EP3352196B1 - Dispositif de production d'ions - Google Patents

Dispositif de production d'ions Download PDF

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Publication number
EP3352196B1
EP3352196B1 EP17152429.1A EP17152429A EP3352196B1 EP 3352196 B1 EP3352196 B1 EP 3352196B1 EP 17152429 A EP17152429 A EP 17152429A EP 3352196 B1 EP3352196 B1 EP 3352196B1
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EP
European Patent Office
Prior art keywords
sample
sprayer
ion generation
solvent
sample stage
Prior art date
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Active
Application number
EP17152429.1A
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German (de)
English (en)
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EP3352196A1 (fr
EP3352196B8 (fr
Inventor
Bernhard Spengler
Sabine Schulz
Florian LOTZ
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.)
Justus Liebig Universitaet Giessen
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Justus Liebig Universitaet Giessen
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Priority to EP17152429.1A priority Critical patent/EP3352196B8/fr
Publication of EP3352196A1 publication Critical patent/EP3352196A1/fr
Publication of EP3352196B1 publication Critical patent/EP3352196B1/fr
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    • 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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0409—Sample holders or containers
    • 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
    • H01J49/165—Electrospray ionisation

Definitions

  • the present invention relates to a device for direct ion generation of solid sample materials by means of desorption electrospray ionization in the field of ambient surface analysis in particular mass spectrometry.
  • the one ambient ionization technique that can be used in mass spectrometry for chemical analysis. It is an atmospheric pressure ion source that ionizes gases, liquids and solids outdoors under ambient conditions.
  • the method Desorption electrospray ionization coupled with mass spectrometry (short: DESI-MS) is to qualitatively and / or quantitatively examine the chemical composition of a sample directly from the surface of a sample object without complex sample preparation. By operating the DESI method under atmospheric conditions, it is not necessary to introduce the sample into a vacuum, combined with the appropriate instrumentation. Ionization methods with these properties are called ambient ionization methods.
  • the method DESI is written US2005 / 0230635 A1 described
  • a field of application of the DESI-MS is the quality control of the import of food and commodities across national borders.
  • samples of a product are currently collected and placed in appropriately equipped laboratories.
  • banned and over-concentrated pesticides as well as harmful contaminants and additives are the focus of the investigations. These are deliberately added by producers or migrate unintentionally during the manufacturing process or from the packaging to the product.
  • the detour of the samples through laboratories spends valuable time in which the questionable goods are already traded, without ensuring that they meet the respective requirements and limit values.
  • the situation is similar with harmful plasticizers in children's toys and packaging materials, the use of which is being increasingly stricter regulated.
  • the factor of time becomes even clearer when it comes to the identification of prohibited drugs and warfare agents.
  • the DESI-MS allows to simultaneously identify and / or quantify single or multiple chemical species from complex sample materials.
  • a high sample throughput and easy operation are possible, so that it is suitable for use directly at the location of the otherwise necessary sampling. Potential hazards can then be determined directly and the goods may be withheld by the authorities in due time.
  • Spray means an aerosol, i. a heterogeneous mixture (dispersion) of solid and / or liquid suspended particles in a gas.
  • Desorption refers to the process in which uncharged or already charged atoms or molecules leave the surface of a solid.
  • Ionization is any process in which one or more charge carriers are removed or added to an atom or molecule so that the atom or molecule remains as a positively or negatively charged ion.
  • the resulting ions in the gas phase are then transferred to a mass spectrometer and analyzed. Since ionization is possible directly from the untreated sample surface, sample preparation is generally low. The amount of desorbed material from the sample surface is so low that DESI can be described as a nondestructive ionization method.
  • analyte is meant a mixture of at least one substance, which is at least one substance of chemical and / or biological and / or biochemical origin.
  • the device according to the invention for generating ions 100 is intended for use with various mass spectrometers. It can be used with any mass spectrometer known to those skilled in the art having an atmospheric pressure inlet system.
  • the ion generating device 100 in this case comprises at least one desorption electrospray ionization source 200.
  • This is designed so that it can produce a spray which serves for the desorption and ionization of a sample for examination by means of a mass spectrometer.
  • the desorption electrospray ionization source 200 comprises at least one sprayer 3 with a sprayer tip 2.
  • the device according to the invention for generating ions 100 comprises a sample table 1, which is designed so that a sample 4 can be applied to its upper side.
  • the side of the sample table on which a sample 4 can be applied is referred to as the top side of the sample table.
  • the opposite side of the sample table 1 is referred to as the underside of the sample table.
  • the sample table 1 has at least one contact region 5 with at least one opening through which a spray can pass from the underside of the sample table 1 through the sample table 1 to a sample 4 located on the upper side of the sample table 1.
  • the contact region 5 may, for example, have a gap or a grid.
  • the sprayer 3 is arranged below the underside of the sample table 1.
  • the sprayer tip 2 is aligned in the direction of the underside of the contact region 5.
  • the sample table 1 comprises at least one contact region 5, through which the spray can pass from the desorption electrospray ionization source 200 to a sample 4.
  • a contact region 5 may be formed, for example, as a gap.
  • the sprayer tip 2 of the sprayer 3 has a minimum distance from the sample table 1 so that it does not directly contact the sample 4 on the sample table 1 can come. This minimum distance is 2 mm to 10 mm, preferably 2 mm to 5 mm. The contact of the spray from the sprayer 3 with the sample 4 is possible only over the contact area 5 in the sample table 1. The probability of contamination of the sprayer tip 2 with sample components is thus significantly reduced.
  • Desorption electrospray ionization source 200 and the sample stage 1 are preferably made movable relative to each other.
  • the device contains a region for receiving an ion transfer capillary 7.
  • the ion transfer capillary 7 is connected to a mass spectrometer.
  • the ion transfer capillary 7 is preferably arranged within the sample stage and extends to the contact region 5 (see FIG Fig.1 ).
  • the spray tip 2 is sensitive to mechanical stresses such as contact with a sample object.
  • the risk of contact with the sample object or by the operator is almost impossible in this structure.
  • the distance and angle of the sprayer to the sample table and the sample can be adjusted and locked.
  • the sample table 1 forms a fixed surface and enables simple orientation of the sample surfaces to the sprayer by simply laying on different samples. The geometrical parameters are therefore identical during the measurement and the results more comparable. All you have to do is level the sample on the sample table. Since the distances of the sprayer do not have to be adapted to the size and shape of the sample, measurements can be carried out much faster. Larger specimens do not have to be crushed but can be examined directly become. In this way, the sample preparation for DESI-MS examinations is further reduced and the measuring process for the operator is greatly simplified, so even laypersons can carry out analyzes.
  • a positioning means for adjusting the position of the sprayer 3 to the sample table 1.
  • the positioning means as x, y table 8 for change in the x, y plane and a slot plate in z-direction be formed.
  • the positioning means may also comprise a rotary table 9. The angle to the sample table or sample surface can be varied as desired via the 360 ° rotatable rotary table 9.
  • the positioning means may also comprise a lock in order to fix the geometric parameters of the sprayer, the sample table and the sample, in particular their position relative to one another during the measurement. This allows more comparable and more repeatable measurement conditions. For example, detents, safety bolts, screws and / or clamping or tensioning devices are suitable as locking.
  • the ion generating device 100 further comprises a unit for supplying the sprayer 3 with air and solvent for generating the DESI spray.
  • the supply unit comprises at least one compressor 10 with dampers 11 and an air filter 12, a drying tube 13 for drying the air sucked in by the compressor, a hose 14 for guiding the sucked air to the sprayer 3, a pressure reducer 15 and at least a pressure-stable vessel 16 with solvent reservoir 17 for receiving a solvent.
  • a compressor 10 This is designed for example as a reciprocating compressor.
  • the mechanical vibration of the compressor is largely intercepted by an elastic mounting on dampers 11. This is designed for example as a silicone damper.
  • the supply unit works as follows:
  • the compressor 10 draws in atmospheric air through an air filter 12.
  • the filter protects the compressor and the DESI spray from particles from the ambient air.
  • Via a hose the compressed air flows into a drying tube 13, which is filled with a desiccant.
  • the humidity is adsorbed, so that the humidity of the ambient air has no influence on the nebulizing gas flow or the desorption ionization process.
  • the gas stream is split.
  • the majority of the air flows via a hose 14 directly to the sprayer 3 and is used there for nebulization and acceleration of the highly charged solvent droplets.
  • a small volume of gas is used to generate the solvent flow, according to the principle of a pressure pump.
  • the air is passed through a pressure reducer 15 in a pressure-stable vessel 16.
  • a solvent reservoir 17 In the vessel 16 is a solvent reservoir 17. This has a capacity of preferably 5 ml to 15 ml.
  • About a sprayer capillary 20 is the outflow of the solvent from the Pressure vessel allows.
  • the thin liquid capillary between the solvent reservoir and the sprayer 3 generates a flow resistance, so that the solvent flow in the DESI-relevant range can be varied exactly via the relative pressure on the solvent in the range of a few hundred millibar, so that the spray of air and solvent emerge from the sprayer tip 2 can.
  • the ion generating device 100 further comprises a controllable pressure pump on the sprayer capillary 20 adapted to allow a constant and infinitely variable solvent flow of any solvent composition.
  • the corresponding pressure settings are infinitely variable with the pressure reducer 15 and allow from a minimum flow rate of preferably 1 .mu.l / min accuracy of the flow setting of preferably 0.05 ul / min.
  • the ion generating device 100 further comprises a flow sensor 18 and preferably an output means configured so that the flow sensor can measure the flow rate of the solvent and the output means can output the flow rate at any time.
  • the flow sensor 18 is decoupled from the electrical high voltage of the sprayer 3 and the solvent.
  • the ion generating device 100 has, for example, a long and thin solvent capillary 19 between the sprayer and the flow sensor. About this solvent capillary 19, the voltage drops significantly.
  • the sprayer capillary 20 is grounded during operation directly in front of the sensitive flow sensor 18.
  • the measured value of the flow rate measured by the flow sensor 18 can be detected continuously and output via an output means, e.g. issued a computer and / or transmitted, for example, to the mass spectrometer.
  • an output means e.g. issued a computer and / or transmitted, for example, to the mass spectrometer.
  • the flow rate can also be transmitted to a controllable pressure pump as in the fifth embodiment of the device according to the invention for generating ions 100 and used to control them.
  • the ion generating apparatus 100 further includes an accumulator 21 configured to supply the desorption electrospray ionization source with electrical energy.
  • the compressor 10 is electrically powered via an accumulator 21, which is designed as a lithium iron phosphate accumulator. This has a capacity of, for example, 5 to 25 Ah, preferably 8 to 15 Ah, a rated voltage of 11 to 40 V, preferably 20 to 30 V, so as to supply the desorption electrospray ionization source for several hours without interruption.
  • the high voltage required for the sprayer potential is preferably provided by a high voltage output of the mass spectrometer and connected via a high voltage port for sprayer 22. However, it is possible to add an internal voltage converter powered by the accumulator to the desorption electrospray ionization source.
  • the device for ion generation fulfills all the necessary conditions for a longer application away from laboratory locations. It can be combined with transportable or stationary mass spectrometers to form a mobile analytical device. This can also be referred to as desorption electrospray ionization mass spectrometer (DESI-MS) unit.
  • DESI-MS desorption electrospray ionization mass spectrometer
  • One use of the ion generating apparatus 100 of the present invention is to combine it with a portable mass spectrometer to form a mobile analytical device. This allows on-site analysis without depending on additional equipment.
  • the ion generating device 100 is suitable for carrying out a method for surface analysis by spraying the sample with spray from sprayer 3 through the contact region 5 of the sample table 1.

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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)

Claims (9)

  1. Dispositif de production d'ions (100) pour examen par analyse de surface, comprenant au moins une source de désorption-ionisation par électronébulisation (200) avec au moins un pulvérisateur (3) et une pointe de pulvérisateur (2), ainsi qu'un porte-échantillons (1) pour recevoir un échantillon sur sa face supérieure, caractérisé en ce que le porte-échantillons (1) présente au moins une région de contact (5) avec au moins une ouverture, à travers laquelle un spray peut passer de la face inférieure du porte-échantillons (1) à travers le porte-échantillons (1) jusqu'à un échantillon (4) situé sur la face supérieure du porte-échantillons (1), dans lequel le pulvérisateur (3) est disposé sous la face inférieure du porte-échantillons (1) et la pointe de pulvérisateur (2) est ainsi orientée dans la direction de la région de contact (5), de sorte que le pulvérisateur (3) peut pulvériser un échantillon (4) avec un spray à travers la région de contact (5) du porte-échantillons (1).
  2. Le dispositif de production d'ions (100) selon la revendication 1 est caractérisé en ce qu'il comprend en outre une région pour recevoir un tube capillaire de transfert d'ions (7), qui est positionné de telle sorte que les composants d'échantillon désorbés et ionisés peuvent être transférés directement dans un spectromètre de masse via le tube capillaire de transfert d'ions (7).
  3. Le dispositif de production d'ions (100) selon la revendication 1 ou 2 est caractérisé en ce qu'il comprend en outre un moyen de positionnement pour ajuster la position du pulvérisateur (3) vers le porte-échantillons (1) et vers le tube capillaire de transfert d'ions (7).
  4. Le dispositif de production d'ions (100) selon l'une des revendications précédentes est caractérisé en ce qu'il comprend en outre une unité d'alimentation du pulvérisateur (3) en air et en solvant pour générer le spray DESI, l'unité d'alimentation comprenant au moins un compresseur (10) avec au moins un amortisseur (11) et un filtre à air (11), un tuyau de séchage (13) pour sécher l'air aspiré par le compresseur, un tuyau flexible (14) pour acheminer l'air aspiré vers le pulvérisateur (3), un réducteur de pression (15), au moins un récipient (16) résistant à la pression avec un réservoir de solvant (17) pour recevoir un solvant.
  5. Le dispositif de production d'ions (100) selon l'une des revendications précédentes est caractérisé en ce qu'il comprend en outre une pompe à pression réglable adaptée pour permettre un débit de solvant constant et variable en continu de toute composition de solvant.
  6. Le dispositif de production d'ions (100) selon l'une des revendications précédentes est caractérisé en ce qu'il comprend en outre un capteur de débit (18) et un moyen de sortie, qui sont agencés de telle sorte que le capteur de débit (18) peut mesurer le débit du solvant et le moyen de sortie peut émettre ce débit à tout moment.
  7. Le dispositif de production d'ions (100) selon l'une des revendications précédentes est caractérisé en ce qu'il comprend en outre un accumulateur (21) adapté pour alimenter la source de désorption-ionisation par électronébulisation (200) en énergie électrique.
  8. Dispositif d'analyse mobile comprenant un dispositif de production d'ions (100) selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend en outre un spectromètre de masse transportable pour analyser un échantillon traité par le dispositif de production d'ions (100).
  9. Procédé de préparation d'échantillons pour examen par analyse de surface à résolution spatiale, caractérisé en ce qu'on utilise un dispositif de production d'ions (100) selon l'une des revendications 1 à 7 et on pulvérise l'échantillon avec un spray d'un pulvérisateur (3) à travers la région de contact (5) du porte-échantillon (1).
EP17152429.1A 2017-01-20 2017-01-20 Dispositif de production d'ions Active EP3352196B8 (fr)

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EP17152429.1A EP3352196B8 (fr) 2017-01-20 2017-01-20 Dispositif de production d'ions

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EP17152429.1A EP3352196B8 (fr) 2017-01-20 2017-01-20 Dispositif de production d'ions

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EP3352196A1 EP3352196A1 (fr) 2018-07-25
EP3352196B1 true EP3352196B1 (fr) 2019-08-28
EP3352196B8 EP3352196B8 (fr) 2019-10-02

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Publication number Priority date Publication date Assignee Title
CN117476433B (zh) * 2023-11-14 2024-07-02 北京亦庄国际生物医药科技有限公司 解吸附电喷雾电离质谱快速进样装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060250138A1 (en) * 2005-05-06 2006-11-09 Sparkman O D Metastable CID

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7335897B2 (en) 2004-03-30 2008-02-26 Purdue Research Foundation Method and system for desorption electrospray ionization

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060250138A1 (en) * 2005-05-06 2006-11-09 Sparkman O D Metastable CID

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EP3352196B8 (fr) 2019-10-02

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