EP3352196B1 - Device for ion generation - Google Patents

Device for ion generation 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
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Prior art keywords
sample
sprayer
ion generation
solvent
sample stage
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EP17152429.1A
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German (de)
French (fr)
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EP3352196B8 (en
EP3352196A1 (en
Inventor
Bernhard Spengler
Sabine Schulz
Florian LOTZ
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Justus Liebig Universitaet Giessen
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Justus Liebig Universitaet Giessen
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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)

Description

Vorrichtung zur IonenerzeugungDevice for generating ions

Die vorliegende Erfindung betrifft eine Vorrichtung zur direkten Ionenerzeugung von festen Probenmaterialen mittels der Desorptions-Elektrospray-Ionisation auf dem Gebiet der ambienten Oberflächenanalytik insbesondere der Massenspektrometrie.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.

Stand der TechnikState of the art

Die eine Umgebungs-Ionisationstechnik, die in der Massenspektrometrie zur chemischen Analyse eingesetzt werden kann. Es ist eine atmosphärische Druck-Ionenquelle, die Gase, Flüssigkeiten und Feststoffe im Freien unter Umgebungsbedingungen ionisiert. der Methode Desorptions-Elektrospray-Ionisation gekoppelt mit der Massenspektrometrie (kurz: DESI-MS) ist es, ohne aufwändige Probenpräparation die chemische Zusammensetzung einer Probe direkt von der Oberfläche eines Probenobjektes qualitativ und/oder quantitativ zu untersuchen. Durch die Arbeitsweise der Methode DESI unter atmosphärischen Bedingungen ist ein Einschleusen der Probe in ein Vakuum, verbunden mit der entsprechenden Instrumentierung, nicht notwendig. Ionisierungsmethoden mit diesen Eigenschaften werden ambiente Ionisierungsmethoden genannt. Die Methode DESI wird beispielsweise in der Schrift US2005/0230635 A1 beschrieben
Ein Einsatzgebiet der DESI-MS ist die Qualitätskontrolle bei der Einfuhr von Lebensmitteln und Bedarfsgegenständen über Landesgrenzen. Im Rahmen einer Probennahme werden derzeit Stichproben eines Produkts gesammelt und in entsprechend ausgestattete Labore gebracht. Bei Lebensmitteln stehen verbotene und zu hoch konzentrierte Pflanzenschutzmittel, sowie gesundheitsschädliche Verunreinigungen und Zusatzstoffe im Fokus der Untersuchungen. Diese werden von Produzenten gezielt zugesetzt oder migrieren unabsichtlich während des Herstellungsprozesses oder von der Verpackung in das Produkt. Durch den Umweg der Proben über Labore vergeht wertvolle Zeit, in der die fragwürdigen Waren bereits in den Handel gelangen, ohne dass sichergestellt ist, dass sie den jeweiligen Auflagen und Grenzwerten genügen. Ähnlich verhält es sich mit gesundheitsgefährlichen Weichmachern in Kinderspielzeugen und Verpackungsmaterialen, deren Einsatz zunehmend strenger reglementiert wird. Noch deutlicher wird der Faktor Zeit, wenn es um die Identifizierung von verbotenen Medikamenten und Kampfstoffen geht.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. For example, 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. As part of a sampling, samples of a product are currently collected and placed in appropriately equipped laboratories. For food, 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.

Durch die Kopplung mit einer geeigneten Datenbank erlaubt es die DESI-MS gleichzeitig einzelne oder mehrere chemische Stoffe von komplexen Probenmaterialen zu identifizieren und/oder zu quantifizieren. Dabei sind ein hoher Probendurchsatz und eine einfache Bedienung möglich, sodass sie sich für den Einsatz direkt am Ort der sonst notwendigen Probennahme anbietet. Gefahrenpotentiale können dann direkt festgestellt und die Ware gegebenenfalls rechtzeitig von den Behörden zurückgehalten werden.By coupling with a suitable database, 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.

Die Methode DESI ist bislang jedoch an die Laborumgebung gebunden, da die benötigte Druckgasmenge und der sehr geringe und konstante Lösungsmittelfluss durch externe Quellen, wie Gasflaschen und Spritzenpumpen, zur Verfügung gestellt werden muss.However, the DESI methodology is so far linked to the laboratory environment, as the required amount of compressed gas and the very low and constant flow of solvent through external sources, such as gas cylinders and syringe pumps, must be made available.

Für die Desorption/Ionisation von Probenbestandteilen werden hochgeladene Lösungsmitteltröpfchen in Form eines Sprays auf die Probenoberfläche beschleunigt. Spray meint hierbei ein Aerosol, d.h. ein heterogenes Gemisch (Dispersion) aus festen und/oder flüssigen Schwebeteilchen in einem Gas.For the desorption / ionization of sample constituents, charged solvent droplets are accelerated in the form of a spray onto the sample surface. Spray here means an aerosol, i. a heterogeneous mixture (dispersion) of solid and / or liquid suspended particles in a gas.

Desorption bezeichnet hierbei den Vorgang, bei dem ungeladene oder bereits geladene Atome oder Moleküle die Oberfläche eines Festkörpers verlassen. Ionisation heißt jeder Vorgang, bei dem aus einem Atom oder Molekül ein oder mehrere Ladungsträger entfernt oder ihnen hinzugefügt werden, sodass das Atom oder Molekül als positiv oder negativ geladenes Ion zurückbleibt.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.

Die resultierenden Ionen in der Gasphase werden anschließend in ein Massenspektrometer überführt und analysiert. Da die Ionisation direkt von der unbehandelten Probenoberfläche möglich ist, fällt die Probenvorbereitung generell gering aus. Die Menge des desorbierten Materials von der Probenoberfläche ist so gering, dass DESI als zerstörungsfreie Ionisationsmethode bezeichnet werden kann.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.

Unter Analyt wird ein Gemisch aus mindestens einer Substanz verstanden, wobei diese mindestens eine Substanz chemischen und/oder biologischen und/oder biochemischen Ursprungs ist.By 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.

Aufgabetask

Aufgabe der vorliegenden Erfindung ist es, eine Vorrichtung zur Ionenerzeugung bereitzustellen, welche besonders kompakt ist, geeignet ist autark zu arbeiten und mit einem Massenspektrometer für Vor-Ort-Analysen von verschiedenen Probenoberflächen kombiniert werden kann.It is an object of the present invention to provide an apparatus for ion generation which is particularly compact, capable of operating autonomously and combined with a mass spectrometer for on-site analysis of various sample surfaces.

Lösung der AufgabeSolution of the task

Diese Aufgabe wird erfindungsgemäß gelöst durch eine Vorrichtung mit den Merkmalen des Anspruchs 1 und ein Verfahren mit den Merkmalen des Anspruchs 9. Vorteilhafte Ausführungsformen und Weiterbildungen der vorliegenden Erfindung ergeben sich aus den Unteransprüchen.This object is achieved by a device having the features of claim 1 and a method having the features of claim 9. Advantageous embodiments and further developments of the present invention will become apparent from the dependent claims.

Die erfindungsgemäße Vorrichtung zur Ionenerzeugung 100 ist dabei für die Verwendung mit verschiedenen Massenspektrometern vorgesehen. Sie kann mit allen dem Fachmann bekannten Massenspektrometern verwendet werden, die über ein Atmosphärendruck-Einlasssystem verfügen.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.

Die erfindungsgemäße Vorrichtung zur Ionenerzeugung 100 umfasst dabei wenigstens eine Desorptions-Elektrospray-Ionisationsquelle 200. Diese ist so ausgebildet, dass sie ein Spray erzeugen kann, welches zur Desorption und Ionisation einer Probe zur Untersuchung mittels Massenspektrometer dient. Die Desorptions-Elektrospray-Ionisationsquelle 200 umfasst wenigstens einen Sprayer 3 mit einer Sprayerspitze 2.The ion generating device 100 according to the invention 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.

Weiterhin umfasst die erfindungsgemäße Vorrichtung zur Ionenerzeugung 100 einen Probentisch 1, welcher so ausgebildet ist, dass eine Probe 4 auf seine Oberseite aufgebracht werden kann.Furthermore, 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.

Im Folgenden wird die Seite des Probentisches auf der eine Probe 4 aufbringbar ist als Oberseite des Probentisches bezeichnet. Die gegenüberliegende Seite des Probentisches 1 wird als Unterseite des Probentisches bezeichnet.In the following, 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.

Der Probentisch 1, weist wenigstens einen Kontaktbereich 5 mit wenigstens einer Öffnung, durch welche ein Spray von der Unterseite des Probentisches 1 durch den Probentisch 1 zu einer auf der Oberseite des Probentisches 1 befindlicher Probe 4 gelangen kann. Der Kontaktbereich 5 kann beispielsweise einen Spalt oder ein Gitter aufweisen.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.

Der Sprayer 3 ist unterhalb der Unterseite des Probentisches 1 angeordnet. Die Sprayerspitze 2 ist dabei in Richtung der Unterseite des Kontaktbereiches 5 ausgerichtet.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.

Diese Anordnung des Sprayers 3 mit der Sprayerspitze 2 und des Kontaktbereiches 5 ermöglicht, dass der Sprayer 3 eine Probe 4 durch den Kontaktbereich 5 des Probentischs 1 hindurch mit einem Spray besprühen kann. Der Probentisch 1 umfasst wenigstens einen Kontaktbereich 5, durch welchen das Spray von der Desorptions-Elektrospray-Ionisationsquelle 200 zu einer Probe 4 gelangen kann. Ein Kontaktbereich 5 kann beispielsweise als Spalt ausgebildet sein.This arrangement of the sprayer 3 with the sprayer tip 2 and the contact area 5 allows the sprayer 3 to spray a sample 4 through the contact area 5 of the sample table 1 with a spray. 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.

Die Sprayerspitze 2 des Sprayers 3 weist einen Mindestabstand zum Probentisch 1 auf, damit sie nicht direkt mit der Probe 4 auf dem Probentisch 1 in Kontakt kommen kann. Dieser Mindestabstand beträgt 2 mm bis 10 mm, bevorzugt 2 mm bis 5 mm. Der Kontakt des Sprays aus dem Sprayer 3 mit der Probe 4 ist dabei nur über den Kontaktbereich 5 im Probentisch 1 möglich. Die Wahrscheinlichkeit einer Kontamination der Sprayerspitze 2 mit Probenbestandteilen ist so deutlich reduziert. Desorptions-Elektrospray-Ionisationsquelle 200 und der Probentisch 1 sind bevorzugt relativ zueinander beweglich ausgeführt.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.

In einer zweiten Ausführungsform der erfindungsgemäßen Vorrichtung zur Ionenerzeugung enthält die Vorrichtung einen Bereich zur Aufnahme einer Ionentransferkapillare 7. Die Ionentransferkapillare 7 ist mit einem Massenspektrometer verbunden. Dazu ist die Ionentransferkapillare 7 vorzugsweise innerhalb des Probentisches angeordnet und reicht bis zum Kontaktbereich 5 (siehe Abbildung Fig.1).In a second embodiment of the device according to the invention for generating ions, the device contains a region for receiving an ion transfer capillary 7. The ion transfer capillary 7 is connected to a mass spectrometer. For this purpose, the ion transfer capillary 7 is preferably arranged within the sample stage and extends to the contact region 5 (see FIG Fig.1 ).

Die Sprayerspitze 2 ist empfindlich gegenüber mechanischen Belastungen wie z.B. der Berührung mit einem Probenobjekt. Die Gefahr einer Berührung mit dem Probenobjekt oder durch den Bediener ist in diesem Aufbau nahezu ausgeschlossen. Der Abstand und Winkel des Sprayers zum Probentisch und zur Probe ist justier- und arretierbar. Der Probentisch 1 bildet eine fixierte Fläche und ermöglicht durch einfaches Auflegen verschiedener Proben identische Orientierungen der Probenoberflächen zum Sprayer. Die geometrischen Parameter sind dadurch während der Messung identisch und die Ergebnisse vergleichbarer. Es muss lediglich für eine ebene Auflage der Probe auf dem Probentisch gesorgt werden. Da die Abstände des Sprayers nicht an Größe und Form der Probe angepasst werden müssen, können Messungen sehr viel schneller durchgeführt werden. Größere Probenkörper müssen nicht erst zerkleinert werden, sondern können direkt untersucht werden. Auf diese Weise ist die Probenvorbereitung für DESI-MS-Untersuchungen weiter reduziert und der Messvorgang für den Bediener deutlich vereinfacht, sodass auch Laien Analysen durchführen können.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.

In einer dritten Ausführungsform der erfindungsgemäßen Vorrichtung zur Ionenerzeugung 100 umfasst diese weiterhin ein Positionierungsmittel zur Einstellung der Position des Sprayers 3 zum Probentisch 1. Dabei kann das Positionierungsmittel als x,y-Tisch 8 zur Veränderung in der x,y-Ebene und eine Langlochplatte in z-Richtung ausgebildet sein. Weiterhin kann das Positionierungsmittel noch einen Rotationstisch 9 umfassen. Der Winkel zum Probentisch bzw. Probenoberfläche kann dabei über den 360° drehbaren Rotationstisch 9 beliebig variiert werden. Weiterhin kann das Positionierungsmittel noch eine Arretierung umfassen, um die geometrischen Parameter des Sprayers, des Probentisches und der Probe insbesondere ihre Position zueinander während der Messung zu fixieren. Das erlaubt vergleichbarere und besser wiederholbare Messbedingungen. Als Arretierung geeignet sind beispielsweise Rasten, Sicherungsbolzen, Schrauben und/oder Klemm- oder Spannvorrichtungen.In a third embodiment of the device according to the invention for generating ions 100 further comprises a positioning means for adjusting the position of the sprayer 3 to the sample table 1. Here, the positioning means as x, y table 8 for change in the x, y plane and a slot plate in z-direction be formed. Furthermore, 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. Furthermore, 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.

In einer vierten Ausführungsform umfasst die Vorrichtung zur Ionenerzeugung 100 weiterhin eine Einheit zur Versorgung des Sprayers 3 mit Luft und Lösungsmittel zur Erzeugung des DESI-Sprays. Die Versorgungseinheit umfasst wenigstens einen Kompressor 10 mit Dämpfern 11 und einen Luftfilter 12, ein Trockenrohr 13 zur Trocknung der vom Kompressor eingesaugten Luft, einen Schlauch 14 zur Leitung der einsaugten Luft zum Sprayer 3, einen Druckminderer 15 und wenigstens ein druckstabiles Gefäß 16 mit Lösungsmittelreservoir 17 zur Aufnahme eines Lösungsmittels.In a fourth embodiment, 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.

Der Fluss des Lösungsmittels sowie die Versorgung mit komprimiertem Gas zur Erzeugung des Sprays werden durch die Verwendung eines Kompressors 10 ermöglicht. Dieser ist beispielsweise als Pendelkolbenkompressors ausgeführt. Die mechanische Schwingung des Kompressors wird weitestgehend durch eine elastische Lagerung auf Dämpfern 11 abgefangen. Dieser ist beispielsweise als Silikondämpfer ausgeführt.The flow of the solvent and the supply of compressed gas to produce the spray are made possible by the use of 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.

Die Versorgungseinheit arbeitet dabei folgendermaßen:
Der Kompressor 10 saugt atmosphärische Luft durch einen Luftfilter 12 an. Der Filter schützt den Kompressor sowie das DESI-Spray vor Partikeln aus der Umgebungsluft. Über einen Schlauch strömt die komprimierte Luft in ein Trockenrohr 13, das mit einem Trockenmittel gefüllt ist. Im Trockenrohr wird die Luftfeuchtigkeit adsorbiert, sodass die Luftfeuchtigkeit der Umgebungsluft keinen Einfluss auf den Vernebelungsgasstrom oder den Desorptions-Ionisationsprozess hat. Nach dem Trockenrohr wird der Gasstrom gesplittet. Der Großteil der Luft strömt über einen Schlauch 14 direkt zum Sprayer 3 und wird dort zur Vernebelung und Beschleunigung der hoch geladenen Lösungsmitteltröpfchen genutzt. Ein geringes Gasvolumen wird zur Erzeugung des Lösungsmittelflusses, nach dem Prinzip einer Druckpumpe, verwendet. Dazu wird die Luft über einen Druckminderer 15 in ein druckstabiles Gefäß 16 geleitet. Im Gefäß 16 befindet sich ein Lösungsmittelreservoir 17. Dieses besitzt ein Fassungsvolumen von vorzugsweise 5 ml bis 15 ml. Über eine Sprayerkapillare 20 wird das Ausströmen des Lösungsmittels aus dem Druckgefäß ermöglicht. Die dünne Flüssigkeitskapillare zwischen Lösungsmittelreservoir und Sprayer 3 erzeugt einen Strömungswiderstand, sodass über den relativen Druck auf das Lösungsmittel im Bereich von einigen hundert Millibar der Lösungsmittelfluss im DESI-relevanten Bereich exakt variiert werden kann, sodass das Spray aus Luft und Lösungsmittel aus der Sprayerspitze 2 austreten kann.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. In the drying tube, 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. After the drying tube, 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. For this purpose, the air is passed through a pressure reducer 15 in a pressure-stable vessel 16. 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.

In einer fünften Ausführungsform umfasst die Vorrichtung zur Ionenerzeugung 100 weiterhin eine regelbare Druckpumpe an der Sprayerkapillare 20, welche so ausgebildet ist, dass sie einen konstanten und stufenlos einstellbaren Lösungsmittelfluss einer beliebigen Lösungsmittelzusammensetzung erlaubt. Die entsprechenden Druckeinstellungen sind stufenlos mit dem Druckminderer 15 möglich und erlauben ab einer Mindestflussrate von vorzugsweise 1 µl/min eine Genauigkeit der Flusseinstellung von vorzugsweise 0,05 µl/min.In a fifth embodiment, 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.

In einer sechsten Ausführungsform umfasst die Vorrichtung zur Ionenerzeugung 100 weiterhin einen Flusssensor 18 und vorzugsweise ein Ausgabemittel, welche so ausgebildet sind, dass der Flusssensor die Flussrate des Lösungsmittels messen und das Ausgabemittel die Flussrate jederzeit ausgeben kann.In a sixth embodiment, 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.

Vorzugsweise ist der Flusssensor 18 von der elektrischen Hochspannung des Sprayers 3 und des Lösungsmittels entkoppelt. Dazu weist die Vorrichtung zur lonenerzeugung 100 beispielsweise eine lange und dünne Lösungsmittelkapillare 19 zwischen Sprayer und Flusssensor auf. Über diese Lösungsmittelkapillare 19 fällt die Spannung deutlich ab. Zur Sicherheit ist die Sprayerkapillare 20 während des Betriebs direkt vor dem empfindlichen Flusssensor 18 geerdet.Preferably, the flow sensor 18 is decoupled from the electrical high voltage of the sprayer 3 and the solvent. For this purpose, 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. For safety, the sprayer capillary 20 is grounded during operation directly in front of the sensitive flow sensor 18.

Der Messwert der vom Flusssensor 18 gemessenen Flussrate kann kontinuierlich erfasst und über ein Ausgabemittel z.B. einen Computer ausgegeben und/oder beispielsweise an das Massenspektrometer übermittelt werden. So ist eine Kontrolle des vernebelten Lösungsmittelvolumens ähnlich genau wie bei üblichen stationär arbeitenden Spritzenpumpen möglich. Die Flussrate kann weiterhin auch an eine regelbare Druckpumpe wie in der fünften Ausführungsform der erfindungsgemäßen Vorrichtung zur Ionenerzeugung 100 übermittelt werden und zu deren Regelung verwendet werden.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. Thus, a control of the atomized volume of solvent is similar to that possible with conventional stationary syringe pumps. 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.

In einer siebten Ausführungsform umfasst die Vorrichtung zur Ionenerzeugung 100 weiterhin einen Akkumulator 21, welcher so ausgebildet ist, dass er die Desorptions-Elektrospray-Ionisationsquelle mit elektrischer Energie versorgen kann. In einer beispielhaften Ausführung wird der Kompressor 10 über einen Ackumulator 21, welcher als Lithium-Eisenphosphat-Akkumulator ausgeführt ist, elektrisch versorgt. Dieser hat eine Kapazität von beispielsweise 5 bis 25 Ah, bevorzugt 8 bis 15 Ah, eine Nennspannung von 11 bis 40 V, bevorzugt 20 bis 30 V, um so die Desorptions-Elektrospray-Ionisationsquelle für mehrere Stunden ohne Unterbrechung zu versorgen. Die für das Sprayerpotential notwendige Hochspannung wird vorzugsweise durch einen Hochspannungsausgang des Massenspektrometers zur Verfügung gestellt und über einen Hochspannungsanschluss für Sprayer 22 angeschlossen. Es besteht allerdings die Möglichkeit, der Desorptions-Elektrospray-Ionisationsquelle einen internen Spannungswandler, gespeist durch den Akkumulator, hinzuzufügen.In a seventh embodiment, the ion generating apparatus 100 further includes an accumulator 21 configured to supply the desorption electrospray ionization source with electrical energy. In an exemplary embodiment, 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.

Die Vorrichtung zur Ionenerzeugung erfüllt dabei alle notwendigen Voraussetzungen für eine längere Anwendung fern von Laborstandorten. Sie ist dabei mit transportablen oder stationär arbeitenden Massenspektrometern zu einer mobilen Analytikvorrichtung kombinierbar. Diese kann auch als Desorptions-ElektrosprayIonisation - Massenspektrometer (DESI-MS) Einheit bezeichnet werden.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.

Eine Verwendung der erfindungsgemäßen Vorrichtung zur Ionenerzeugung 100 besteht darin, sie mit einem transportablen Massenspektrometer zu einer mobilen Analytikvorrichtung zu kombinieren. Dies erlaubt Vor-Ort-Analysen, ohne dabei von zusätzlicher Ausrüstung abhängig zu ein.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.

Die Vorrichtung zur Ionenerzeugung 100 ist geeignet zur Durchführung eines Verfahrens für die Untersuchung mittels Oberflächenanalytik, wobei das Besprühen der Probe mit Spray aus Sprayer 3 durch den Kontaktbereich 5 des Probentischs 1 hindurch erfolgt.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.

Abbildungslegenden und BezugszeichenlisteFigure legends and list of reference numerals

  • Fig. 1 zeigt die eine beispielhafte Ausführungsform der erfindungsgemäßen Vorrichtung zur Ionenerzeugung 100 mit dem Sprayer unter der Probe und dem Probentisch vor dem Einlass der Ionentransferkapillare 7. Teilabbildung A zeigt die Vorrichtung zur Ionenerzeugung 100 in Seitenansicht, Teilabbildung B in der Frontalansicht und Teilabbildung C in der Draufsicht. Die Pfeile zeigen in diesen die Flussrichtung der Luft durch den Schlauch 14, des Lösungsmittels durch die Sprayerkapillare 20 und die Ausstoßrichtung des Sprays aus der Sprayerspitze 2. (Die Probe wurde hier nur zur Verdeutlichung des Konstruktionsprinzips abgebildet, bildet aber keinesfalls einen Teil der Vorrichtung zur Ionenerzeugung selbst) Fig. 1 Figure 1 shows the one exemplary embodiment of the ion generation device 100 according to the invention with the sprayer below the sample and the sample table in front of the inlet of the ion transfer capillary 7. Figure A shows the ion generation device 100 in side view, part image B in the front view and part map C in the top view. The arrows in these show the flow direction of the air through the hose 14, the solvent through the sprayer capillary 20 and the ejection direction of the spray from the sprayer tip 2. (Die Sample was shown here only to illustrate the design principle, but in no way forms part of the apparatus for ion generation itself)
  • Fig. 2 zeigt eine Ausführungsvariante der erfindungsgemäßen Vorrichtung zur lonenerzeugung zur Installation vor einem üblichen transportablen Massenspektrometer. Die Teilabbildung D zeigt hierbei die Draufsicht, die Teilabbildung E eine rechte Seitenansicht, die Teilabbildung F eine linke Seitenansicht und die Teilabbildung G eine Frontansicht. Die lonenquelle ist dabei vollständig in ein solides Aluminiumgehäuse integriert, wobei der Probentisch Teil des Gehäuses ist. Einstellungen der Sprayerposition sowie der Austausch des Akkumulators sind durch die abnehmbare Seitenwand auf der rechten Seite leicht möglich. Durch den geschlossenen Aufbau ist eine aktive Kühlung des Kompressors notwendig. Dazu sind in der gezeigten Ausführungsvariante zwei Lüfter 23 direkt über dem Kompressor installiert. Fig. 2 shows an alternative embodiment of the device according to the invention for ion generation for installation in front of a conventional portable mass spectrometer. The partial image D shows the top view, the partial image E a right side view, the partial image F a left side view and the partial image G is a front view. The ion source is completely integrated into a solid aluminum housing, with the sample table being part of the housing. Adjustment of the sprayer position as well as the replacement of the accumulator are easily possible due to the removable side wall on the right side. Due to the closed structure, active cooling of the compressor is necessary. For this purpose, two fans 23 are installed directly above the compressor in the embodiment shown.
Bezugszeichenreference numeral

11
Probentischsample table
22
Sprayerspitzesprayer tip
33
Sprayersprayer
44
Probesample
55
Kontaktbereichcontact area
66
Massenspektrometermass spectrometry
77
Ionentransferkapillare des MassenspektrometersIon transfer capillary of the mass spectrometer
88th
x,y-Tisch des Sprayersx, y table of the sprayer
99
Rotationstisch des SprayersRotation table of the sprayer
1010
Kompressorcompressor
1111
Dämpferdamper
1212
Luftfilterair filter
1313
Trockenrohrdrying tube
1414
Schlauchtube
1515
Druckmindererpressure reducer
1616
Druckstabiles GefäßPressure-stable vessel
1717
LösungsmittelreservoirSolvent reservoir
1818
Flusssensorflow sensor
1919
LösungsmittelkapillareLösungsmittelkapillare
2020
SprayerkapillareSprayerkapillare
2121
Akkumulatoraccumulator
2222
Hochspannungsanschluss für SprayerHigh voltage connection for sprayers
2323
LüfterFan
100100
Vorrichtung zur IonenerzeugungDevice for generating ions
200200
Desorptions-Elektrospray-IonisationsquelleDesorption electrospray ionization

Claims (9)

  1. Device for ion generation (100) for examination by means of surface analysis, comprising at least one desorption electrospray ionization source (200) with at least one sprayer (3) and one sprayer tip (2), as well as a sample stage (1) for receiving a sample on its upper side, characterized in that the sample stage (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 stage (1) through the sample stage (1) to a sample (4) located on the upper side of the sample stage (1), wherein the sprayer (3) is arranged below the underside of the sample stage (1) and the sprayer tip (2) is thereby aligned in the direction of the contact region (5), so that the sprayer (3) can spray a sample (4) with a spray through the contact region (5) of the sample stage (1).
  2. The device for ion generation (100) according to claim 1 is characterized in that it further comprises a region for receiving an ion transfer capillary tube (7), which is positioned such that the desorbed and ionized sample components can be transferred directly into a mass spectrometer via the ion transfer capillary tube (7).
  3. The device for ion generation (100) according to claim 1 or 2 is characterized in that it further comprises a positioning means for adjusting the position of the sprayer (3) to the sample stage (1) and to the ion transfer capillary tube (7).
  4. The device for ion generation (100) according to one of the preceding claims is characterized in that it further comprises a unit for supplying the sprayer (3) with air and solvent for generating the DESI spray, wherein said supplying unit comprises at least one compressor (10) with at least one damper (11) and an air filter (11), a drying pipe (13) for drying the air sucked in by the compressor, a hose (14) for conducting the sucked-in air to the sprayer (3), a pressure reducer (15), at least one pressure-stable vessel (16) with a solvent reservoir (17) for receiving a solvent.
  5. The device for ion generation (100) according to one of the preceding claims is characterized in that it further comprises a variable pressure pump adapted to permit a constant and continuously variable flow of solvent of any solvent composition.
  6. The device for ion generation (100) according to one of the preceding claims is characterized in that it further comprises a flow sensor (18) and an output means arranged such that the flow sensor (18) can measure the flow rate of the solvent and the output means can output this flow rate at any time.
  7. The device for ion generation (100) according to one of the preceding claims is characterized in that it further comprises an accumulator (21) which is adapted to supply electrical energy to the desorption electrospray ionization source (200).
  8. Mobile analytical device comprising a device for ion generation (100) according to one of the preceding claims, characterized in that it further comprises a transportable mass spectrometer for analyzing a sample treated by the device for ion generation (100).
  9. Method for preparing samples for analysis by means of spatially resolved surface analysis, characterized in that a device for ion generation (100) according to one of claims 1 to 7 is used and the sample is sprayed with spray of sprayer (3) through the contact region (5) of the sample stage (1).
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