised between said inclined plane (8) and the grid.
  • sample holder device of the present invention could be employed for several kinds of DESI-based imaging measurements.
  • the system could be for instance provided with a needle held at a predefined voltage and employed to finely select the area of the sample to be probed.
  • the needle could be housed for instance in the notch (5) of the protruding portion (4) located at the bottom of the inclined plane (8) of the sample holder (1).
  • Fig. 2 shows a cross-sectional view of a cylindrical ionization chamber (9) provided with a sample holder device according to a preferred embodiment of the present invention.
  • the sample holder device comprises a base (2) and a sample holder (1).
  • the sample (10) is located on a plate (3) placed on the inclined plane of the sample holder (1).
  • the ionization chamber is provided with an active spray source (6) and with an ion collector (7).
  • the curvature radius of the curved portion of the base (2) of the sample holder device corresponds to the curvature radius of the ionization chamber (9).
  • the position of the sample holder device with respect to the spray source (6) and the ion collector (7) can be easily adjusted.
  • the sample holder device can be translated in the direction parallel to the axis of the ionization chamber; at the same time, it can be rotated around this axis, for instance by sliding the curved portion of the base (2) along the internal surface of the ionization chamber (9).
  • the sample holder device can be fixed to the internal surface of the ionization chamber (9) at any predefined position. Alternatively, the sample holder device can be simply leaned on the internal surface of the ionization chamber (9). In this case, inserting and extracting the device from the ionization chamber (9) is extremely easy and not time- consuming. Moreover, the sample holder device could be provided with an automated system for the adjustment of the position and orientation inside the ionization chamber
  • the position of the sample (10) inside the ionization chamber (9) and, in particular, with respect to the position of the spray source (6) and of the ion collector (7) can be easily adjusted. More in particular, it is possible to precisely control and optimize several parameters particularly relevant for the measurements such as the distance from the spray source (6) to the sample (10), the distance from the sample (10) to the ion collector (7), the angle of incidence ⁇ of the DESI-active spray on the sample (10) and the ion collection angle ⁇ of the ion collector (7) with respect to the sample (10).
  • ⁇ and ⁇ could be, for instance, easily and precisely adjusted by rotating the sample holder device around the axis of the ionization chamber by sliding the curved portion of the base (2) along the internal surface of the ionization chamber (9).
  • ⁇ and ⁇ could be adjusted by adjusting the slope angle ⁇ of the inclined plane (8) of the sample holder (1).
  • the distances of the sample (10) from the spray source (6) and from the ion collector (7) can be adjusted for instance by translating the sample holder device inside the ionization chamber. Alternatively, they can be adjusted by rotating the sample holder device inside the ionization chamber. In particular embodiments of the present invention, these distances could be adjusted by adjusting the position of the sample holder (1) on the supporting means (2") of the base (2).
  • the position of the sample (10) could be varied also during the measurements in order to desorb ionized molecules of the analyte from different areas of the sample, to create, for instance, a map of the distribution of constituents of a sample.
  • the arrangement of the system shown in Fig. 2 shows that the sample holder device according to the present invention allows to perform DESI measurements in a ionization chamber equipped with spray source (6) and ion collector (7) for standard ESI measurements without structural modifications of the ionization chamber itself.
  • the spray source (6) provides the DESI- active spray: several kinds of substances can be employed to form the DESI-active spray and the operation of the spray source is similar to the operation for the ESl measurements. For instance, several parameters regulating the spray formation process can be adjusted as listed in Table 1 below.
  • the droplets of the DESI-active spray impinge on the surface of the sample (10) causing the desorption and ionization of the molecules of the sample.
  • the ionization of the molecules of the sample can take place before or after the desorption.
  • the ionized molecules are collected by the ion collector (7) and analyzed in the mass spectrometer analyzer according to the standard procedures employed for instance for the analysis during the ESI measurements.
  • the measurements can be performed in ambient conditions, for instance at atmospheric pressure, or under vacuum conditions by properly establishing a vacuum environment in the ionization chamber by any kind of vacuum means known to the skilled person.
  • an automated sample transfer system for mass spectrometers.
  • the automated sample transfer system comprises sample holder devices according to the present invention.
  • the automated sample transfer system may comprise flexible supporting means such as a conveyor belt. The distances between the samples on the supporting means are adjusted according to the kind of samples to be analyzed and to the duration of the measurement process.
  • the automated sample transfer system may be controlled by a software. The employment of such an automated sample transfer system allows to minimize the time-per-analysis and, thus, to improve the time-per-analysis rate and, at the same time, to guarantee the high quality and precision of the analysis.
  • the ionization chamber employed is a standard ionization chamber equipped with the facilities to perform ESI measurements (electrospray source, ion collector, triple quadrupole analyzer) and it has a cylindrical shape.
  • ESI measurements electrospray source, ion collector, triple quadrupole analyzer
  • a sample holder device according to the present invention has been inserted in the ionization chamber in order to perform DESI measurements on the sample carried by the sample holder device.
  • a first step of the experimental procedure several measurements parameters have been optimized as shown in table 1. For each parameter (column 1) a wide range of values has been tested (column 2) and the optimum value inside said range has been registered (column 3).
  • the sample employed for this step is an amino acids mixture with the following amino acids concentrations: Phe 70 ⁇ M; Leu 160 ⁇ M; VaI 30 ⁇ M; Tyr 100 ⁇ M; Met 35 ⁇ M.
  • the sample employed for this step is an amino acids mixture with the following amino acids concentrations: Phe 70 ⁇ M; Leu 160 ⁇ M; VaI 30 ⁇ M; Tyr 100 ⁇ M; Met 35 ⁇ M.
  • the measuring parameters correspond to the optimal settings listed in Table 1. The results are shown in Table 2.
  • the DESI-mass spectrum of the amino acid Methionine (quasi-molecular ion, m/z: 150) employing a sample holder device for ionization chambers according to a preferred embodiment of the present invention has been measured.
  • the measurement parameters employed correspond to the optimal settings listed in Table 1.
  • the results are shown in Fig. 3.
  • a fourth step of the experimental procedure the results of the DESI measurements performed on an amino acids mixture employing a sample holder device according to the present invention are compared with the ESI measurements performed in the same ionization chamber on the same amino acids mixture.
  • the analysis has been performed with the "neutral loss" function and the results are shown in Fig. 4.
  • the spectra obtained with both techniques display an excellent agreement showing that the sample holder device of the present invention allows for the easy and, at the same time, reliable switching between the two measuring techniques in the same ionization chamber.
  • a fifth step of the experimental procedure normal and pathological-MSUD blood samples have been analyzed with the DESI technique employing a sample holder device according to a preferred embodiment of the present invention.
  • the blood samples are rapidly extracted from the patients and deposited on the sample holder without any further preparation procedure.
  • the results are shown in Fig. 5.
  • Asterisks (*) show the internal standard signals. The differences between the two spectra are clearly visible showing that the sample holder devices according to the present invention allow for the quick, easy, reliable and high quality analysis of biological samples.
  • sample holder device according to the present invention is particularly advantageous. It is in fact possible to perform DESI measurements by simply inserting the sample holder device according to the present invention in a ionization chamber equipped with ESI facilities. No further modifications (neither structural, nor instrumental) of the mass spectrometer are required. Similarly, it is also possible to perform DESI measurements by simply inserting the sample holder device according to the present invention in a ionization chamber equipped with APCI (Atmospheric Pressure Chemical Ionization) facilities.
  • APCI Admospheric Pressure Chemical Ionization
  • sample holder device By simply and easily inserting the sample holder device according to the present invention in a ionization chamber equipped with ESI or APCI facilities, it is possible to obtain desorption and ionization of molecules of any analyte supported by said sample holder device. It is, thus, possible to work with a further ionization technique (DESI) in the same ionization chamber without costly and time-consuming modifications of the chamber. It is therefore possible to profit of all the advantages of the DESI technique and, at the same time, to eventually compare the results obtained with those obtained with other ionization techniques such as ESI or APCI.
  • DESI further ionization technique

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

L'invention concerne un dispositif de support d'échantillon pour chambres d'ionisation qui permet d'effectuer des mesures de DESI (spectrométrie de masse à ionisation-désorption par électropulvérisation) dans des chambres d'ionisation équipées d'installations permettant de mettre en œuvre d'autres techniques d'ionisation de spectrométrie de masse, telles que l'ESI (spectrométrie de masse à ionisation par électropulvérisation) et l'APCI (ionisation chimique à pression atmosphérique). En insérant simplement et facilement le dispositif de support d'échantillon de l'invention dans une chambre d'ionisation équipée, par exemple, d'installations d'ESI ou d'APCI, on peut travailler avec une autre technique d'ionisation (DESI) dans la même chambre d'ionisation sans devoir soumettre la chambre à des modifications longues et coûteuses. On peut ainsi profiter de tous les avantages de la technique DESI, et en même temps comparer les résultats obtenus avec ceux d'autres techniques d'ionisation telles que l'ESI ou l'APCI.
PCT/EP2008/004499 2007-06-05 2008-06-05 Dispositif de support d'échantillon destiné à des chambres d'ionisation pour spectrométrie de masse Ceased WO2008148557A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM2007A000312 2007-06-05
IT000312A ITRM20070312A1 (it) 2007-06-05 2007-06-05 Dispositivo porta campione per camere di ionizzazione di spettrometri di massa

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WO2008148557A2 true WO2008148557A2 (fr) 2008-12-11
WO2008148557A3 WO2008148557A3 (fr) 2009-11-12

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WO2016083805A1 (fr) * 2014-11-25 2016-06-02 University Of Huddersfield Appareil d'analyse et son procédé d'utilisation
EP3800657A1 (fr) * 2015-03-06 2021-04-07 Micromass UK Limited Analyse par spectrométrie de masse avec désorption-ionisation par electronébulisation (« desi-ms ») ou par focalisation d'électroflux (« deffi-ms ») d'échantillons biologiques sur cotons-tiges
US11031222B2 (en) 2015-03-06 2021-06-08 Micromass Uk Limited Chemically guided ambient ionisation mass spectrometry
US11037774B2 (en) 2015-03-06 2021-06-15 Micromass Uk Limited Physically guided rapid evaporative ionisation mass spectrometry (“REIMS”)
US11094519B2 (en) 2015-03-06 2021-08-17 Micromass Uk Limited Collision surface for improved ionisation
US11133164B2 (en) 2015-09-29 2021-09-28 Micromass Uk Limited Capacitively coupled REIMS technique and optically transparent counter electrode
US11139156B2 (en) 2015-03-06 2021-10-05 Micromass Uk Limited In vivo endoscopic tissue identification tool
US11239066B2 (en) 2015-03-06 2022-02-01 Micromass Uk Limited Cell population analysis
US11270876B2 (en) 2015-03-06 2022-03-08 Micromass Uk Limited Ionisation of gaseous samples
US11282688B2 (en) 2015-03-06 2022-03-22 Micromass Uk Limited Spectrometric analysis of microbes
US11289320B2 (en) 2015-03-06 2022-03-29 Micromass Uk Limited Tissue analysis by mass spectrometry or ion mobility spectrometry
US11454611B2 (en) 2016-04-14 2022-09-27 Micromass Uk Limited Spectrometric analysis of plants
US11515136B2 (en) 2015-03-06 2022-11-29 Micromass Uk Limited Spectrometric analysis

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DE19937439C1 (de) * 1999-08-07 2001-05-17 Bruker Daltonik Gmbh Vorrichtung zum abwechselnden Betrieb mehrerer Ionenquellen
US7087898B2 (en) * 2000-06-09 2006-08-08 Willoughby Ross C Laser desorption ion source

Cited By (15)

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WO2016083805A1 (fr) * 2014-11-25 2016-06-02 University Of Huddersfield Appareil d'analyse et son procédé d'utilisation
US11139156B2 (en) 2015-03-06 2021-10-05 Micromass Uk Limited In vivo endoscopic tissue identification tool
US11289320B2 (en) 2015-03-06 2022-03-29 Micromass Uk Limited Tissue analysis by mass spectrometry or ion mobility spectrometry
US11037774B2 (en) 2015-03-06 2021-06-15 Micromass Uk Limited Physically guided rapid evaporative ionisation mass spectrometry (“REIMS”)
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